10114
10114
10114
10114
LUBRICATING OILS
BY
VLADIMIR A. KALICHEVSKY,
RESEARCH AND D'WEI.OPJllENT LA BORATORlES,
SOCONY-VACUU1r OIL
CO-AUTHOR OF
~'Cnv.M{C_'&'L
Co.,
RRFl:NING
INC.
OP
PRT1tOL1~U\Tl!
COPYRIGHT,
1938, By
GENERAL INTRODUCTION
American Chemical Society Series of
Scientific and Technologic Monographs
service. is to present the knowledge avail~lblc upon the chosen topic in <l
form intelligible to those whose activities may he along a wholly different
line. Many chemists fail to realize how closely their investigations may
be connectecl with other work which on the surface appears far afield fr0111
their own. These monographs enable such men to form closer contact
with work in other lines of research. The second purpose is to promote
research in the branch of science covered by the monograi)h, by furnishing
a well-digested survey of the progress already made, and by po.inting out
directions in which investigation needs to be extended. To facilitate the
attainment of this purpose, extended references to the literatl11:e' enable
anyone interested to follow up the subject il1 more detail. If the literature
is so voluminous that a complete bibliography is impracticable, a critical
selection is made of those papers which are most important.
L.
F. FIESER
PREFACE
The l~st few years have witnessed radical changes in the methods of
refining and manufacturing luhricating oils. The conventional sulfuric
acid treating and naphtha clewaxing processes are now gradually being
displaced by the newly developed solvent processes, while the use of
additives for improving certain particular characteristics of petroleum
products are beginning to assume an increasingly greater commercial
importance. Until recently these new refining methods had not yet been
sufficiently clarified and standardized, and the available -information has
been inadequate for presenting a generalized discussion 011 the subject.
By now, however, many of the controversial aspects of the solvent refining processes and tbeir commercial applications have been, to a greater
or less extent, clarified and have made possihle the publication of the
present volume.
The primary ohject of this book is the systematization of our knowledge on the modern methods of refining, and classification of the lltlll1erottS processes proposed in the course of the last few years for commercial
llse. The discussion is restricted, however, only to the general principles
ullderlying these refining methods and to the description of the processes
which have found actual commercial applications. The literature and
patent references nevertheless \\'ere made as complete as possible in order
to facilitate an evaluation of the relative merits of the various proposed
substitutes and of their proper locatioll in the general scheme of refining.
In the description of various processes it will be noted that dewaxillg
methods are discussed prior to deasphalting methods, while in practice
deasphaltillg usually precedes dewaxing. Such an arrangement has been
founel, however, to facilitate the presentation of the subject matter
covered in this book.
The writer wishes to express his gratitude to Dr. A. B. Brown and
others of the staff of the Standard Oil Co. of Indiana, ane! to Dr. A. N.
Sachanen 01' their valuable technical criticisms of the manuscript anel to
Mr. T. A. Petry for his collaboration in preparing the chapter on theoretical principles of the solvent refining processes; to Dr, J. n. Rather,
in charge of the General Laboratories o the Socony-Vawul11 Oil Co.,
Inc., and the late Dr. D, P. \Veld, formerly in charge of the Research
and Development Division of the SOCOl1Y- Vacuum Oil Co., Inc., for per-
mission to publish this hook and for the encouragelllent received in the
course of its preparation; to Mrs. N. N. Menshih, for careful editing of
the manuscript; to Mr. R. H. Hammel, for preparing the drawings; and
to many others who are mentioned in the. pages of this book who have
so kindly permitted the nse of data and results of their work
V. A. KALICHEVSKY
Paulsboro, N. J.
January, 1938.
CONTENTS
PAGE
PREFACE.............................. . . . . . . . . . . . . . . . . . .
11
22
29
Types of vVaxes Present in Petroleum Oils, 29. Wax Content of Petroleum and Its Products, 30. Effect of Wax on Oil Properties, 33. Crystallization of Wax, 34. Conventional Dewaxing Methods, 35.
CHAPTER IV.-DEWAXING WITH FILTER-AIDS. . . . . . .. . . . ..
38
Modern Dewaxing Processes, 38. Filter-Aids, 38. Electrical Precipitation Methods, 41.
CHAPTER V.-SOLVENT DEWAXING...........................
43
Ideal Dewaxing Solvent, 43. Practical Dewaxing Solvents, 44. Separation of Water from Solvents, 48. Commercial Solvent Dewaxing
Processes, 51. Propane Dewaxing Process, 51. Benzol-Acetone
Dewaxing Process, 57. Dewaxing with Chlot'inated Solvents, 60.
Separator-Nobel Dewaxing Process, 62. Bari-Sol Dewaxillg Process,
63. Dewaxillg with Various Organic Solvents, 65. Solvent Dcwaxiug Plants, 69.
CHAPTER VI.-REMOVAL OF OIL FROM PETROLEUM WAXES. . . . .
73
Nature of Asphaltic
Refiniilg, 82.
Sl1bstance~,
80
86
DcaSllhalting by Distillation, 86. neasphaltin~ with Clay, 87. lJeasphalting with Sulfuric Acid, 90. Deaophalting' with M(~tallic Chlorides, 91.
CHAPTER lX.-DEASl'IIALTI N G
\V ITH
SOLVENTS. . . . . . . . . . . . . . ..
93
X.-GENERAL
PRINCIPI.ES
OF
Sell,VENT
H.El'lNINU
PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
106
112.
CHAPTEI( XI.-VMUABLES INVtlLVED IN
REF] NING
OILS
Vvnn
I1G
134
14(j
155
163
168
179
Nature of Viscosity Index Improver, 179. Effect of Blending on Viscosity Index of Oils, ISO. Exanol, 180. Univis Oils, 181. Proposed
Viscosity Index Improvers, 182. Pre-Diluted Oils, 183.
CONTENTS
PAGl,
185
Oil iness, 185. Oiliness of Mineral Oils, 186. Oiliness Carriers, 187.
Effect of Oiliness Carriers on Oil Properties, 188.
CHAPTER XIX.-OXllJATlCiN IN HlH'rToRs . . . . . . . . . . . . . . . . . .
190
196
Fluorcsccnce
201
ApPENDIX
201
204
205
206
207
209
INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
211
AUTHOR INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
217
SUBJECT INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
225
PATENT
12
while too Iowa viscosity at the operati11g' temperatl1re lllay not leave a
film of thickness sufficient to prevent metal to llletal contacts. An unduly
high viscosity also results in lat'ge power consumption due tu increased
friction, ~dthot1gh the oil consumption will be less with high viscosity oils
than with low viscosity oils. The actual adjustment of oil viscosity,
evidently, depends on the. specific engine design, but in general it is
preferable to ttse an oil of lower viscosity than that required hy specifications.
For oils which are. empluyee! at approximately constant temperatures,
such as turbine oils, the viscosity-temperature charnctcristics arc of very
little or no imp@rtance, and the controlling factor is the viscosity at the
exact service temperature conditiotJs. The viscosity-temperature specifications for these types of products are, therefore, usually omitted.
The viscosity-temperature characteristics of mineral oils can be estimated over a wide temperature range from viscosity determinations at
two different temperatures by employing the viscosity-temperature chart
of the American Society for Testing' Materials. l
A supplementary chart has been developed by
Grosholz,~
13
The oil having the smaller coefficient (Oil L) was' assigned a viscosity index of 100. and the oil with the larger coefficient (Oil H) a
viscosity index of O. The viscosity index of an unknown sample of oil
(Oil U) is determined hy suhstituting its viscosity at 210 F. in the above
equations and by determining the viscosities of Oils Land H at 100 F.
which have the salllc viscosity at 210 0 F. as the unknown sample. The
viscosity index is then calculated from tbe equation:
Viscosity index
VL - Va
=.
VL
VII
100
0'"
Ducksey, Hands, and Hayward" developed equations and (.:harts which permit
calculations nf the viscosity indexes from kinematic viscositics. lVIcC[uel' and
Fcnske 0 developed conversion factors for expressing kinematic viscosities in terms
of Saybolt viscosities, and Hersh, Fisher. and Fenske 11) worked out the necessary
tables for estimating the "kinematic viscosity index" on the basis of their cal'cful
viscosity measurements of the represelltative oil fractions.
The above equations ,yere developed for oils 'which have a viscosity
not less than 4S and not more than 160 Saybolt Universal seconds at
210 0 F. For the very light oils the experimental error in determining
Saybolt viscosities is very great in comparison 'with the total spread
between the two standard oils of 0 and 100 viscosity indexes and absolute viscosities should, therefore, be employed for calculating the Saybolt
viscosities to be used in the equations. Oils of viscosities above 160
seconds at 210 F. were 110t investigated by Dean and Davis and the
extrapolations into these viscosity index regions are, therefore, unreliable.
Several attempts have beell Illade to extend the viscosity index range beyond
the above viscosity limits, as well as to change the formulas recommended by Dean
and Davis. It is, therefore, always desirable to specify the system which is adopted
for calculating the viscosity index. In this book the system of Dean and Davis is
used throughout as the one most generally accepted.
The approximate viscosity index of ul1l'efined lubricating oil fractions obtained hy distilling typical crucles is given in the following table:
TABLE
14
U.
Viscosity-Gravity Constant
Viscosity-gravity constant is sometimes employed instead of viscosity
index for expressing those changes in the chemical composition of the
oil, bearing particularly on the temperature-viscosity characteristics,
which are brought ahont by refining- processes. This constant 'Nas originally developed for classification of crude oils.18 *
Although the inventors of this constant cautioned against its application to semi-refined or refined products, it is frequently employed as a
stlhstitnte for viscosity index. It is so used particularly for oils of low
A very convenient aligntlJent chart for calculating this constant has been prepared by Houghton and Rohb. '11 Another similar chart was also developed.'
15
10 - log (V _ 38)
a = viscosity-gravity constant,
V = Saybolt Universal viscosity at 100" F.
G = specific gravity at 60' F.
'or
a=
where:
The viscosity-gravity constant is based on the well known relationship that the paraffinic oils exhihit a low speciilc gravity. and the
naphthenic oils a high specific gravity for any given viscosity and is.
therefore. a useful indication of the sonrce of a given crude. As the
naphthenic oils have a low viscosity index. and the paraffinic oils have a
high viscosity index. attempts have been made to correlate the viscosity
index with viscosity-gravity constant and to apply snch correlations to
refined oils.
The following data on four typical but untreated luhricating oils were pl'esented by Ferris and Houghton 21 to show the correlation he tween the viscositygravity constant Cv.G.c.) and the viscosity index (V.l.). McCluer and Fenske""
recommend the use of gravity index. which was selected so -that gravity index
numbers, which are functions of the viscosity-gravity constant. become similar to
viscosity index numbers for the same oils. See also a correlation between viscositygravity constant and viscosity index.'"
T AnLF: 2-Relation Between Viscosity-Gravity Constant and Viscosity Index
Type of C,"de
V.C.C.
Penn"y1vania ......................... 0.812
Mid-Continent ........................ 0.846
Gulf Coast ............................ 0.885
Extreme Gulf Con,qt .................... 0.935
V.I.
105
72
18
-145
10
ons
developed by Jackson.'"
and Ancler,on on llse specific dispersion method for similar [lurposes.
17
Color
Although it is generally agreed that the color of the oil has little
relation to its quality, it still appears in trade specifications and is, therefore, of importance. The consumer ~llso frequently dcmands that the
oils have the fluorescellce or "bloom" characteristic of Pennsylvania oils.
The color of the oil is measured by comparing it with certain standards
by using transmitted light. A variety of colorimeters have been proposed for measuring colors of petroleum oils and can be classified in
several difTerent ways:
1. By the method of taking observations: human eye or mechanical
device (photoelectric cells).
2. By the method of matching colors: variable or fixed thickness of
the oil layers with the respective fixed or adjustable standard.
3. By the mdhocl of illuminating the instrument: artificial or sunlight, white or monochromatic light.
4. By the method of defining standard colo1"s: colored glass discs,
colored solutions, intensity of color without reference to hue, or hue
without reference to the intensity of color.
5. By the method of expressing the results: arbitrary scales or
approximations of additive or "true" color scales.
18
Fluorescence
Oxidation Stability
19
change in several of them. A variety of oxidation tests were thus developed (Table 6, Appendix). Some of these tests are particularly suitable for motor oils (Indiana oxidation test, Socony oxidation test, and
the Sligh test, which is of more importance to light distillate oils than
to heavy products), airplane engine oils (British Air Ministry test as
well as tests applied to motor oils), transformer and turbine oils (German
Tar Number test, Michie test, Belgian test, Brown-Boveri Transformer
oil test, Brown-Boveri Turbine oil test), etc. The large variety of these
tests shows in itself that none of them guarantees the perfect performance of an oil in service. It is likewise not infrequent that results
obtained with one of such tests are in direct contradiction with the results
of another test of similar nature. Thus the German Tar Number
increases while the quantity of sludge formed in the Michie tcst decreases
with the clepth of refining. In general, however, the closer the test
approaches the actual conditions in the engine the more reliable are the
results, but this requires the use of relatively low temperatures and long
periods of time thus depriving the research worker of the benefit of
accumulating experimental data at the required nlte of speeel. Many of
the above tests employ catalysts which are usually chosen from metals
of which the engine is built. This tends to approach more closely the
practical conditions.
The oxidation stability of a motor oil should be, evidently, high,
particularly if the engine is equipped with oil filters, in which case
the oil remains in use for a long period of time and is only seldom
changed. It is of less importance whenever the oil changes are frequent.
Pout and Cloud Points
The solidifying characteristics of the oil should be low so as to insure
good lubrication as S0011 as the engine is started. It is measured by the
cloud and pour point test,42 * cold test,44 01' other similar tests. These
tests are performed under exactly specified conditions since the change
in the shape or volume of the vessel, heating of the sample before testing,
the quantity of the oil used, rate of chilling, etc., influence considerably
the results. An oil which will not flow ill a small container may be quite
fluid \vhen a large container is used. In general the high pOUl" test oil
is not necessarily associated with the difficulty of starting the engine,
but it is undesirable as the flow of such oil from the oil sump to the
pump intake is unsatisfactory. This results in the excessive wear of
moving parts before the oil is sufficiently heated. On the pressure sideof the system the flow will usually he satisfactory even with a relatively
high pom test oil, provided the pUl1IP can "take suction."
* See
20
\Vhile flash alld fire points are of practical significance for certain
types of petrolel1m products Stich as transformer oils, etc., in an engine
they are lowered at once as the fresh oil is introduced and mixed with
the heavy gasoline fmctiol1S that accumulate in the crank-case due to
their incomplete combustion. The flash and fire points may have a certain bearing, however, on other oil properties such as oil consumption
in the engine, etc. * In general, removal of asphalt from all oil tends to
decrease slightly its flash and fire points while the removal of wax may
raise them by a few degrees. This tI1ay be frequently attributed, however, to the removal of the light portions of an oil in distilling off the
de1vaxing solvent.
21
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
2().
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
Chapter II
Modern Refining Methods
The general object of lubricating oil refining is the improvement of
oil properties and rendering oil suitable to service condition;;. Oil properties can be improved, however, in a variety of ways which may he
classified as follows:
1. Elimination of the undesirable constituents from the crllCle
products.
2. 1X_endering the undesirable constituents harmless or even beneficial by neutralizing their action through the introduction into the oil
of various inhibitors and similar protective substances, and
3. Converting the undesirable constituents into desirable ones hy
changing their chemical structure through hydrogenation, condensation
or other chemical processes.
The first two methods are described in the succeeding clmpters while
the third method cannot be considered as a true refining process and is,
moreover, only in limited practical use, except in countries deficient in
oil resources which, for various reasons, are anxious to maintain their
economic independence.*
It is to be expected, however, that with the exhaustion of onr present
oil resources this third method of improving crude products will everywhere become of increasing commercial importance as the increased value
of crude will result in sufficient savings for justifying the additional
expense of securing larger yields of refined materials than those ohtained
by the present refining methods.
* The fundamental
treatises of Ellis 1,
"
22
23
hydroxide and clay as the main reagents for removing asphaltic bodies
and the low viscosity index or chemically unstable constituents from the
crude oils. Of these reagents sulfuric acid was by far the most important one due to its remarkable ability of effectively eliminating most of
these undesirable components. The action of sulfuric acid, however, is
very complex and is, apparently, both of chemical and physical nature.
By modifying the treating conditions it is possible to exercise a certain
control over the relative predominance of these two major actions of sulfuric acid, although it is practically impossible to eliminate either one
of them completely. 3
For this reason oils refined with sulfuric acid may contain certain
amounts of substances produced in the course of refining, such as sulfonated bodies or products of polymerization and condensation reactions,
which are not necessarily of desirable nature. Moreover, the disposal of
the acid sludge and the degradation of oil to sludge in the course of
refining introduce other undesirable features in the plant operation.
This versatile action of sulfuric acid permits its utilization for the
removal of both asphaltic and low viscosity index constituents. However, contrary to the action of sulfuric acid, the new solvent methods are
of physical natme only and both the desirable and undesirable constituents are recovered in their original state. These solvent methods are
inefficient for separating asphalt from oil. This may possibly be
explained by the colloidal nature of the asphaltic particles the removal
of which f1'0111 the oil is, apparently, a colloidal and not a solubility phenomenon. Deasphalting or precipitating agents are, therefore, employed
for elimination of asphalt, and sulfuric acid refining is thus substituted
by two distinct refinery operations; c1easphalting, which is frequently
synonymous to distillation, and solvent refining proper.
Elimination of wax fro111 petroleum oils has always been and continues to be a separate refining operation although the development of
new dewaxing methods accomplishes the same purposes more economically than before.
24
the above processes and thus eliminating the necessity of using a large
variety of solvents for different purposes. It is thus possible by properly modifying treating conditions to see propane both as a deasphalting
and de\vaxing agent, henzol-liquid sulfur dioxide as a solvent refining
and dew<txing medium, while the deasphalting and solvent refining operations can be likewise carried out simultaneously as exemplified by the
Duo-Sol process.
25
1932
(Percolated and Dcwaxed)
RAE-20
SAE-60
26.2
Gravity, deg. API ....................... 28.4
5
20
Pour point, dell'. F. . ......................
510
Flash point. deg. I? ....................... 430
575
Fire point, deg. F ..................... 485
1.736
Viscosity (Saybolt Universal) at 100 F., sec... 373
57
123
Viscosity (Saybolt Universal) at 210 F., sec .
100
98
Viscosity index .................... "
0.6
1.5
Carbon residue, per cent ..... , .......... .
120
300
Color CLavi bond) .......................... .
4.0
1.0
Sligh oxidation No ............................. ..
1937
,---( Solvent-relined)~
SAE40
SAE-60
28.8
28.0
a
5
515
460
520
585
660
1.437
73
110
100
0.2
98
0.:1
80
0
60
o
1937
(Solvent-refined.
Percolated, and
,...----Dewaxed) - - .
SAE-ZO
31.1
430
480
294
55
117
0.3
70
SAE60
28.5
0
540
610
1,543
122
105
0.4
30
26
However, considering the inherent differences between the solvent retiniug and acid treating processes, it is to be expected that the actual advantages and disadvantages of the two methods may vary depending upon
the properties of the oil which ri1llst be improved in the course of refming.
Very heavy sulfuric acid treats arc capable of yielding oils which, at least in
some of their characteristics, resemble the solvent refined j)roduct~. Thus refining
a Mid-Continent rcsid!.Il1IIJ of 21.8" API gravity, 150 Saybolt Universal seconds at
210 F., 70 viscosity index (after removing the wax) aud 4.3 carbon residue after
dewaxing, with one pound of 980/0 sulfuric acid and 5.4 pounds o[ fuming acid per
gallon followed hy contacting with clay and lieW<lxing to a 10 F. pour test, gave
an oil of 30.8 0 API p;ravity, 72.2 Saybolt Universal seconds at 210 0 F., 105 viscosity
index and zero carbon residue. Refining' of the same residUllll1 wi til Olle pOt1l1d of
98% sulfuric aciel per galloIl which rnight be considered as ;l feasible COlllmercial
treat, gave an oil of 25.0 API gravity, 112.5 Sayholt Universal seconds at 210 0 F.,
83 viscosity index and 0.9 carbon residue. The oxidation stability of the sulfuric
acid refilled products was, however, unsatisfactory as compared to that of the solvent
refined products. MoreOVC1" losses to sulfuric add sludge in refining thc nil to a
105 viscosity index were tremcnc10us lind only a small fraction of the ehargc could
be recoverec1 as finished oiL
* Whitehead
27
yield a product which is vcry stable for this purpose, but the improvement in the viscosity index of such an oil 'which accompanies the solvent
extraction for improving its stability is considerable and makes the product less suitable for use than the conventionally refined one. Similarly,
when an oil must be treated to color specifications only, sulfuric acid
refining is frequently capable of accomplishing it with the minimum
expenditure of acid ane! a small loss of oil, while solvent refining to the
same color results in considerably larger losses due to the simultaneous
improvement in other properties which are of no interest to the refiner.
Thus a Coastal distillate of 2.45 Tag-Robinson color and 64 Sayholt
Univetsal viscosity at 210 F. when treated wit.h 15 Ibs. 98'1i) sulfuric
acid and neutralized with soclimn hydroxide yielded a product of 9.25
Tag-Robinson color at a 970 refming loss. By refining the same stock
with solvents employing normal plant conditions to the same 9.25 TagRobinson color the loss in refining was as high as 21.570. Moreover,
when an additional improvement in the color of the oil was attempted by
clay percolation. the two oils, though of equal color, required different
quantities of clay in order to obtain an equal improvement to a 12.5 TagH.obinson color, the acid refined and neutralizecl oil requiring less clay
than the solvent refinecl oil. These differences in the refining methods
are particularly noticeable with oil distillates which are stored for a more
or less considerable length of time before refining, probably clue to the
formation of color boclies which are more susceptible to sulfuric acid
than to solvent treats. The above examples. therefore, indicate that the
solvent refining methocls should be regarded as relatively inflexible, which
is to a certain extent contrary to existing opinions.
The inl1exihility of the solvent refining methods is likely to be more
pronounced with the modern double solvent systems than in the ordinary
single or mixed solvent processes. Double solvent systems are designed
to refine asphalt bearing residual stocks in one operation, thus eliminating
one more variable which can be altered at the will of the refiner, since with
the single or mixed solvent methods a separate deasphalting operation is
introduced when refining these types of stocks. The double solvent
system employs a solvent refining agent and a deasphalting agent sinmltaneotlsly and hence the treating conditions reqt1ired for the solvent
refining operation may not coincide with those required for the deasphalting operation. Under such circumstances it might be necessary either to
sacrifice certain properties of the oil in favor of others or to select intermediate treating conditions for obtaining a reasonable overall quality of
the product.
The above shows that while in preparing certain types of products,
notably 111otor oils, the solvent nifining methods are superior to the sulfuric acid methods, the same relationship may 110t necessarily hold for
some of the other oil products. As already shown, it may be possible to
treat an oil to color specifications more economically with sulfuric acid
28
than with solvents, as sulfuric. acid can be mack to exercise more sl'.lective
properties towards color bodies than solvenls. For this reason, the
actual economical advantages or disadvantages of the i \\'0 refllling methods may vary depending upon the degree of refining desired and 011 the
particular properties of the oil which must be impl'ovc(L Although the
solvent refining methods are able to prel)are better oils for a majority uf
pnrposes, in some instcmces the conventional sulfuric acid lllethoc1s may
still be of economic value. The choice between the two methods is,
therefore, dependent entirely upon the particnlar needs of the refinery.
The rapid growth of the various types of inhibitors or allied substances for the improvement of the properties of lubricating oils has
resulted in the development of new methods of rendering oils suitable to
service conditions without removing all of the constituents which are
gcnerally considered to be harmful. The substances of this type, which
are now availablc, frequently become of value only when applied to scmirefined or highly refined products. More complete c1iscussioll is given
in the last chapters of this book. The possibility of applying them to
oils introduces, however, additional complications into refinery practice
due to the necessity or establishing additional economic halances for the
most efficient refinery operations, provided the use of sllch suhstances is
justified by their hehavior in service.
The above discussion shows that the introduction of new rdining
methods has resulted in a.dditional complications rather tlmll simpli[i.('a~
tions of refinery operations. It likewise can be expected that ncw methods will appear in the future which will complicate the refining still
further and force the refiner to make [mther changes in his equipment
for succ.essful competition with other modern plants.
Bibliography
Chapter III
Petroleum Waxes
The presence of wax in lubricating oils is generally considered objectionable as wax crystallizes from the oil at relatively high temperatures
and causes loss of fluidity and prevents the normal circulation of oil in
the engine. However. if the engine is operated at temperatures at which
wax remains dissolved in the oil the presence of wax does not appear to be
harmful and may even be beneficial as disctlssed in more detail in connection with the pour point clepressants.
See
30
similar chemical treatment, * as it is well known that such treats are frequently indispensable for obtaining the type of crystals suitable for
pressing operations. To the writer's knowledge, however, no reliable
experimental data have yet been presented which would show that petrolatum can be effectively separated into two distinct portions-wax and
inhibitor-and that after such separation the inhibitor coultl be blended
with crystalline wax to yield the petrolatum wax. In carrying out such
investigations the crystalline wax separated from petrolatum has been
invariably found to be incorporated in the petrnlat:mn as an impnrity but
not as its trt1e component.
According to another theory two distinct types of waxes are pn;sent
in petroleum: paraffin waxes associated with the light distillates and
petrolatum or ceresin waxes fonnd in the heavy residual stocks.o
On distillation, some of the ceres ins change to paraffins clue to thermal decol11positiol1.** although this transformation is never complete. In
the cathode vacuum, however, ceresins can be distillecl without clecomp()S]tlon. These ceresins differ from paraffins in having a much higher
molecular weight than the paraffins as well as a higher specific gravity
and a higher refractive illdex.t The presence of only a few tenths of
one per cent of ceresins changes the properties of paraffins to an extent
which becomes very noticeable ill pressing and sweating operations.:I:
The important property of c('resins is their ability of retaining oil to a
much greater extent than that exercisecl hy paraffins.
SlIllJll1ing up our present rather I11cager knowledge on this subject
it appears best to assume that two distinct types of waxes are present
ill the oil, namely, paraffin wax ancl ceresin wax, hut that the structure
of paraffin wax may be modified hy the presence of crystallization inhihitors which mayor may \lut always be identical with the c('resins. However, by modifying the structure of paraffin wax by means of stich
inhibitors the resl1lting product may approach hut not become identical
in its properties to that of ceresins.
For instance Musselman' eliminates "amorphous" wax hy trcnliIlg" the oil with
aluminum chloride. 1. G. Farbcninclustrie A.-G." employs for the sallle pur[lo"e
antimony pentachloride, etc.
Lindgren and ]\hlm," an(\ Ward,S improve filtering" charaderisties by pal"tiany cracking the parafl1n (listillate.
t Mii\1er and Pilat U.Hl believe that eyclic cOlll[Jounds may he present in petrolet1111
c~resil1~ instead of sainrated paraftin hydrnl'arhoJls which are considere(l to he
characteristic of petroleum paraffins.
i: Higgs," in th~ very interesting" artkle on utilization of parafiln wax aud petnltetlin ceresin, shows that candles cQntaining 0.2-0.3% of petroleum ceresin are
sti fened and do not bend easily.
**
PETROLEUM WAXES
31
9
11
13
POUlo
Test of Oil
011'.
75
30
20
10
32
The above discussiun shows that the wax colltelli of oils has little
significance unless some data arc presented which indicate the degree of
separation between oil and wax attained ill the experimental work. This
is usually accomplished by specifying the pour test and preferably also
the cloud test of the recovered oil, and penetration, tensile strength or
some other characteristic of the wax which is appreciably affected by its
oil content.
High cloud test indicates that the oil contains SOlllC high melting' [loint waxes
which tend to separate from the oil before the oil loses its tendency to flow. Such
waxes are frequently encountered in heavy fractions of crudes of Coastal tyV'~.
These waxes should be removed for improving the appearance of the oil altho\1gh
their actual effect on the pour test and fluidity of the oil are insufl1cient for rendering the oil unfit for service conditions.
Tensile strength of wax is now being gradually adopted by the industry for
characterizing the properties of this product. Espach 17 describeR this testing
method which consists ill determining' the load required for breaking a sample oE
wax under exactly specified experimental conditions, and shows the marked effect
of the presence of small quantities of oil in lowering the tensile strength of wax
samples. The load is applied at a constant rate and the rate of loading has a
cOllsiderable influence Oll the reported value of the tensile strength of the wax.
According to the writer's experience it appears bettcr to use conrlitions of constallt
loading and to record the length of time required to break the wax sample. The
resulting logarithmic plot of time of bre;!ldng the sample against the load applied
is a straight line which can be conveniently used for characterizing the properties
of waxes uncleI' examination.
The complete analysis of the wax content of oil will t.hen be represented
as a fUllction of the pour test of the recovered oil and the quantity of the
"wax" removed. while the analysis of wax for its oil content will be
similarly expressed as the function of its penetration or tensile strength
and the quantity of the "oil" removecl.
In employing the pour test of the oil as a criterion of its wax content
another complication may arise, however, with certain type of stocks,
particularly of asphaltic nature. The presence of asphaltic suhstances
may have an effect similar to that of wax on the pour test of the oil, an<l
heavy residual stocks may often show only a small change in thei!" pour
test even after they are thoroughly clewaxecl. Such stocks will show an
additional, and frequently considerahle, lowering of the pOll!' test after
the removal of asphalt. Thus by dewaxing a Mid-Continent residuum
of 150 Saybolt Universal seconds at 210 F. with a mixture of benzolacetone at -100 F. the original pour tcst of the oil of 800 F. could not
be reduced belo,v 20 F. irrespective of the experimental conditions userl
in these extractions. Howevcl", a subsequent deasplmlting operation
reduced the pour test of the clewaxed oil to below 0 'F. The asphalt,
however, possesses also somc pour point depressant qualities, which are
discussed in connection with the pour point depressants, and in certain
instances removal of asphalt from the oil may result in raising and not
in lowering the pour test.
33
PETROLEUM WAXES
Pressing Tenlpernture
of.
Before Dew.xing-
After Dewuxing
100
114
66
69
68
74
-IO
-lR
58
55
+ 15
+ 8
-
5
5
75
66
70
82
68
76
63
57
34
The color of the oil and its carbon residue are heightened after
dewaxing as the wax can be considered colorless and having a carbon
residue of O. The effect of the quantity of wax added to the oil 011 its
carbon residue has been thus shown to follow the law of simple dilution
represented by the following equation:Hl
Cb
TV
-=--1-1
C"
IOO
where W is parts by weight of wax added to 100 parts of original oil, C.- the
carbon residue of original oil ane! Cb - the carbon residuc of the oil after adding
wax.
The change in the refractive index on separating oil from the wax
can be even utilized as an analytical method for determining the oil content of waxes. 20
Crystallization of Wax
Paraffin wax is known to crystallize in three different forms: plates,
needles and mal-crystalline. 21
According to one theory the wax can crystallize into these various
forms by changing conditions of crystallization, s11ch as viscosity of the
medium, rate of cooling, etc., while another theory assumes that the
crystal form is an inherent property of the different type of compounds
present in the wax and is substantially unaltered, except in detail, by the
crystallization conditions. This second theory states further that both
needle and particularly the mal-crystalline waxes have marked powers,
under the proper conditions, of impressing their forms upon plate waxcs.*
A paraffin distillate which can be easily pressed is characterized by plate
crystals as in the crystallization process the concentration of oil is so
high that the needles are kept in solution until the plates are formed as
such. The resulting slack wax, however, has little oil present and plates
and needles separate simultaneously. The needle f01"m is then impressed
upon plates resulting in a wax cake of good sweating characteristics
associated with the needle structure. t Similarly the wax constituents
which are associated with the higher boiling lubricating oil fractions have
a mal-crystalline stmctme capable of impressing this structme on other
wax constituents. This explains the difficulties encountered in pressing
wax distillates containing the so-called "amorphous" wax as already discussed in cOllnection with the ceresin waxes.
The rate of cooling is known to be of great importance to the crystal
size although the rate of cooling before the separation of crystals occurs
seems to have little if any effect,26 as well as the rate of cooling after the
oil is chilled considerably below a certain optimum tell1perature. 27 The
PETROLEUM WAXES
35
wh~re:
of Impurity, rate of cooling and method of stirring, 11 the absolute viscosity of the
medium, c concentration of paraffin, and s solubility.
An inspection of the wax crystals present in the oil is helpful in drawing conclusions with respect to the behavior of this oil in dew axing.
If crystals are large and well defined the oil may be pressed.* They
cannot be centrifuged, however, as the separated wax is not sufficiently
fluid to permit its continuous discharge fro111 the centrifuge unless the
centrifuge is equipped with scrapers, a rather recent al1clnot yet common
development. They can also be cold settled because they fail to form a
complicated network peculiar to crystalline wax. However, the cold
settling experiments do not necessarily align with the centrifuge experiments as is frequently believed. If the crystals are exceptionally small
the oil cannot be centrifuged because the mass of the crystals is not
sufficient to overcome the viscosity of the oil medium in ordinary dilutions.
Conventional Dewaxing Methods
The first method which has been applied for clew axing petroleum
oils was cold settling of the crude. The crude or its lubricating oil fraction was settled during the winter months in large tanks and the main
portion of the wax which crystallized out frol11 the oil was then separated
from the upper relatively wax-free layer. As a further development of
this method, which was formerly used altogether for dew axing bright
stocks, the oil was diluted with light naphtha, usually about 700/0 by
volume, chilled and settled. This process is unfavorably affected by the
presence of moisture in the oil, overheating the oil in the distillation
process, faulty acid treatment, and improper rate of cooling as for best
results the wax must be present in an "amorphous" rather than in a
crystalline state. The viscosity and the specific gravity of the oil solution must be also low so as to permit easy settling of the wax.
The cold settling" method was soon replaced by filter pressing and
centrifuging of the wax. As already mentioned the wax present in light
distillates on chilling crystallizes out in sufficiently rigid and well defined
crystals so as to permit their separation from the oil by filtration. The
heavy residual stocks on t he other hand contain a type of wax which
Davis and Campbe1l 1B describe a laboratory procedure developed for this purpose. I t is eviclent that utmost care must be exercisecl in carrying out this procedure as the lack of standardization of the method of preparing the crystals will
affect their relative sizes and shapes and make the method valueless.
36
cannot be separated frol11 the oil by filtration and the separation is, therefore, effected by centrifuging. For this reason, in distilling the lubricating oil fractions the crude is divided so as to obtain pressable distillates
and a residue which can be clewaxed by centrifuging. A slop cut is
sometimes obtained, however, which can be neither filter pressed 110r
centrifuged and causes many inconveniences in the refinery operation.
For the same reason difficulties are frequently encountered in dewaxing
overhead cylinder stocks as they contain both crystalline (paraffin) and
amorphoLls (ceresin) types of waxes and are for this reason inconvenient
in dew axing operations.
When wax is removed from the distillate fractions by filtration the
oil is chilled first either ,yith or without naphtha dilution depending on its
viscosity. Dilution is, evidently. undesirable both because it requires
additional distillation for removing naphtha from the dewaxecl oil and
fr0111 the wax ancl also because the differential between the chilling temperature and the pour test of the product must be higher as some wax is
soluble in naphtha used for dilution. Distillates of 70-80, and -frequently
100 Saybolt Universal seconds at 100 0 F., can he dewaxed without dilution; but for distillates of 100-200 seconds, fro111 40 to 50% by volume
of naphtha is required, while for heavier stocks the quantity of naphtha
11lay be raised even to 7070. The rate of chilling' down to about 10" F.
above the cloud test is apparently of no importance, but further chilling
is carefully controlled and is lIsually about 1_20 F. or, as a maximum,
3-5 0 F. per hour, until the temperatme of the oil reaches 0 F. It seems
also that further chilling can be done at a much fasLer rate without
undesirable effects on the filtering characteristics of the wax, but, nevertheless, 1110st of the refiners continue to chill slowly until the oil is chilled
to the required temperature. The importance of slow chilling rates
within a certain temperature range is explained by the importance of
forming relatively large crystals so as to facilitate flltering operation.
The chilled oil is then filtered through filter cloth, sometimes in presence
of small quantities of filter ;tid to prevent the wax fro111. forming ~U1
impervious mass on the filter cloth. Afterwards the iiltration naphtha,
if used, is distilled off from the oil, although some refineries may percolate the oil through clay while still in naphtha solution and only then
remove the diluent naphtha.
The differential between the pour test of the oil and the chilling te11lperature is usually about 40-50 F. when naphtha is used for dilution.
but may be as low as 5-10 0 F. when dilation is not resorted to. This is
explained by the rather considerable solubility of wax in naphtha which
becomes an il~lportant factor, particl11arly in dewaxing' oils to low pour
tests.
In the centrifuging operation the oil is usually diluted with 60-70%
naphtha as the residual stocks are too viscous at low temperatures for
centrifuging them without dilution. They are then chilled in the same
0
37
PETROLEUM WAXES
Bibliography
1. Buchler, C. C., and GrClvcs, G. D., Ind. Eng. Chell'., 19, 718-24 (1927).
2. Fussteig, R., Rev. chi",. il'd. (Paris), 43, 71-80, 96-101 (1934).
3. Lederer, E. R., and Zublin, E. W., Oil Gas .T., 29, No. 32, 64, 101 (1930).
4. Musselman, J. M., U. S. Patent 2,014,629 (Sept. 17, 1935).
S. L G. FarLJenindustrie A.-G., French Patent 803,470 (Oct. 1, 1936).
6. Sa~hanen, A. N., Zherdeva, L. G., and Vltsilyev, A. N., NnU. l'etro/wlI! Ne",."
No. 16,
49-52; No. 17, 67-70; No. 18, 51-3; No. 19, 71-4 (1931).
7. Lindgren, H. 0., ,md MaIm, K. G., U. S. Patmt 1,847,488 (Mar. 1, 1932).
8. Ward, J. T., U. S. Patent 2,054,777 (Sept. 15. 1906).
9. Muller, J., and Pilat, S., Nature. 134, 459 (1934).
10. MlHle!-, J., and Pilat, S., l. I"st. Petrole"m Tech., 21, 887-94 (1935).
11. Higgs, P. G., J. 11'sl. Petro/emit Tech., 21, 1-14 (1935).
12. Holde, D., Kohle1lwasserstofJe "I'd Fette, 105 (1924).
13. Sachanen, A. N., Neftyanoe i Slanceva" Khoz., 7, 933-53 (1924).
14. Fussteig, R., Z. angew. Chem., 91, 418-21 (1933).
15. R'LVikovich, A. M., and Shile, V. N., .T. Apj)Zicd CT.em. (U.S.S.R.), 8, 172-6 (1935)
16. Heinze, R., and Zwergal, A., De! Kahle Erdoe! Teer, 2, 7_12, 154-7 (1934).
17. Espach, R. H., U. S. B"r. Mines Bull., 388, (1935).
18. Davis, L. L., and Campbell, D. S., Oil Cas l., 32, No. I, 49-50, 62 (1933).
19. Rics, E. D., Ind. Eug. Cltem., Anal. Eri., 1, 187-91 (1929).
20. W'ilson, R. E., and Wilkin, R. E., I"d. Eng. Che", .. 16, 9-12 (1924); Piotrowski, W. J., and
Winkler, J., Erdol u. Teer, 6, 447-8, 463-5 (1930).
21. Ferris, S. W., Cowles, H. C. Jr., and Henderson, L. M., Ind. E1tg. Chem., 23, 681-8 (1931);
Padgett, F. W., Hefley, b. G., and Henriksen, A., Ind. Eng. Chem., 18, 832-4 (1926).
22. Katz, E., .T. lust. Petroleum Eng., 16, 870-88 (1930); 18, 37-52 (1932).
23. Tanaka, Y., Rei)ts. Imp. Fuel Re.<earch Inst. lapan, No. 8 (1929).
24. Padgett, F. W., Petro/e",,, Eng., 2, No.4, 80, 83-4 (1931).
25. Tanaka, Y., Kobyashi, R., and Arakawa, L, l. Fac1tZty Eng., To/,yo 1",1). Un;".. 18,
109-15 (1929).
26. Ellsberg, E., U. S. Patent 1,974,398 (Sept 18, 1934).
27. Lederer, E. R., British Patent 369,975 (Mar. 29, 1932).
2"
Chapter IV
Dewaxing with Filter-Aids
The major disadvantages of the old conventional dew axing methods
described in the preceding chapter lie in the necessity of distilling oils
before dew axing in order to separate the paraffin and the ceresin types
of waxes requiring different dewaxing methods for their rcmoval from
the oil; in the inability of these methods to remove wax fr0111 certain
types of distillates such as slop cuts or overhead cylinder stocks; in the
necessity of employing high temperature differentials between the
required pour point of the oil and the dewaxing temperature; and in thc
lack of a sharp separation between the oil and wax which results in high
oil losses. Moreover, commercial application of these processes is frequently associated with further inconveniences such as the necessity of
slowly chilling oil solutions to be dewaxed, the importance of pretreating
certain types of oils before dewaxing in order to obtain a reasonable
degree of separation between the two phases, etc.
39
40
system.
The filter-aid is usually "Hyflo Super Ccl" or "White Speed
Flow." The quantity of the filter-aid used varies with the type of stock
and the nature of the liiter-aid and may be as high as 150/0 by weight of
the oil used.
The rcsulting mixtl11'e is filtered using pressure or vacuum type filters,
but the use of centrifuges has also been reC0111111ellcled. 12 Filtering rates
usually vary between 0.3 to 1.0 gallon of dewaxecl oil per square foot
of filtering area per hour. The wax cake is washed on the filters with
cold solvent, dried with cold incrt gas, and the filter-aid is then recovered
by dissolving the deposited wax in hot naphtha. The recovered filtcraid gives the rates of flow which are about 50-60% of those of the new
filter-aid, but this lowered eniciency is claimed to remain unaltered
irrespective of the number of regenerations.
Fussteig13 discl1sses the possibility of recovering paraffin frol11 fuller's earth
used in treating lubricating oils by extracting it with a light gas oil at 195 0 F.
According to Selskii,'" separation of pal'affin wax from clay with hot water is
exceedingly difficult or even impossible due to the emulsifying properties of the
clay.
'Veir 1r. decolodzes the oil first by heating' it with an adsorbent 1111([ then cooling the mixture below the crystallization temperature of the wax before filtering.
Weir 10 also claims that clay used for color treatment of variol1s stocks is satisfactory for dewaxing purposes and that the clay used in dcwaxing can be regenerated
repeatedly for this purpose without loss in efficiency.
* Mitchell-Roberts
11
41
* Deutsche Gasolin A._G;17 Pfaff, Bottger, and Sieweke ;18 Deutsche Gasolin
A.-G,'" Katz 2. claims that the crystallization of wa..-.r in presence of naphthalene
proceeds very satisfactorily and that the resulting wax cake is easily filtered out
f1'0111 the oil.
t Burk" uses for this purpose from 50/0 to 250/0 phenol. See also Fnsste.ig.'"
42
MODERN
~METHODS
Biblio graphy
1.
2.
3.
4.
S.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
Chapter V
Solvent Dewaxing
The rapid growth of chemical industries in the course of the last few
years and the development of new processes for manufacturing different
types of chemicals have snpplied the market with a variety of relatively
cheap solvents which are superior to naphtha when applied to the
dewaxing of petroleum products. The industrial application of these
new commercial solvents by the petroleu111 iudustyy wa.s further Y<!udered
feasible by the recent engineering developments which insnre continuous
plant operation at a minimum loss in handling such solvents at the
refinery.
Two methods are apparent which can be applied for separating oil
from wax by means of solvents, namely, the wax can be separated as a
solid by crystallizing it from the oil solution at low temperatures and as
a liquid by employing the selective solvent methods described in connection with solvent refining, provided a solvent is available which is capable
of differentiating between the hydrocarbons of high and low melting
points on the basis of preferential selectivity at temperatures above the
melting point of the wax. The present solvent dew axing methods employ
the first of these principles, but a few isolated laboratory attempts to
obtain the desired separation of oil and wax in the liquid phase are also
recol'ded. 1 If such attempts are successful the cost of dewaxing petroleum oils will be greatly reduced due to possibility of eliminating expensive refrigeration and -filtering or centrifuge operations which are indispensable with the present type of processes. Further discussion in this
chapter is confined, however, only to processes in which wax is removed
from the oil solution as a solid phase because these processes alone have,
as yet, a practical significance.
44
bility sufli.ciently high to dissolve all of the wax so a::; to insl1t'e a uniform
solution and a proper distribution of solvent amI oil.
3. The solvent must be recoverable from Loth components and easily
separated from water. As separation is usually effected by distillation,
the boiling point of the solvcnt must he sufficiently low in order to permit
easy removal of the solvent without danger of contalllinating it with the
low boiling oil fractions.
4. The solvent 111ust be capable of separating the wax ill such a
form that it can be easily removed from the oil by mechanical means.
5. The solvent must have no chemical action 011 either oil or wax.
6. The solvent shottld not introduce complications in the design of
the plant equipment by reql1iring expensive materials to withstand corrosion or high pressures. The solvent should also present: 110 excessive
hazards due to its poisonous or inHa1l11llabie nature.
Several very interesting articles on the poisonous character of commercial
solvents employed in petroleulII rciining, have been published by Franci~, covering- Benzene,"" Phenol,"~ Chlorex,"" Cresol,"" Nitrobenzene," Furfural,"' Sulfur
Dioxide,"" Aniline,'" Ketones,"' Aldehydes;J and Trichlorocthylene:k
45
SOLVENT DEWAXING
certain optimum, results in a higher pour test of the recovered oil because
the quantity of the wax left in the oil aIter distilling the solvent is directly
proportional to the volume of the solvent used. However, clue to the
negligible solubility of wax in 1110St of the commercial solvents at the
extraction temperatures, the above considerations are usually of little
commercial importance. This is so because the effect of increasing the
quantity of solvent on the pour point of the oil becomes detectable only
with solvent ratios considerably above those, which are economical at
the plant. The llse of very small quantities of solvents may also result,
however, in an increase in the pour test because the solubility of wax in
oil may be greater then than after addition of the solvent, notwithstanding the increase in the total volume of the liquid phase. The above considerations are illustrated by the experimental data presentcd in Figure 1
1.1
\
'"
18
/5
........
~ ........_
81. 7F.
12
...............
..........
...........
...__
r-
..._
71.2 F.
39.0 oF.
o
.2.
. .3
.4
.5
. to.7 .8.9/.0
2.
4- S
which show the solubility of 122 0 F. melting point wax III Pcntasol,*
and L)ij mixtures, the quantity of oil used being constant:!
A considerable amount of highly interesting work 011 the relative
;ioluhilities of paraffin waxes and lubricating oils in a large variety of
A trade name for an isomeric mixture of amyl alcohols synthesized from the
pentane fraction of natural gasoline by chlorination ane[ hydrolysis.
46
solvents has been carried out by Poole and his collaborators during the
last few years. U
Solubility of wax in acetone and nitrobenzene was determined by Henderson
and Ferris," and that of wax and lubricating oils in acetone by Wy~llt: ancl Mars~:
Velikovskii and Zuikov S give a review of literature on the soluhlhty of waxes 111
naphtha, ethylene dichloride, iso-propyl alcohol, acetone, methyl-ethyl ketone and
white and yellow ketone oils.
Of the solvents they examined they found that butanol, butyl formate,
paraldehyde, pentasol, n-btttyl aldehyde anel diethyl carbinol secmed to
offer the most promise as cOll1mercial dcwaxil1g solvents. On the basis
of their extensive experimental data they recolllmended the use of the following equation for expressing the solubility of wax in any solvent with
respect to temperature:
log W = A (log T - K)
011 the nature of wax, and ]( = constant dependent on the nature of the
solvent. The above equation shows that the plot of solubility against the
absolute temperature on a logarithmic paper is a straight line. However, the above equation does 110t give even approximate results when
applied to solutions containing oil, though by making certain assumptions the constant K. which characterizes the nature of the solvent with
respect to its ability of dissolving wax might be calculated.
The above work although of considerable theoretical interest does not
reproduce exactly the conditions encountered in commercial practice, ancl
for this reason, the value of a dew axing solvent for the refinery should
~llways be determined by investigating the effect of the particular solvent
on the lowering of the pour point of actual plant stocks to be clewaxed.
This is particularly true due to the existence of a series of compounds
intermediate between oil and wax mentioned in Chapter III which are
not taken into consideration in the above solubility measurements.
Ra Thi, Strang, Hunter, and Nash 0 discuss principles of solvent clewaxing and
recommend a method for graphical interpretation and yield computation by means
of triangulal' diagrams. However, the lise of this method does not seem to PI'Oc\tlce
entirely reliable results, particularly dl1e to the incorrect assnmptiOll that the melting lwint of the wax se[larated from a given oil fraction depends only on its oil
content.
47
SOLVENT DEWAXING
required in dewaxing. Benzol and toluo I, however, are capable 0 [ dissolving large quantities of oil with which they are miscible in all proportions, though they likewise dissolve appreciable quantities of the wax.
By mixing two such types of solvents in proper proportions a blend can
be obtained which has low solvent power for the wax and large solvent
power towards the oil under the temperature conditions required for
dewaxing. Similar relationships are found among a variety of other solvents such as ethylene dichloride and chloroform, or ethylene dichloride
and benzol, furfural and benzol, etc. It is, therefore, possible to obtain
the desired solubility characteristics from a dewaxing solvent either by
"
EXTRACTED
80
,.
VOLUME
40
.50
60
70
/0 BV
OIL -
2D
30
or
100
Bo
-........
It.:
I>
60
f:::.
~
<q;
40
\
-......."
i ......
.1,:&
~ ~.s
10 PENETRATION WAX\
.~-9~
>0
~ot<'
~ :v
~)'
.\~,,1~
% ~~"
'\.~
~./",
tJ'i:J..
"
'><
l<.I
l.a...
:r~
20
~b&"~~~V" ~
"C:l
~" ~_,.~
<:>,t,,"
\.~
\'1&~:~~~
\1 Of '(19 ".
0 ... '''' :'
\'
2{)
3D
40
SO
WA X FIGURE
60
to
10
80
BY VOLUME
48
ons
49
SOLVENT DETFAXING
[or all solvents employed ill oil relining aile! fur this reason the discussion
helow is not rcstricted to dewaxing solvenls alolJc.
In general, solvents can be divided into those which do form, and
those which do not form, constant boiling mixtures with 1\'ater, while in
respect to their solubility chantderistics they lllay he immiscible, partially miscible 01' completely miscible with the water. The table below
presents these characteristics of co1llmercial solvents. '1'
TABLE
Boiling
IPoint
Solubilities at 100" F.
Solvent
\Vatcr
ill ,Vater
in Solvent
Solvent
Deg. F.
Acetone
Aniline
Benzol
Carbon tetrach loricle
Chlorcx
a-Crcsol
m-Crcsol
j>-Crcsol
Ethylcne dichloride
Furfural
Methyl cthyl ketone
Nitrobenzene
133
<Xl
364
3.8
Phcnol
Propane
Sulfur dioxide
Toluol
Trichloroethylcne
17G
17(]
353
Wt.%
O.1G
0.09
l.2
Wt.%
c/O
5.6
0.11
0.01
1.1
375
396
3.0
182
2.5
2.2
14.5
14.5
16.5
0.9
9.0
19.0
10.2
391;
323
175
412
0.3
3SR
9.4
-48
6.5
0.35
ns
14
231
188
0.05
0.16
0.05
Boiling
Mixture ,
Bolling
Point
Deg. Ii'.
Compositiun
Constant
Boiling
:M:ixture
Overhead
Wt.%
SOIV~llt
none
none
none
none
none
209
204--207
210
210
210
158
208
11i4
211
23.1
none
6
6
Ii
91.8
35
88.6
15.3
(14)
210
none
none
none
167
9
none
none
none
Vlhenever a solvent cloes not form constant boiling mixtures and the
differential between the hoiling point of the solvent and that of the water
is reasonable. separation can be accomplished by fractional distillation
provided corrosion difficulties, such as are encountered in sulfur dioxidewater mixtures, arc 110t beyond the usual tolerances of the present COlllmercial equipment. In tertiary mixtures. such as bel1zol-acetone-water,
complications may arise tiue to the sohtbility of one of the components,
acetone, in the two other components, water and benzol, which are
mutually insoluble. The presence of acetone in water, hO\vever, results
in the solubility of benzol in such mixtures. This difficulty can be
avoided by keeping the concentration of one of the components, acetone,
in water below the point where any appreciable solubility of the other
component, benzol, in the water phase would result.t
* Smoley and Kraft 10. 11 give a very interesting discussion 011 this subject to
which the readers are referrcd for further details.
l' Myers'" describes methods which are applicable for separating water from
acetone-benzol mixtures.
50
MODERN METHODS
or
Solvents forming constallt hoiling point mixtures with water but having relatively sl11aIl mutual solubilities, stlch as ethylene dichloride, trichloroethylene, chlorex or nitrobenzene, can be recovered to a large
extent free from water. The small portion of the solvent forming the
constant boiling mixture is passed into a separatur [rom which the solvent
phase, saturated with waler, is acltlcd directly to the dry sol vent, since
the total quantity of water thus introduced into the dry solvent is usually
insufficient to have an adverse effect on its characteristics. The
water phase from the separator is then distilled in order to obtain free
water and the constant boiling mixture of water and solvent, the latter
being handled in the way above described.
Solvents forming" constant boiling mixtures and having appreciahle
mutual solubilities in water are handled in a variety of ways, depending
OIl the nature of the mixtures, which can be classified as follows:
Solvent-water mixtures which show a considerable difference in composition between that of the constant boiling point mixture and that of
the solvent phase of the cooled condensate may be separated by distilling
the two phases separately. This results in separating the solvent from
the constant boiling point mixture ill olle still and water fro111 the constant boiling point mixture in another still. The two phases obtained on
liquefaction of the constant boiling point mixtures in either still are then
redistilled in the respective stills, in order to obtain further separationP
This method is applicable to separating mixtures of water with furfural
or with alcohols, etc. For mixtures where the difference in the composition of the constant boiling point mixtnrc and the condensate is small,
such as mixtures of water with cresol, phenol, ur aniline, the saturated
water phase may be converted into steam which is then introduced at the
bottom of the fractionating tower.I-!
It appears feasible also to add to the constant boiling mixture a third
component which is capablc of fonning a constant boiling mixture with
water at the expense of the water present in the original constant boiling
mixture. This may be accomplished by simply supplying the third component as reflux at the top of the fractionating column. 1ii
It is likewise possible to separate the const~mt boiling point mixtures
by saturating them with salts such as sodium chloride or sodium sulfate
which resolve the solutions into two phases by "salting out" the solvent,
by dissolving" the Rolvent fro111 water through use of another solvent
which is immiscible with water but which dissolves the other component
of the constant boiling mixture, etc. The commercial application of the
above methods depends 011 the individual problems encountered in refin~
ery practice which l11ust, therefore, be studied separately.
SOLVENT DEWAXING
51
52
MODERN METHODS
or'
53
SOLVENT DETYAXING
TABLE
Temperature
F.
C.
Jl-Pcnianc
Hcx:tnc
15
20
25
of Solvent
iso-Dec~me
oll-0ctane
1.37
2.18
3.55
5.06
7.18
14.36
0.99
1.69
2.90
4.24
0.94
1.44
2.74
5.93
4.98
11.66
9.17
3.69
4.81
6.07
8.31
16.23
5.11
6.94
9.53
17.16
C.l:.
H-lTcptanc
2.77
0
5
III
32
41
50
59
68
77
The above shows that heavy naphtha is preferable to the light naphtha
from the viewpoint of wax solubility relationships, although the use of
light naphtha is obviously desirable for effecting the maximum possible
,90
,......- ........
,80
" ,'"
K'
'~'\
"\
v
L
II
,.,.,
- r<.
1'-1<.
---
"- ,
"'-
""-
......
-::.. !.e...0p,
'-...
"-
i'-- r--........
_/'_
.... ~r-
o
3D 40
..sO 60 70 80 90 100
MOLECULAR
FIGURE
lt~
/50
/70
WEIGHT OF SOLVENT
0
54
decrease in viscosity
ratio.
1)[
Dahlke, Giles, and Adams" give the following cumparisons of the specific
gravities and viscosities of butane aud naphtha solutiom of an S.A. E. 50 distillate
nil at - 10" F.
TAllLE 8-Solutions of S.A.E. 50 Distillate Oil
vIa Oil
% Solvent
,---SpeciJic Gravity____,
Naphtha
Butane
Snll1tion
Solution
0.813
0.u(;7
Nitl'lltha
Solution
0.025
B\\tane
Snlution
[)'OIIS
15
85
2.1
75
O.H2S
0.700
a.()17
0.009
35
65
0.841
0.73:1
0.101
11.1118
II'
crystal oil.
The naphtha employerl at the different nncries is usually the one which
gives a proper balance between these two opposing tendencies.*
The above investigations covered, however, only hydrocarbons which
are liquid at ordinary temperatures. Further researches of the similar
type with liquefied normally gaseous hydrocarbons showed that soluhility
of wax with the decrease in the molecular weight (or boiling point) of the
hydrocarbon solvent reaches a certaiull1axill1111ll after which the solubility
begins to decrease, apparently reaching its maximum somewhere between
hutanes and pentanes, as illustrated by the curves in Figure 3 on ~oIt1-
_-
CUANER5 $OLVNT(BP32.(,-3%F:)- - l I I
CLeANERS NAPHTflA(B.P2tJS-29S"f),
I I I
METHYL CYcLOIl{; ><AN--1
I
I
I
v-t
C \;~
,,~
/
//
"l
./
/
1//
./
V f f ,/ /
./
,"_
k::_
~;9 f - - -
./
././
./
~V
/ /
~J v
'/)).
/
~
~ /
'v.f:
.1/
",0/
~c,'V,
'/ /
/'~~~~ v
~<,V
'!/~
./
'/ ~tf}
'c~
VV
p~7
1/
/0
/5
20
25.3"
3.5'
40
4-5'
SO
SS
TE MP/fATURc oF.
FIGul\g 4.-Solubility of 123" F. Melting Point Wax in
V(lriOl1S
Hydrocarhon Solvents.
GO
6$
SOLVENT DEWAXING
55
TAIlLE 9~Physical
Properties of Propane
44.03
-4,).8
-43.7
107.2
134.2
186.S
199.1
269.6
212.2
643.3
0.06896
0.5111
0.5116
145.1
4.265
0.9841
0.001836
0.11S3
8.451
l.5461
3r..05
36.63
lS.tO
780.0
0.fi5H
0.404
1.162
21,493
19,940
91,670
85,050
2,555
2,376
2,511
2,335
2.3-9.5
S6
For further details see Lacey and Sage,"' who carried out an extensive investigation of the properties of propane over a wide range of temperature and pressure
conditions and developed a series of graphs which are of much importance ill
designing plant equipment.
t Voorhees"" tlses the same principle of self-refrigeration with other solvents
than propane, namely, with alkyl and alkylclle ethers which he recommends as
dewaxillg solvents.
=!: Auderson and Talley 27 present the results of their thorough study on wax precipitation from propalle solution, as applied to a residual oil.
SOLVENT DEWAXING
57
58
solution clue to its high melting point. Toluol is also more effective than
benzol in lowering the miscibility temperature of oil-solvent mixtures
and preventing separation of valuahle hig-h viscosity index constituents
with the solidified wax.* Nlcthyl-ethyl ketone is somewhat cheaper and
has slightly better soluhility characteristics than acetone which justifies
its use at the plant, although it is frequently necessary to employ it in
somewhat larger quantities than acetone in oreler to obtain similar results.
These differences are insufficient, however, to warrant a separate discussion of these solvent substitutes. Besides methyl-ethyl ketone other
ketones were also recommended as suhstitutes for ac.etone, while solvents
similar in their solubility characteristics to benzol or toillol were likewise suggested.
Gove.rs "" s[lccit:ies a l11ixlun: of acetone, lllcthyl-cthyl ketone, benzol and toluol;
vVagner "" substitutes mcthyl-ethyl ketone for acctone; Gruss and Obcrbaugh,'" and
Texaco Development COl"p.,'17 use l1Iethyl-iso-butyl ketone blended or not blended
with gasoline, benzol, propanc, butane and other similar solvents; Kellogg "" employs
a blend of acetone and solvent keroscne extract rich in aromatic compounds;
McCarty and Skelton "" use a mixture of propane, ortho-dichlorohenzene and
acetone or methyl-ethyl ketone.; van der \Vaerden -10 and N. V. de Bataafsche Petroleum Maatschappij;"" dewax with acetonc or methyl-ethyl ketone and tctrahydronaphthalene; Texaco Devclopment Corp:'" uses cyclic ketoncs containing from fonl"
to seven carbon atoms, particularly cydohexanone, in presence or absence of dilucnts such as propane or benzol; Peverc1I speciHes cyc1ohexanollc; Knowles dn
employs a mixture of ketones; Govers <" utilizcs lllethylcthyl ketone and toluene,
xylene or cumenc.
10-Properties of Solvents
Methyl-Ethyl
Acetone
Ketone
Molecular weight
Sll-OS
72.06
Boiling point, F.
133.0
175.3
Melting point, 0 F.
-123 ..1
-137.7
Specific gravity at 68 F.
0.8050
0.7915
Viscosity at 77 F" ccntipoises
0.316
D.401
0
Vapor pressure at 68 F. mm, I-Ig.
184.8
77.5
Flash point (closed cup), 0 F.
2
19
0,527
Specific heat, B. t. u./lb,/' F.
0.550
190.8
- Latent heat of vaporization, B. t. u./lb. 225.0
1.3591
1.3791
Refractive index at 68 F.
llenzo\
'l'nluol
78.05
92.06
175.3
230.9
4].9
-139.2
0,878
0.8(J6
0.647
0.586
76.0
22.0
10
0.410
0.398
169.7
155.7
1.5014
1.4902
01"
* HaJJ
59
f'
~
~
~
~
c
~
0
"
~
h
"
t:
~
..;
'E
:::J
bJJ
.S
~
OJ
'5..,
..?;
0
en
..,
......,
~I
'0N
5
I
o-i
.....
P=l
f.<
-<:
...l
Poi
60
times be required, however, in c1cwaxing oils of rather ullusual characteristics or when the maximum oil recovery is o[ primary economic COllsideration. The mixture of solvent and oil is chilled rapidly at a rate
which may be as high as 90-100 F. in 1 to 3 hatHS. These rapid chilling
rates do not appear to be objectionable with respect to the filtering rates.
The cooled solution is iilterell ,uld solvents recovered by distillation. Pressure or vacuum filters are used, the vacuum filters being advantageotls
by permitting continuous plant operation. The procedure is substantially
the same for distillate or residual stocks. The wax cake is washed with
cold solvent for removing the oil and this wash solvent is then cmployed
for diluting the fresh portion of the oil charge.
Pretreatment of stocks to be dew axed with clay or sulfuric acid and
clay, which is customary in naphtha clewuxing, is not required. Some
difficulties may be encountered only in clew axing highly treated oils
containing small quantities of low melting point waxes, hut these conclitions are seldom, if ever, encountered in commercial practice. In preparing the initial solvent-oil blend it is likewise frequently possible to avoid
the use of high mixing temperatures in order to obt'lin a homogeneotls
solution, although this is often desirable with high viscosity or residual
stocks in order to improve filtering rates and yields of the clewaxed oil.
With such type of stocks heating to temperatures 50-60 F. llbove the
complete solution temperatures may he of importance.
The benzol-acetoue process is now being used by a number of large
petroleU111 companies which include the Texas Oil Co., Socony-Vact1t11l1
Oil Co., Inc., Atlantic Refining Co., Gulf Refining Co., ctc.
SOLVENT DEWAXING
61
benzol, naphtha ~r simi1al solvents; McCarty and Skelton" use a dewaxing solvent
composed of o-dtchlorobenzene, an alkyl ether of ethylene and diethylene glycol;
McCarty and Skelton 7(\ recommend a blend of o-dichlorobenzene and amyl alcohol;
Voorhees,7. and Livingstone,'" '" specify mixtures of two solvents one of which is
a poor wax solvent such as ethylene dichloride, and the other a good wax solvent
such as benzol; McCarty and Skelton 70 use ethylene dichloride and amyl alcohols;
Tanne and Oherlander '" employ chloroform or carbon tetrachloride to which acetic
or similar acids might he added; McCarty and Skelton 81 employ orthodichlorobenzene and ethylene dichloride; McCarty and Skelton R2 specify a blend of 60%
amylene dichloride and 40% methyl-ethyl-kctone; McCarty and Skelton" use isopropyl ether and ethylene or propylene dichloride; McCarty and Skelton 8, specify
propylene dichloride and ethylene glycol ethyl ether; L G. Farbenindustrie A.-G."
uses mixtures of a chlorinated hydrocarbon such as carbon tetrachloride, with
methyl-ethyl ketone or alcohols such as butyl alcohol or a mixture of methyl-ethyl
ketone with alcohols; Bray so employs propane with di- or tri-chloroethylene;
Sharples Specialty Co." employs ethylene dichloride and benzol; St;Jndard Oil
Development CO.AS dewaxes with carbon tetrachloride, ethylene dichloride, bmmoform, chlorobenzol or with a mixture of dichloroethylene and benzol or dichloropropane, toluol and xylol; Aktiebolaget Separator-Nobel so employs ethylene chloride and acetone; Jones" l1ses dichlol"oethane and a properly selected petrolel1m
fraction; N. V. de Bataafsche Petroleum Maatschappij 01 l1ses chloro- or brOlllOhydrocarhon derivatives; Sharples Specialties Co. o, recommends trichloroethane:
Covers" c1ewaxes with a mixture of ethylene dichloride and a polar substance.
such as liqllid sulfur dioxide, acetone or methyl-ethyl ketone; Wiles u, uses ethylene
dichloride.
The use of such mixtures is frequently desirable for the same reasons
as those explained in connection with the benzol-acetone p1"Ocess.
Although chlorinated hydrocarbons may be employed in connection
with both -filtering or centrifuging methods for separating the wax, they
are practically always employee! in connection with the centrifuge methods
for which they are particularly adapted clue to the high specific gravity of
the solvent. For improving- the yield of the clewaxed oil double centrifuging is sometimes employed. Do
Centrifuges which are llsed in connection with the chlorinated solvents
are of a different type than those commonly used in naphtha dewaxing
as wax separates out at the bowl of the centrifuge anclllot on the outside
of the revolving cylinder. Scrapers are frequently employed for the
removal of crystalline wax when such wax is present in sufficient quantities
to interfere with the smooth discharge of the separated wax. Such
centrifuges are, therefore. suitable for removing wax from both residual
and distillate stocks.
In general, thc chlorinated solvents have a tendency toward liberating
chlorine (or hydrochloric acid) on heating, which results in darkening of
the oil when the solvent is removed by distillation, and in the corrosion of
the refinery equipment. For this reason special care should be exercised
in selecting the proper chlorinated solvent of sufficient chemical stability
and in employing low distillation temperatures at which the decomposition
of the solvent is negligible. Some of the chlorinated solvents, such as
carbon tetrachloride, may be in this respect more objectionable than
others as represented by trichloroethylene,9o or ethylene dichloride, which
to a great extent determines their practical application,
62
131.4
Molecular weight (CoHC1:,) .......................... .
Specific gravity at 32 F. . ........................... .
1.4996
1.4762
Specific gravity at 59 F. . ........................... .
1.4514
Specific gravity at 86 F. . ........................... .
1.4262
Spccific gravity at 113"0 F ............................ .
1.3937
Sp~~iilc gl:avit at 139 F. . .......................... .
BOlhng' pomt, F.. ..................................
188
Freezing point, 0 F. . ................................ . -126
0.550
Viscosity (centipoises) at 77" F ....................... .
0.446
Viscosity (centilloises) at 122 0 F ...................... .
Viscosity (centiJloises) ;It 167 F ...................... .
0.23
Specific heat, n. t. n./lb. 0 F. . ........................ .
104.5
J ,atent heat of vaporization, B. t. 11./lb. . ............... .
0,017
Solt1bility of watcr in trichloroethylene, % wt. at 500 F.
0.035
Sol11bility of water in trichloroethylene, % wt. at 82 0 F.
0
o.m
It is also claimed that trichloroethylene is l1on-eorrnsive, does not hydro1ize 1101' decompose all heating up to about 265 0 F. and that when distilled
with steam at below 265 0 F. there is no danger of corroding the equipment. It may, however, decompose on heating or 011 expostlre to light
in the presence of oxygen unless antioxidants are present.
In commercial practice the oil is blended with from} tn I} volumes
of trichloroethylene in a mixing colul11n at ahont 100-120' F. The soltltion is chilled at the rate of 10-15 F. per hour although in exceptional
cases the rate may be lowered to about 8 0 F. per honr. Sometimes it
appears desirahle to chill to + 32 F. at the rate of 9 F. per hour and
then increase the rate to 14-15 F. per hour. In order to nhtain an oil of
0 F. POlll" test, tbe oil solution is usually chilled to -20 F. although
this 20 F. c1ifferenti~ll may vary with the properties of the stock to be
c1ewaxed or the pour test of the oil desired. The chilling operation can
be thus accomplished in approximately 10 hOl1rs.
The chilled sollltinn is charger! to ccntrifuges which are vapor-tight
and cliffer in the design frol11 the conventional type of centrifuges. The
semi-solid wax is discharged from the central part of the bowl into a
steam heated wax receptacle whereas the clewaxed solution is discharged
63
SOLVENT DEWAXING
into a carefully heat insulated receptacle and ttsell for precooling the
fresh oil-solvent blend. Because of the considerable difference in gravity
between the oil and wax phases when trichloroethylene is employed as the
clewaxing solvent the centrifuges can be operated at relatively low speeds
of 8,000-9,000 r.p.m., instead of 15,000-17,000 r.p.lll., when naphtha is
used. Trichloroethylene is removed from the oil and wax phases by
distilling at about 230 0 F. first in the absence and then in the presence
of steam.
98.95
1.257
182.7
- 31.5
0.90
Ci4
SOLVENT DEWAXING
65
then recovered and the solvent containing the oil is used together with
the fresh solvent for diluting the new oil charge to primary centrifuges.
The solvent is recovered from the oil and wax phases at a temperature of
about 290 0 F.
66
stituents, and the nlflitlate phase is thcll diluted with benzol and, jf llCCQSsary, with additional quantities of the refining solvent. The possibilities
of using such combinations cOllllllercially arc illllstrated hy the following
experimental data obtained in dewaxing a Mid-Continent residuum of
50 Saybolt Universal seconds at 210 0 F., with three volumes of variollS
furfural-benzol blends at - 50 F.
13-Dewaxing with Blended Solvents
(3 Volumes of Solvent pCI 1 Volume of Oil)
TADL]c
,---Solvent lVIi.xlul'c~
% Furfural
% Benzol
95
10
20
30
90
80
70
p11lt~c?:o
a.re IOnlit~il.
Dewaxed Oil
T'ml), Tpst
%Yieltl
OF.
82
82
25
20
5
77
57*
Extraction of the same oil with three volumes of a 35 ~Y) acetone and
650/0 hell7.olmixture gave a yield of 7870 of the dewaxecl product of a
+ 10 F. pour test.
The ahove datLl. >.how that within the limits uf experimental crror the
yield and properties of the oil clewaxecl with hear-oJ-acetone or with a
mixture containing 20% furfural and 80% benzol are the same. Similar
to the conditions encountered in benr-oi-acctone extractions, the decrease
ill the quantity of furfmal in the furfural-benzol hlend resnlts in highel
differentials between the ]lour test of the oil and the chilling temperature
and in lower fi.ltering rates. The use of excessive quantities of furfural.
however, separates tile oil into two liquid phases which can he expected
with any solvent used fur removing the low viscosity index constituents.
Solvents which can be used both as c1ewaxing and c1easphalting agents
are represented, besides propane, which was already discussecl, primarily
by the aliphatic alcohols. Their deasphalting properties ,tre discussed in
the later chapters and the present description refers ollly tn their rlewaxiug characteristics.
In general, alcohols suitable [or dew;txing a1"l~ huty1, amyl or hexyl
alcohols anel their mixtures with lighter alcohols or other solvents. Addition of snch solvents is frequently illdispensable in order to modify the
soluhility characteristics so as to avoid excessive losses of the heavy oil
fractions by preferential solubility.
Experimental data presented in l<'igul"e 5 show the results obtained
in c1cwaxing a Mid-Continent residuum of 100 Saybolt Universal seconds
at 210 }'. and a pour point of 100" F'. with various quantities of fuseI oil*
at different temperatures, The relatively low yields of the dewaxed oil
are to a great extent explained by the simultaneous precipitation of
SOLVENT DEWAXING
67
asphalt as the primary purpose of these experiments was tbe determination of the overall effect of fusel oil extractions on the pour point of the
oil. Undoubtedly, precipitation of the heavy oil fractions also occurred,
which is frequently observed with other solvents of the similar type.
100
90
I.(
80
70
(J
.....
'"
60
.50
4..t
40
"'<::l
30
f2
20
Jo
~o
-~ ~ ~ ",-
1\- \:
--~ --\
- '\
..0
o~
-~o ~
~~ '-"- __
I- ~
'\
~o
1.-0
~
~ __ -r1.0
~\
- -~I
--t-
_..),.,
0
--:c"
0
__ ~-s:,..--
~
\1
?,~\ 2,:\
I
TO 01L- RAT!
SOLV Er41
1
-/0
/00
~o
-- r\- ~ '\1\
t.w
ac:
10
....".- -~ r;-
90
YIELD -
80
70
7a
BY VOLUME
60
50
FIGURE
It can be noted from the data plotted on Figure 5 tbat the pour test
of the dewaxed oil is generally equal to but usually lower than the chilling
temperature, which is particularly noticeable in dewaxing the oil to higher
pour tests. This negative differential decreases as the quantity of fuse!
oil llsed is increased. The high solvent ratios lllust be employed, however, in order to improve the yield of the dewaxed oil. The data are
characteristics of alcohols in general and of the variolls types of oils to be
68
A very large variety of other organic solvents which mayor may 110t
have more or less pronounced solvent refining and cleasphalting characteristics has been proposed for cIewaxing purposes alone or in combination with other modifying solvents. The work of Poole llU has been
particularly extensive in this connection and indicated that, besides
butanol and Pentasol, butyl formate and paraldehyde are particularly
TABLE 14-Solvent Dewaxing Plants in Operation
Cit'
DudeI' Construction
(Db18/Day)
J,ocation
Cnlllpany
1,850
750
1,600
l,OOO
500
500
3,800
1,170
1,700
2,500
500
1,000
1,500
3,000
21,370-67.2%
T/Il~
Propane Process
Standard Oil Co. Indiana ........... Wood River, Ill.
Union Oil Co ...................... Olcu111, California
Shell PetroleUIll Co ................. Wood River, Ill.
BraMon1 Penn. Refilling Co ......... \Val'ren, Pa.
Kendall Refining" Co ................ Bradford, Fa.
1,300
2,000
2,400
250
1,200
7,150-22.4%
2,000
500
2,500-7.80/0
850-2.6%
Total
31.870-100%
69
I,atz, E., PrzcmysZ CIw",., 18, 408-19 (1934); Diggs, S. H., and Page, J. M., Jr, U. S.
Patent 2,063,369 (Dec. 8, 1936); Dearborn, R. J., and Gee, W. P., U. S. Patent 2,074,254
(Mar. 16, 1937).
2. Poole, J. W., Oil Gas J., 28, No. 19, 99, 185-6 (1929), and Gee, W. P., Kicrsted, W., and
McCarty, n. Y., Refill"r Natural Gasolille Mfr., 15, 205-9 (1936).
2a. Francis, C. 1(" Oil Gas J., 34, No. 31, 64 (1935}.
210. Francis, C. Ie, Oil Gas J., 34, No. 34, 41 (1936).
2e. Francis, C. Ie, Oil GllS J., 34, No. 35, 46 (1936).
2d. Francis, C. 1(" Oil Gas J., 34, No. 36, 46 (1936).
20. Francis, C. K, Oil Gas J., 34, No. 37, 71 (1936).
2f. Francis, C. K, Oil Gas J., 34, No. 38. 42 (1936).
2g. han cis, C. K.. Oil Gas J., 34, No. 39, 45 (1936).
211. l'rancis, C. K., Oil Gas J., 34, No. 4G, 47 (1936).
21. Francis, C. K., Oil Gas .T., 34, No. 41, 47 (1936).
2j. Francis, C. K., Oil Gas J., 34, No. 42, 54 (1936).
2k. Francis, C. K., Oil Gas J., 34, No. 43, 56 (1936).
3. Carlisle, P. J., and Levine, A. A., Ind. Eng. Clre",., 24, 384-7 (1932).
4. Foole, J. W., Murray, W. C., and Wilson, R. M., Inri. Eng. Chem., 23, 176-7 (1931).
5. Poole, J. W., and Collaborators, Ind. Eng. Chell'" 21, 10981102 (l9Z9) , 23, 170-7 (1931), 24,
12158 (1932); Oil Gas J., 28, No. 19, 185-6 (1929).
6. Henderson, L. M., and Ferris, S. W., Ind. Ellg. Chew., 19, 262-4 (1927).
7. Wyant, L. D., and Mar"h, L. G., U. S. Bur. Mines, Tech. raj,er, 368 (1925).
8. Vclikovskii, A.. S., and Zuikov, B. Y., Nettyano" Klwzvuisl'Vo, 24, 123-8 (1933).
9. Ba Tbi, M., Strang, L. C., Hunter, T. G., and Nash, A. W., J. 11"1. Petrolelt'" Tech., 23,
2'26-52 (1937).
10. Smoley, E. R., and Kraft, W. W., Ind. Enl/. Chem . 'Xf. 1418-22 (1935).
11. Smoley, E. R., and Kraft, W. W., Refiner Natural Gasoline Mfr .. 15, 33-7 (19.16).
12. Myel'S, W. A., U. S. Patent 2,070,611 (Feb. 16, 1937).
13. Lewis, W. K, U. S. Patent 1,911,832 (May 30, 1933).
14. Lummus, W. E., U. S. Patent 1,603,851 (Oct. 19, 1925).
15. Stines, D. E., U. S. Patent 2,006.186 (June 25, 1935).
16. Sachanen, A. N., Petrolellm Z., 21, 735-40 (1925).
17. Weber, P.; and Dunlap, H. L .. hd. Eng. CTtelll., 20, 383-4 (1928). See also Sullivan, F. W.,
Jr., McGill, W. J., and Freneh. A., lutZ. Eng, Clt,m., 19, 1042-5 (1927); Pruitt, H.,
Refiner Nat1tral Gasoline Mfr., 10, No.6, 75 (1931); etc.
18. Ba11Ikc, W. R., Giles, R. N., ~nd Adams, C. E., Refiner Natural Casoli"" Mfr., 12, 229-34
(1933).
19. Sage, B. H., Sherborne, J. E . and Lacey, W. N., Ind. Eng. Chem., 'Xf, 9546 (1935).
20. Towne, C. C., U. S. Patent 2,064,506 (Dec. IS, 1936).
21. Bray, U. B., Swift, C. E., and Carr, D. E., on Gas J . 32, No. 24, 146, 20-2, (1933);
and Refiner Nat1<ral Gasoline Mfr., 13, 3336, 3539 (1934).
70
22.
ons
Adams,~. E., U. S. IJatent 1,IJ)H J 747 (Apr. 23-, 1935); Ad,tn1:;, C. E.., an.d Rchci_ncn\~u', F. W.,
U. S. Patml 2,038,624 (AI"" 28, 1936), and Canadian l'alent 348,34Y (Feb. 19, 1935);
Aka l'ro<lucts Inc., Hrili"ll Patent 123,:l03 (l,w. 23, 19,15), French Patent 758,853
(fan. 24, 19.14), French Patent 79(),634 (Nov, 25. 19:15), and French Patent 790,786 (Nov.
27, 19,15); Aldridge, B. G" U. S. P"tcnt 1,988,768 (J,m, 22, 1935); Aldridge, B. G., and
Hopper, B., U, S. I'atent 1,1)88,767 (Jan. 22, 1935); Atwell, H. V" U. S. Patent 1,976,535
(Oct. 9, 1934), u. S. Patent 2.006,011 (June 25, 1935), and British Patent :190,222 (Apr. G,
1933): B'lllks, D. B., a!HI Harton, 1'. D., Canadian Patent 360,{j(j8 (Sept. ~'" 1936), and
British Patent 458,1;70 (Dcc. 18, 1936); Hr<LY, U. n., u. S. Patent 2,048,244 (July 21,
1936); Brown, B. K., U. S. Patent 2,005,988 (June 25, 1935): Forrest, H. 0., U. S.
Patent 2,076,141 (Apr. 6, 19.17): liard, E. W., U. S. I'alcllt 1,989,355 (Jan. 29, 1935):
Giles, R. N., U. S. Po.tent 1.943,236 LLm. 9, 1934), lJ. S. \'atent 1,977,()54 (Oct. 16, 1934),
Canadian Patent :156,955 (Mar. 31, 1'1:16), anr\ Cana(lian 1'"tont 357,2()9 (Apr. 14, 19.16);
Hopper, H., U. S. Piltont 2,031,107 (Fell. 18, 19,6): .Tohnsrlll, .T. Y., British I'a~e:nt
411,86(, (June 1.1, 1934): Mr.(;ill, W. [., U. S. P"lent 2,069,170 (Jan. 21i, 1937); Me('lll,
W . .T., ane\ Adrl1\\s, C. E., U. S. rrrtent 1,977,055 (Oct. 16, 1(34); M,mlty, R .. K,
U. S. Patent 2,067,]28 (Jan. 5. 19.17), anri U. S. Patent 2,067,19R OrIn. 12, 1937); Mer.
rill, D. R., U. S. Palent 2,031,118 (Feb. 18, 1936), 'LI1rl 1I. S. Patent 2,060,517 (Nov. 10,
19.16): Merrill. U. R., and Sullk"w, P .. U. S. Patent 2,031,117 (Feb. 18, 1936); Petty, E.,
U. S. Patents 1.940.D14-r, (Dec. 19, 19,10), and U. S. Patent 2,007,546 (July 9, 1935);
Pelty, E., and Finstel'lmsch, K, U. S. Patent 2,079,182 (May 4, 19,17): Roberts, J. K.,
and Carpenter, M. T., U. S. Patenl 2.077,712 (Apr. 20, 1937): Stanrlard Oil Co., French
Patent 739,264 (June 29, 1932), ilnd British l'atcnt 409,110 (Apr. 2(', 1934); Swill. C. E.,
U. S. Patent 1,988,706 (Jan. 22, 1935); Voorhees, V., U. S. Patent 1,862,874 (June 14,
1932); Voorhees, V.. and Andel'soH, J. A. A., U. S. l'alent 1,980,649 (Nov. 131 1934);
Wilson, R. E., U. S. Palent 2,fJ2(',:U6 (Dcc. 31, 19.15): U. S. Patent 2,077,656 (lrp!'. 20,
1937), ,mil Cl1la(lian Patent 343,452 (July 24, 1934). The l"st pate.nt refers particularly
to the usc of hutane. Tears, C. r., u. S. Patent 2.000,427 (M"y 7, 19.15), applies propa.ne for cxtri1ctin~ oil frnm petmlatllms and producing high melting point waXC}l.
Leslie, R. '1'.,
Stand",.,ls J. Research, 10, (J09-1S (1933) developed a method for pll1'ifying hydroc:u'bons of the paraffin type by crystrtilization from liquid mt~lhall~,
23. Cox, E, B., Oil Gas .T., 33, No. 3:l, 16 (1935).
24. Lacey, W. N., and Sage, H. B., Oil Cas .T., .13, No. 39, 4952 (1935).
25. Vor)lhee.~, V., Canadian Patent 34.1.449 (July 24, 1934),
n.,.,.,
2li.
27,
28.
29.
.r'.
(19J6): Dahlke, \V, H., Giles, R. N., nnrI Ada.ms, C. E., R(l/i1U~r Natural Gasoliue Mfr.,
12, 229-34 (1933); Wilson, .R. E., and Keith, P. C. Jr., 1'1'01:. 1111. l'e/rDleltill 11<"'., 15,
III, 106 (19.14): Bown, Eo E., Oil Cas .T., 35, No. 4.1, 107 (1937); Conine, R. C" Oil
Gal .r., 33, No. 31, 17. 33 (1934); and Anderson, A. 1'., alld Talley, S. R., Am. C1U'.nl.
Soc. ,Directing Sept. 7-11. 19~1i, Petroleum Division,
Anderson. A. P. t and Talley, S. K., Iud. EH{/. Chrm' 29, 4~2-9 (1937).
Horlus, L. W. Oil Gas .T., 32, No. 45, 42 (1934).
Anderson, .T., U. S. Prltcnt 1,907,70:, (M"y 9, 19J3); Hry,ult, G. R., and Govers, F. X.,
U. S. Palent 1,969,201 (Aug. 7, 19M); Gee, \'1'. P., CrLlmdian P,llcl1t 357,477 (Apr. 28,
19,16): r:overs, F. X .. U. S. Patent 1,802,9'12 (Apr. 28, 1931), U. S. Patent 1.920,125
(July 25, 19.13), U. S. Patent 1,945,350 (Jan. 30, 1934),
S. Patent 1,964,985 (July
3, 1(34), u. S. Patent 2,fJ03,664 (June 4, 1935), u, S. Patent 2,041,677 (May 19, 1936),
n, S. Patent 2,054,416 (Sept. 15, 19,16) and Canadian Patent 355,522 (Jan. 21, 1936):
India" Refining Co., B,.itiRh Patent 345,632 (Oct. 18. 192R) , German Patent 600,GI9
(Sept. 25, 1929), }'rench Palent 734,254 (Mill.. 26, 1932), French Patent 734,797 (Apr.
6, 1932), French Patent 741,633 (Aug. 30, 1932), and French Patent 44,791 (Allr. ("
1935), which is an adclition to French Patent 682,330; IGscr, M., U. S. 1'"to11t
2.020,066 (Nov. 5, 1(35); L"np;worth, M. L., U. S. Patent 1,956,036 (April 24, 19.14):
and Can~(li"n l'atent 334,198 (July 18, 1933): 1\I.mley, R. E., U. S. I'alent 1,980,n71
(Nov, 0, 19.14); N. V. de Hat",,[sdle Pelroleum MaatRchappij, French Patent 805,512
(Nov. 21, 19361; Texas Cll., French Prrlcnt 734,403 (March 3() ln2)' etc,
Wiles, E. R .. U. S. Patent 1,684,42(, Ukpt. 1R, I92R).
"
Brrll, F. W., and McCarty, B. Y., "World Petroleum Con~re"," Paris, (1937);
Petroleu", Ncmr, July 14, 1937, R-15.
Govers, F. X., U. S. 1'.. tont 2,Olil,541 (Nrll'. 17, 19,10), ,,1111 Canndian Patent 3.14,130 (Nov.
12, 19;15).
Wagner, C. R., U. S. PiLtent 1,1i09,151 (1\",v R. 1928).
Gross, II. II., and Ohcl'haugh, W. V., ll. S. Patent 2,047,412 (.July 14, 19.16).
Gross, H. E., nnrl Oberliuugh, W. V., Canadian I'atcnt :lfiO.5fi7 (Sept. IS, 19.16).
Gross, II, II., and O"c1'''01ullh, W. V., Ilritbh Pillellt 445,172 (Apr. 3, 193(,).
Texaco Development Corp, French PaWnt 790,HJ8 (Mllr. ,11, 19,16).
.
I\elln),;g, C. :M., U. S. Patent 2,047,R2fi (.111ly J.I, 193(,).
McCnrty, 11. Y., and Skelton, W. E" U. S. Patent 2,024,107 (Dcc. 10, 1935).
van del' Wllen!cn, H., Canadim I'(I\ent 357,974 (May 19, 19.1ti).
N, V. de Bat(Lafscl1e Petroleum MnatsehaPl?,ij, British Patent 430,485 (June 19. 193,,),
N. V. de J3ataafsche petroleum MaatschaPPl], German P<Ltent 643,277 (AIl!', 2, 19.17).
Texaco Development r.orp., French Patenl 780,468 (Apr. 2(>, 1935).
Pcvcrc, E. F., Can adinn I\Ltcnt JSJ,fi95 (Od. 22, 19.1.,),
Knowles, E, C., U. S. Palent 2,054,429 (Sept.
1936).
Govers, F. X., U. S. Patent 2,060,80., (Nov. 17, 193(,).
Govers, 1", X., and Bryant, G. R., Refiller Nat1tral GasoUllC Mfr., 12, 222-8 (1933):
[;oc, W. 1'., KiersterJ, W., and Mr:Carty, B. Y., Oil Gas J., 35, No.1, 50,
57 (1936), Refiller Nlttural Gasoli"" Mfr., 15, 205-9 (1936), and Nail. 1"'frol"1I/II News,
j
u.
.10.
.11.
,12.
33.
34.
.15.
30.
37.
3R.
39.
40.
,11
42.
43.
44.
45.
40.
47.
N"a.
1.'.
SOLVENT DEWAXING
71
28, No. 20, 29-33 (1936); ~I"crs, W. A. Oil Gas J . 33, No. 45. 78. SU (1935); Weber,
G. Oil Gas J . 35, No.9, 46-8 (1936).
Tannc, J., and OberlandCl'. G., British r"tcnt 1.688 (Oct. 27, 1909).
19. rannc, J., lIud Oberlander, (;') German Patent 2J8,..J89 (1911).
50. Tanne. J., and Obel'londcr. G . British Palent 23.125 (Oct. 6. 1910).
51. Tanne. J . and OberHindcr, G. German Patents 236.05U-1 (Oct. 8, 1909).
52. Lederer, E. R, and ilcilttie. R., Natl. Petr%w" News. 21, No. 50, 79-84 (1929).
53. Backlund. N. 0 . U. S. Patenl 1.676,069 (July 3. 1928).
54. Akt!ebolaget Separator-Nobel, French Patent 637,229 (July 8, 1927).
55. AktlebQlaget Separator-Nobel. British Patent 376.658 (Aug. 13, 1937).
56. Bergedorfer Eisenwerk A.-G . German Patent 535.274 (Jan. 7, 1932).
57. Bergedorfer Eisenwerk A.-G . French Patent 632.602 (Apr. 11. 1927).
58, Bergedorfer Eisenwerk A.-G., British Patent 267,038 (Aug. 16. 1926).
59 Carlisle, p. J., and Levine, A. A. Iitd. E1l~. Chew., 24, 384-7 (1932).
60. Carlisle, P. J., U. S. Patent 1.978.0lD (Oct. 23. 19.14).
61. Carlisle, p. J., Canadian Patent 338.604 (Jan. 16. 1934).
62. Edeleanu Ges . British Paten! 373.538 (May 26. 1932).
63. Edeleanu Gcs., Oerlllll11 l)at~nt 573,210 (Nov. 5, 19.')0).
64. Jones. L. D., U. S. Patent 1,930,179 (Oct, 17, 1933).
65. Atwell, H. V., U. S, Patent 2,006,010 (JlIne 25. 1935).
66, Ramser, H., U. S. l'atent 2.009,454 (July 30. 1935)_
67. Sharples Specialty Co . French Patent 788.328 (Oct. 8. 1935).
68. Jones, L, D . n, S. I'atcnt 2,OSJ.337 (Sept. 8. 1936).
69. Jones, L. D., British Patent 445.908 (Apr. 21. 1936).
70. Standard Oil Development Co . French Patent 790.852 (Nov. 28. 1935).
71. Standard Oil Development Co., BriU;;h Patent 454.176 (Sept. 25. 1936). and French Pa.tent
790,853 (Nov. 28. 19.15).
72. Jones, L, D., U. S, Patent 2,067.193 (Jan. 12. 1937).
73. Jones, L. D., British Patent 447,415 (May 18, 19.16).
74, McCarty, B. Y., and Skelton, W. E., U. S. P;ltent 2.0.15,490 (Mar. 31. 1936).
75. McCarty, B. Y . and Skelton. W. K, U. S. Piltent 2,0,15.191 (Mar. 31. 1936).
76. Voorhees, V., U. S. Patent 1.956,780 (l1"y 1. 19:14).
77. Livingstone, C. J.t U. S. ratcnt 1,B4R,(i3(j (Hal'. S. 1932),
78, Livingstone, C. J., TIritish Patent :170.325 (Apr. 7. 19:12).
79. McC,rty, B. Y . and Skelton. W. 1':.. U. S. P,ten! 1.998.398 (Apr. 16. 19.15).
80. Tanne. J., and Oberlttnder. G . British l'a!ent 1.664 (Jan. 20. 1912.)
B1. McCarty. B. Y. and Skelton, W. E . U. S. Patent 1.995,15.1 (Mar. 19. 1935).
82. McCarty, B. Y . and Skeltou. W. E., U. S. Patent 1.969.670 (Aug. 7. 1934).
83. McCarty. B. Y., and Skelton. W. E., U. S. Patent 1,998.397 (Apr. 16. 1935).
R4. McCarty. n. Y . and Skelton. W. E . n. S. Patent 2,027.346 (J"n. 7, 1936).
85. I. G., Farbenilldustrie A.-G . French Patent n7,256 (May 18. 1932).
86. Bray. n. B . U. S. P"tents 2.ml,095-6 (Feb. 18, 1936).
87. Sharples Specialty Co . French Patent 784.813 (July 25. 19.15).
SR. Stand"rd Oil De\'elopment Co., French Patent 7R~.570 (July 22, 19:15).
89. Akticbolaget Sep:trator-Nobel. }'rench Patent 762.949 (Apr. 20. 1934).
90. Jones. L. D., U. S. Pretent 1.930.479 (Oct. 17. 1933).
9!. N. V. (Ie 13alaai,d1e l'etroleum Maatschappii. Frel\ch Patent 801,930 (.\ug. 31. 1936).
()2, Sharples Specialty Co., French Patent 801,583 (Aug. 7. 1936).
93. Govers, F. X., U. S. Patent 2,067.050 (J,n. 5. 1937).
94. Wiles, E. R.. U. S. Patent 2.078.186 (Apr. 20. 1937).
95. Aktiebolaget Separator Co . German Patent (,11,703 (Apr. 16. 1933).
9fi. ('arlisle, P . .T . and Levine. A. A. Ind. F,ng. Clum .. 24. 1164-8 (19.12).
97. Backlund. N. 0 .. I. lnst. Petrolc"m T,ch . 19. 1-34 (1933). and Refi,wr Natural (;rtsolillr
]lffr .. 12, 5 (1933): Pester. C. F . Oil (;as J . 32, No. 1. 52 (1933). and Refiner Natll,,"l
Gasoline Mfr.. 12, 235-7 (1933); Anon.. Refinpr Natllral Gasolin" Mfr., 14, 147-51
(1935). and Clum. Met. E1Iv .. 27, No. 15. 751 (1932).
98. Albright, J. C.. RefillPr Nat1/.rnl (;(l.,o/inp Mfr., 15, 287-92 (1936).
99. Goldberg, D.. Abezgau7,. J . and Margolis, L . Azerbair/zhanslwp. Nrtiyanoe K),n,yaistvl>,
1935, No.3. 74-81.
100. Standard Oil Co. Df Ohio. French 1'ntent 776.76(, (Feb. 4. 1935); 'Edelennu <10 . m.b.H ..
British Patent 432.168 (July 22, 1935), nnd French Patent 784,596 (july 22. 1935).
recommends besides henzol other secondary ",Ivents such as ethyl ether, chloroform.
etc. Gover., F. X., U. S. Patent 2,044.722, and U. S. Patent 2.044.726 (June 16. 1936);
,ee also Hjerpe. E. B . and (lruse, W. A.. U. S. Patent 2.054.750 (Sept. 15. 1936).
101. S ..haa[sma ...... and Versteeg .T. M .. Canadian Patent 359.459 Ouly 28. 1936).
102. ]\fanley, R. E .. n. S. Patent 2.054.433 (Sept. 15. 1936).
10.1. Govers. F. X . U. S. Patent 2.044.721 (,Tunc 16. 1936). and U. S. Patent 2.044,7~1 (June 1(,.
48.
104
lOS.
106.
107.
lOR.
109.
110.
111.
112.
113.
114.
11';.
19.16).
Govers, F. X .. U. S. Patent 1.995.147 (Mar, 19. 1935). U. S. Patcnt 2.!l44,723 (June 10,
1936). and U. S. Patent 2.044,725 (.Tune 16. 1936).
Tilmstra. S . and Mc1(ittrick. D. S .. ('anadian Patent 360.666 (Sept. 22. 1936).
N. V. de Bataafschr Petroleum Maat,rhanpij. French Patent 781.25R (May 11, 1935).
Stamlard Oil Development Co., French P"tent 791.257 (Dec. 6. 1935).
N. V. de Balaafsche Petroleum Maatsdmppij. French Patent 798,061 (May R, 193(,).
Gover F. X . 11. S. Patent 2.041.077 (May 19. 193(,).
Poole. J. W .. anrl Collaborators, [jut. En!!. Clip", .. 21, 109R-II02 (1929): 23, 170-7 (19.11);
24. 1215-8 (1932).
r. G. Fnrbellindustrie A-G . Fr.n ..h Patent 712.06S (Feb. 25. 1931).
Smith, H. M . Oil Gas J., 26, No. 17. 146 (1927).
Govers. F. X .. U. S. Patent 2.049.060 (July 2R, 1936).
Lane. R. S .. U. S. Patent 1,706.120 (Mar. 19. 1929).
Govers. F. X . U. S. Patent 2,060.805 (Nov. 17. 1936).
72
116. Poole,
117.
118.
119,
120.
121.
122.
12.1.
Chapter VI
Removal of Oil from PetroleU111 Waxes
Waxes removed 1'0111 petroleum oils by the methods described in
the preceding chapters always contain more or less oil which must be
separated fro111 the wax before it is placed on the market.*
This problem is in some respects different from that encountered in
the dewaxing of petroleum oils as the quantity of oil present in the wax
is relatively small. For this reason, the methods employed in deoiling
waxes and in dew axing oils are not nccessarily alike.
73
74
arc first filled with water to a depth just sufficient to cover the screen
and the hot wax is then pumped into the pans until the desired thickness
of the wax layer is obtained. The hot liquid wax is solidified by pumping
cold water throllgh the coils, the rate of chilling having, apparently, no
effect on the sweating properties of the wax. After a solid cake is
obtained the water is drained frol11 the bottom of the pans and the temperature of the cake now supported by the screen, is then gradually raised
either by circulating warm water through the coils or by heating the
chamber or "ovcn" wherc the 1)3.115 are located with spedal steam coils
outside of the pans. The rate of heating the wax cake is highly important
in order to obtain the cleanest possible separation of oil from the wax.
This is illustrated by the following clata obtained in laboratory experiments using a Mid-Continent slack wax of 112 0 F. melting point, and a
3270 oil COi1tent. In commercial practice the usual rate of heating the
wax cake is approximately 10 F. per hour.
TABLE
kate of Heating
o
F./Hr.
2.5
10
2.5
10
0/0 Wt.
Melting Point
F.
20
20
20
20
129.0
128.4
127.7
12(i.8
0.39
0.63
1.00
15
19
128.0
128.0
128.0
128.0
0.10
0.38
0.80
1.80
Yield
22
25
%Wt.
0.15
The drippings from the pallS arc usually colle.cted in two separate
fractions: the first fraction consisting primarily of oil and low melting'
point waxes known as "foots oil" and the second fraction or the "intermediate el1t" being a mixture of relatively small quantities of oil, large
quantities of low melting point waxes, and some of the high melting
point waxes. The wax remaining on the pans or "seaJe wax" is then
removed by melting it by circulating hot water through the coils. This
wax is then refined in the I1sual manner by percolating or contacting with
clay with or without prior refining with sulfuric acid, sodium hydroxide,
or other refinery reagents.
The wax strllcture is of considerable imporlance in successful operalion of the sweating' processes. As already mentioIled in the previuus
chapters best results are always obtained with the needle crystals which
permit an easy removal of the melted portions from the main hody of the
crystals by clraining. For this reason, inspection of the slack wax cake
permits one to draw definite conclusions with respect to the ease with
which it can be sweatecl.
Although the process is very inefficient, the quantity of the recoverable
products can be greatly increased by introducing suitable recycling opera-
75
tions. The intermediate cut is usually blended with the fresh charge of
the slacle wax in order to increase the recovery, or a highly complicated
system of recycling may be employed if the refinery is interested in
obtaining a variety of waxes of different melting points.
This conventional method of separating oil fr0111 the paraffin wax
remained practically unaltered for a number of years with the exception
of certain mechanical improvements in the sweating equipment. Recently,
however, suggestions have been made to modify the process by satm'atinothe wax cake with various solvents such as chlorex,2 solvents rich i~
aromatics,~ etc., in order to facilitate the ease of separating the oil fro111
the wax. In applying such processes, however, a careful economical
balance should be made in order to determine whether the cost involved
in separating the solvent from the resulting products and the inevitable
solvent losses are counterbalanced by the adclitional recoveries ot the
sweated products,
Solvent Pressing
From the above it follows that the separation of oil and low melting
point waxes from the high melting point waxes is accomplished by fractional melting, a process which is known to be theoretically inefficient,
For this reason, other processes were recently proposed vvhich involve
the principle of fractional crystallization. These processes involve the
L1se of solvents such as naphtha, benzol-acetone, etc., which were mentioned in connection with the dewaxing of petroleum oils. The wax is
dissolved in the solvent at a somewhat elevated temperature, the mixture
is chilled and the solvent with the dissolved oil is separated frol11 the
crystallized wax by pressing. The quantity of solvent used usually varies
from !- to 1!- by volume of the slack wax and pressures employed for
separating the solidified wax from the solvent-oil solution may be as high
as 300 lbs. per sq, in. or lllore,*
The fractional crystallization processes were employed by the petroleum industry at an early date. The crude paraffin was mixed in the molten state with light
petroleum fractions, allowed to solidify, cut into sheets and pressed to remove the
solvent and the oil. See Pyhae1ae."
It has been abandoned, however, at this time due to its expensiveness.
76
39%. This high recovery could 110t be reached by sweating even 011
repeated recycling operations.
In separating oil from the wax by solvcnt pressing the quantity of
solvent required depcnds on the quantity of oil present in the wax and
the conditions of pressing. Irrespective of the thoroughness of the
pressing oper:J.tion, a certain quantity of solvent is always retained by
the wax cake and after distilling it fro111 the wax the proportionate quantity of the oil dissolved by this solvent will be left in the wax, For this
reason, the adjustment of the actual conditions of pressing with respect
to the quantity of solvent required should be studied ill each individual
case as it depends on the nature of the prcssing equipmcnt 11scd and the
specifications for the finished product.
The pressing' temperature determines the melting point of tht:
recoveree! wax. It is, therefore, also adjusted according to the refinery
requirements. Recycling is employed to a more or less considerable
extent in order to obtain waxes of different melting points or to increase
slightly the yields which may become of some significance whcn the ratios
of naphtha to slack wax are u1ll1sl1ally high.
Considering the commercial applicability of the pressing operations
it should be noted, however, that waxes froll! different crudes differ in
their pressing qualities. SOl11e of them may form slimy cakes which are
difficult or even impossible to press. It should be also noted that the
necessity of ttsing' solvents increases the operating costs and, for these
reasons, a careful investigation is always required before the method of
deoiling paraffin waxes is finally adopted for plant usc.
A few other methuds have been recoll1mended for separating oil and
various melting point waxes into fractions such as contacting the crude
slack wax with a moving stream of alkali phoSllhate,H treating the wax
with water containing a wetting agent of the type of an aromatic sulfonic
acid,7 etc" but these methods up to the present time are of little commercial significance.
.J
-'"
II}
77
c
o
-.;-
'",
,f1 I - I~
'0
~I~
iJ~""
I--
'<:It ....
.~
l-
1\.
1\.
I'
I--
t...:
Q
~
~
..,
~~ If).... I--
''0 ~
t-. I.!l
N"t
j:::
I-~
~\
(;I
\f)
~
~
I-Q~ -.
<:''''t
..J
....
0
...
~
\II
:..c '...."
I--
~
a... ~
f--
~\
oSj;
I~
,,~
\.)
_,
t-..!
", ~\
..sJ
I-
I<)
~t----.
~
l-
~.
" i'\
o:r:
-.
r-...
.\
~ ........
~
';
.'"" ,
D~
~ ~\
\~\
D~
....o
'tO~ -:;\
\0\
!-
I-
:t-
"doLL Ltl
o
~N
NOlltl~lJNJr;J
78
Bibliography
1. Lee, 1<., and NiCholls, E. S., "World Petroleum Congress," P"ris (1937); Belt,. H. S.,
U American
Petroleum Heflning, n D. Van Nostrand Co" Inc., New York; .t'yhaclae,
E., Petroleum Z., 26, :No, 4, 115121 (1930), and Rellner Nat,el'fll Gasoline Mfr., 9,
No.9, 928 (1930); Hausman, J., Oele, Fette, Wadtse, 1936, No.4, 91-114, and lIe/incr
79
4.
5.
6.
7.
S.
Natura! Gasoline Mfr., 15, 6872 (1936); Allan, II. L., J. 1"sl. P,troi<-"", Tech., 17,
657-77 (1931). Espach, R. II., U. S. nt.... .1illC', !lllll., 388, (19.15), gives a very
complete. dcscliptioll of the wax relining and testing methods, wllilc Higgs, P. G.,
1. Inst. Petrolc"", Tech., 21, 1-14 (1935). discusses the utilization of paraffin wax
and ceresins by the various indw~tries. Fan, \V. D., and Samuel, F. E., V. S. Patent
2,062,356 (Dec. 1, 1936), propel partially molten wax by a screw conveyor and discl"tal'f~e into a screen.
Page,.T. M., Jr., U. S. Patent 2,048.513 (July 21, 1936).
Gentil, A. J., British Patent .181,308 (Oct. 6, 1932). Fussteig, R . Petroll'JlII, Eng., 8, No.
3, 90-4 (1936).
pyhaelae, E., Ref"'"' Natural Gasoline Mlr., 9, No.9, 92-4, 98 (1930).
Hausmann, .T., Prze1ll),sl Chew., 18, 401-8 (193-j).
Hill, J. B., U. S. Patent 2,010,819 (Aug. 13, 1935).
Mueller-Cunradi, M., and Ottens, B., U. S. Patent 1,881,861 (Oct. 11, 1932).
Goldberg, D., and Abezgatlz, 1., Azerbairlzhallslwe Ncfty"uoe KllOzyaistvn, 1932, No, 11,
9.
Sachanen, A. N.,
2.
3.
39-45.
j'Ch~mical
CmnposHion of I\:tt'oleum,lI
Ru~sin.,
(1931).
Chapter VII
Asphaltic Substances
Asphaltic substances present in petroleum oils are generally considered as undesirable constituents because they have an unfavorable
effect on the carbon residue or coke number, and color of the oil. They
are likewise held responsible for carbonization and instability of oils in
service and, for these reasons, their removal from the oil is believed to
be desirable.
80
ASPHALTIC SUBSTANCES
81
82
in
ASPHALTIC SUBSTANCES
83
84
ASPHALTIC SUBSTANCES
85
two oils after solvellt refining. This can be, apparently, explained only
by the assumption that the heavy asphaltic particles present in the oil are
capable of associating with the asphaltic substances of lower molecular
weight forming new complexes which are relatively inert to the action of
refining solvents being of distinctly colloidal nature.
As already mentioned, the removal of asphaltic substances frolll
petroleum oils improves their carbon residue and color characteristics.
This docs not aSSllme, however, that all of the colored substances are of
asphaltic nature and that for this reason the oil can be decolorized merely
by removing the asphalt. It only implies that most of the asphaltic substances form colored solutions with the oil. For this reason, the improvement in the color of the oil in cleasphalting operations is an indication
but not necessarily a measure of the amount of asphaltic substances
removed.
Besides carbon residue and color characteristics, remuval of asphaltic
substances is reflected in the change of some of the other properties of
the oil. Viscosity is lowered considerably due to the removal of the
high molecular weight constituents. The viscosity index: of the oil may
remain unchanged but is frequently lowered.':'
The pour test may also be affected as shown in Chapter III. The
specific gravity of the oil is usually 100\-erecl while the viscosity-gravity
constant shows in general only minor variations, The flash and fire
points occasionally show a decrease.
* The reasons for lowering the viscosity index in the deasphalting operations
are explained in connection with the discussion of substances us!!d for improving
the viscosity index of oils.
Bibliography
1. Abrah,uIl, Ii., "Asphalts and Allied Substances/' D. Van Nostmnd Co., Inc" New York,
1929.
2. Sac11allcn, A. N., IIChelnical Composition of l).t!(r(lleum/~ (in l~ussian), 19.H.
3. :MarcllssollJ J'I BUl'l.:hartz, E., and Wilke J P., "Die naLiirliche und kiinstliche Asphalte,'f
\VHhchu Engelma.nn, Leipzig, Gennan)!, 1931.
4. Kalichevsky, V. A., and Fulton, S. C., Nail. Petrolelillt N"IVS, 23, No. 51, 33-6 (1931),
5. Jacobsen, Cllew. Tech. RCj}()rtcr, 2, 107 (lH69).
fl. Holde, Mittcil. aus der Kgl. Materialj,riif"',g.<flllt, 2, 261-2 (1893).
Richanlson, '(The :Modcrn Asphalt I'aVClllent," New York (1905).
S. IIIarcl1sson, J., C/W)). Zt,~., 37, 833 (1914); Z. altg"m CI,illt., 29, 346 (1916), 31, 113 (1918);
Pctro/e,"" Z., 12, 1149 (191i); "Asphalt' (1931).
..
9. Sachanen, A. N., FeUol""", Z., 21, 1441 (1925); SachanCll, A. N., and VasSlheff, N.,
Fetrolcu/I! Z., 23, 1618 (1927).
10. FIllton, S. C., and Kaliehevsky, V. A., U. S. Patent 2,006,199 (June 25, 1935).
11. Schneider and Just, Z. wiss. MUerosieop. 1905, 501.
12. Nellcl1steyn, F. J., 1. Inst. Pctrole"", Tech., 11, 346-8 (1925).
13. Zaharia, A., and Lucatu, E., Bull. Soc. Romania, 12, 90-4 (1930).
14. Fulton, S. C., and Kalichevslty, V. A., U. S. P,ttent 1,926,523 (Sept. 12, 1933).
15. Standard Oil De"e\opment Co., French Patent 800,144 (June 27, 1936).
I,
Chapter VIII
Conventional Deasphalting Methods
A llumber of commercial methods for removing the asphaltic subwere known by the petroleum industry before the appearance
of the solvent deasphalting methods which arc now gntdually being
adopted for processing the residual oils. Of these olcler methods distillation, refming with clay anel sl1lfuric acid, and treatment of oils with
varioLls precipitating agents are the 1110st important ones in connectioll
with the solvent refining operations and are, for this reason, briefly
described in this chapter.*
stanc~s
Deasphalting by Distillation
From the very beginning of petroleum refining it was known that
ltsphaltic substances can be separated from petroleum oils by distillation.
For this reason, distillation should be considered as the first deasphalting
process which was applied in practice. With the advent of solvent refining it has been also found that solvents are most effectively applied to
distillate and 110t to residual oils and, although the exact reasons for such
behavior of solvents may not have been dearly understood, the first solvent refining processes were confined only to the distillate stocks.
In deasphalting oils hy distillation, difficulties are encountered, however, in separating all of the oil from the asphalt as the heavy petroleum
fractions have a low volatility and, dtle to thermal decomposition, cannot
always be obtained as distillates, These distillation problems are of
relatively minor importance with the crudes of the Coastal type which
have a cOlllparatively low boiling point for a given viscosity, but they
become increasingly difficult with tbe oils of Mid-Continent type while
Pennsylvania oils cannot yet be satisfactorily distilled in commercial
equipment without substantial cracking. Considerable progress in the
distillation processes has been achieved, however, ill the course of the last
few years which opened the possibility of applying the distillation methods
for cleasphulting a number of crucle oils of comparatively low volatility.
The work along these lines is being continued by a llumber of industrial
concerns as distillation is a relatively inexpensive operation and can C0111pete successfully with the different physico-chemical deasphalting methods
which were recently developed for refining stich types of oils,
87
These processes are described in the "Composite Catalog of Oil Refinery lind
Natural Gasoline Plant Equipment.'"
88
89
be applied either by mixing the finely ground clay with the oil, heating
to elevated temperatu res, and filtering off the clay (contact method),
or by percolating the oil through a relatively long column of comparatively coarse clay at temperatures usually not exceeding 212 0 F. (percolation method) .*
Either of these two processes is satisiactory for refining solvent
treated oils to color specifications provided these oils were deasphalted
to a greater or less extent by a preliminary deasphalting operation. However, clue to the high cost of the clays used in contact operations their
application for reducing the carbon residue, i.e., the asphalt content, of
an oil is usually impractical. For this reason, the following discussion
is limited to percolation operations.t
The effect of percolation all reduction of carbon residue of lubricating
oils can be visualized from the following experimental data of Kauffman,l1
which were obtained by percolating a heavy lubricating oil in naphtha
solution. The tests refer to the different oil samples after naphtha was
removed by distillation.
TAllLE
Original stock
Stream
10.0
23.0
75.0
148.4
294.6
500.4
589.4
after
bbls.
bhls.
bbls.
bbls.
bhls.
bbls.
bbls.
yields of:
of oil
of oil
of oil
of oil
of oil
of oil
of oil
Sal'lioit
Universal Viscos-ity
210 0 F.
Carhon
U.e:-;irll1c
r;'h \VL.
156
2.25
87
95
125
135
140
140
140
0.027
0.115
O.S4Il
0.932
1.49
1.61
1.79
This shows that although the clay is quite effective in removing the
asphalt when the oil is percolated through very large quantities of clay,
it cannot be used economically for this purpose unless the conditions are
exceptional.:I:
In ordinary refinery practice the solvent refined oils are usually
finished by contacting or percolating through clay in order to insure <t
uniform product of desired specifications. 'When percolation is resorted
to, a small additional reduction in the carbon residue of the already
* For a.lllore complete discussion see Kalichevsky and Stagner.' On the use of
contact clays see also FUl1sten.
t Contacting solvent refilled oils with clays at elevated temperatures is specified
by Stratford and Moor," and Standard Oil Development Co." Distillation of such
oils in presence of clay is recommended by Starr and Edwards," and by Standard
Oil Development Co. 'O
:j: The Atlantic Refming Co., for instance, does llot employ a deasphalting operation in connection with their nitrobenzene process, but finishes the oils directly
with clay.
9()
Gravity,
011
10
25.7
()
AP.I.
24.5
Saybolt Universal Viscosity at 210 F.
143
Vi5cosity index
91
Color, Lovibond Ut tell)
>750
Carbon residue, % wt.
2.8
Q
Extracted Residuum
12H
92
>750
1.5
50
20
21i.4
111-\
27.4
107
95
94
325
104
0.5
0.9
Oil
Ex1ractcd Ilistillatp.
After 1'\11'[111'011
nefo""
Extractil)1\
Gravity, 0 A.P.I.
Saybolt Universal Viscosity at 21[)" F ..
Visr.ositv index
Cal'hon 'residue
21.7
in
('5
(1,73
A([('1'
2o.t
70
75
0.37
26.4
70
87
0.16
91
The effect of sulfuric acid is less pml101.111Ced with stocks, which wcre
very thoroughly deasphaltecl and SOlVCllt reilllCcl before the acid is applied.
This is shown by the follo\\'ing data obtained 011 rcii.ning a heavily DllOSol treated Mid-Continent residuum with v,Lrious quantities of 98~~
sulfuric acid, followed by clay neutralization.
19-Effect of Sulfuric Acid on Duo-Sol Treatecl Residuum
TAJJLE
28.8
]7.
G4.6
99
58
0.22
10
29.0
64.4
lOll
30
0.18
50
29.2
62.8
lOll
25
0.16
The data also show that besides irnproving the mrbon residue of an
oil, sulfuric acid refining has a bendicial effect 011 its colur and viscosity
index characteristics, although the actual necessity of applying the ariel
to solvent refined oils fro111 the viewpoint of the rehner can be determined
only after studying the incliviclmtl characteristics of the stocks processed
at the plant.*
Deasphalting with Metallic Chlorides
Asphaltic substances can be also removed fro111 petroleulll oils by a
variety of precipitating agents, such as metallic chlorides. Of these agents
aluminum chloride is the 1110St active one although ferrous and ferric
chlorides, mixtures of aluminum, calciulll or mercuric chloride,H zillc
chloride,15 finely divided metals in presence of chlorine,IO etc., have similar
effects. These substances are seldom allpliecl in commercial refi11ing dne
to the necessity of installing special equipment, their relative expensiveness, and the difficulties encountered in disposing of sludges resulting
fr0111 such operations. In exceptional instances, however, the solvent
refined oils may be refmecl to an advantage with aluminl1111 chloride
which is being done by at least one of the large petroleum companies
in preparing special grades of lubricating oil stocks.
* Mallley'~ specifies
Bibliography
1. l,,,lichevsky, v. 11.., and Stagner, B. A., "Chemical Refining of l'etrnICUln," The Chemic"l
Cu.talog Co., Inc. (Reinhold Publishing Corp.), New Ymk, 1933.
2. Ben H. S" "American Petroleum Refining," D. Van Nostrand Co., Inc., New York. 1930.
3. "Cofnposite Cat.alog of Oil Refinery and Natural Gasoline Plant Equipment," published by
92
7. Stratford) R. K., ;:meL 1\loor, II. n.) Calladhn Patent 35(1,176 (Fell, 25, l(_)J(i).
8. SI:uHl;tl'r] Oil Development Co., French Patent 7?1,(>~7 (Nov. 2;1, 19.14).
9. Starr, J. Y., and Edwards, D. F., U. S. Palent 2,028,361 (Jan. 21, 19;1(;).
10. Standard Oil Development Co., French I'lL!cn! 7:l7,83(i (MltY 30. 1932).
II. l(ltuffman, II. L., Reline, Nat"ra.! Gasoltlll! liffr., 7, No. ~, 76 (1928).
12. Manic)" R. E., 'McCarly,
Y., and Gross, H. II., Refiller Na.e",a/ i7(w>/illl! Mfr., 12,
420-31 (193.1).
13. Manley, R. E., U. S. Patent 2,038,79H (Apr. 2H, 19.16).
14. Pktet, A., and Lerzcynslm, 1., BIIII. Soc. C/dm., 19, 326-;H (191(,).
15. Randaccio, C" French Patent 670,366 (Feb. 27, 1929).
10. McAfee, A, 1\1" Canadian Patent 163,fJ92 (.func 8, 1915).
n.
Chapter IX
Deasphalting with Solvents
The modern methods for removing asphalt frol11 petroleum oils are
basecl on the ability of certain solvents to precipitate the asphaltic substances when such solvents are mixed with the asphalt bearing stocks.
The present commercial processes employ for this purpose propane and
related hydrocarbon substances. although aliphatic alcohols seem also
to present distinct commercial possibilities. These two types of solvents
are, therefore, discussed in this chapter. Besides the above solvents a
number of other solvents are known which are capable of precipitating
at least some of the asphalt. These solvents, however, which are usually
of oxygenated type, such as organic esters or ethers, are considerably
less effective than liquefied hydrocarbons or alcohols and are, for this
reason, of minor importance. Their detailed discussion is, therefore,
omitted in this book.
Deasphaltillg with Liquefied Hydrocarbons
The ability of light petroleum distillates to precipitate asphalt fro111
residual stocks has been discussed in Chapter VII, but s11ch distillates
do not give the sufficiently sharp separation between the oil and asphalt
which is desired in petroleum refining. However, studies along these
lines, extended to covel' the lighter 1l1embers of the hydrocarbon series,
such as propane. which can he liquefied at ordinary temperatures hy
applying pressure showed gre;lt promise. The use of these liquefied
hydrocarbons for precipitating asphalt from mineral oils had been patentee! by K. Kling of the Polish Institute for Chemical Research
"Metan" as early as 1920.1 He found that methane, ethane, propane
and butane might be employed advantageously for this purpose. This
is well illustrated by the experimental data of Bray, Swift and Carr,::!
which are presented in Figure 7. The data show that by employing
identical conditions of extraction the separation of asphaltic and high
molecular weight substances from petroleum oils pl'oceeds to a greater
extent as the molecular weight of the solvent becomes 1mver.
As already pointed out in Chapter VII, solvents which are used for
precipitating asphalt are also capable of precipitatit~g high molecular
weight hydrocarhons which may not necessarily be of UI1(lesirable
asphaltic nature. The use of lighter solvents tends to increase the
separation of stich high molecular weight substances 1'0111 the oil with
93
94
lLJ
z:
~I
Z
WI-
ll-
10
20 30 40
MOLECULAR WEIGHT
50
(;0
10
80
HYDROCA~50N
90
SOLVENT
7.---Ethct of .Mo\ccular Weight of Sat mated Hy{\rocarboll SolUlI VolUllIe PCI' Cent Asphalt Precipitated [rom TO[l[lt!ci POS!)
C"cck ResitlUlull (10 VOIUlll(!S Solvent at SO F.),
l"IGlIllE
vcnl
the resulting' decrease in the yield and viscosity of the recovered product.
Experimental work showed, however, that liquefIed propane is capable
of giving in this respect a better separation hetween the oily and asphaltic.
constituents of an oil than other similar substances, as the use of hydrocarbons lighter than propane results ill a considerable precjpitati~ll of
the heavy oil fractions, while the use of heiLVier hydrocarbons results in
an incomplete precipitation of the asphalt. For this reason propane has
heen chosen as the proper sCilvent for collllllcrcial lise ancI methods of
applying it to mineral oils werl~, therdore, patented hy a 11u111her uf
large petroleum cOl11panies including the Standard Oil Co. of Indiana,
Standard Oil Co, (If New Jersey, and tIle Unioll Oil CI), of California,:!
It is also possihle 10 use Twoper lllixtllfes uf liquefied hydrocarhuns
other than proP(~llC and to adjust them so as to ohtain the requit-cd de asphalting- properties. It is likewise possihle to use prOllane in 111ixtttres
95
2.0
40
PlR CENT
60
80
100
PNOPAN,
40
\ ~o
\ ~o I
PER
20
96
propyl we, iso-butane, iso-pentane, pClltylcnc, liexylcllc, cydohcxallc, 01' gases and
liquids, whieh are obtained by cracking, destructive hydrogenation or in debutallizing gasoline. Treatment may be done in presence of selective solvents such as
phenol, cresol, xylene, crcsylic acid, nitro-benzol, aniline, crotonaldchyde, levulinic
acid, pyridine, benzyl alcohol, nitro-toluene, furfural, or ethylene-glycol mono ethyl
ether. Bray and Swift," and Standard Oil Developlllent Co.," specify the mixture
of ethane and propane. Bray \I claims that by utilizing' a gaseous hydrocarbon solvent the major portion of which consists of hydrocarbons of kss than thn~.e carbnn
atoms per molecule, asphalt is separated which has a lowe1- carbenc wntent and a
highcr solubility in Jig'ht naphtha than an asphalt of the same melting point produced by distillation. N. V. Bataafsche Petroleu111 M.aatschappij H' divides mineral
nils into fractions of different moleeular weight by treatment in stages with
methane, ethane, propane, hutane, pentanc, ethylenc, acetylene, chloroethanc,
di-chlor-di-fluor methane, carbon dioxide, am11lonia, methyl ether, methyl-ethyl
ether or NH (CHn),. B ray" refines the oil with liquid ethane after a preliminary
treatment with liquid propane, Whitley and Beiswenger '" deasphalt mineral oils
with from 3 to 15 volumes of a liqucfied hydrocarbon mixture containing hydrocarbons with 1 to 5 carbon atoms; etc.
97
(1) The higher the temperature, the less is the solubility of oil in
propane,
(2) The more propane is added to an asphalt bearing oil, the less
asphalt is dissolved,
(3) Pressure has a large effect on solubility,
(4) Compressed propane gas will, at certain temperatmes, dissolve
more oil than liquid propane at slightly lower temperatures and pressures.
The above can be explained by assuming that two independent
phenomena take place when oil is mixed with propane: colloidal precipitation of asphalt particles and true solubility phenomena with respect to
the heavy petroleum constituents other than asphalt. The observation
that gaseous propane dissolves under certain conditions more oil than
liquid propane is in accordance with the principle of retrograde condensation. Within a certain temperature region increase in pressure
has a decided effect on the solubility relationships for complex mixtures
of liquids and gases. For a constant temperature and pressure below a
certain minimum the mixture is in a homogenous vapor state. Further
increase in pressure results in the separation of a liquid phase which is
richer in the high boiling constituents than the vapor phase co-existing
with it. As the pressure is increased the volume of the liquid or more
dense phase increases at first until it reaches a maximum then starts to
decrease, i.e., the Jiquid phase dissolves in the compressed vapor, until
it is completely dissolved and the mixture again becomes completely
homogenous. This behavior is, in all probability, characteristic of
propane-oil mixtures in the temperature region immediately above the
critical temperature of pure propane. It has been also previously
observed in the study of cracking phenomena by E. Peck of the Standard Oil Development Co.
An interesting diagral11!11atical representation of the behavior of
propane and mineral oil mixtures at different experimental conditions all
triangular diagrams has been made by Wilson, Keith, and Haylett,16 and
is shown in Figme 9. These "idealized" diagrams are used, however,
only in a qualitative way as, with the exception of propane, the two other
so-called fixed components, oil and asphalt, cannot be considered as pure
substances. For these reasons, the definition of oil and asphalt varies with
the experimental conditions, asphalt being considered those components
which are rejected from the propane solution, and oil, those constituents
which are soluble in propane under the given temperature and pressure
conditions. Therefore, the greater the quantity of the asphalt rejected,
the lower is the viscosity of the oil and its carbon residue, and the lower
is the "melting point" of the precipitated asphalt.
98
COMPOSITION
LINE
C/fJTICAL POINT
ISOTHERM
AT
/00 Q F.
CRITICIIL
POINT
COMPOSITION
LINE
nASPHALT
OIL
CHIT/CAL POINTS
OIL
A5PJlAL
99
Asphalt has strictly no melting point and the amount of heat necessary for its
liquefaction is dependent upon the consumption of heat caused by the specific heat
of asphalt."7, 1R For this reason, whenever the reference is made to the "melting
point" of asphalt it simply implies the reading'S of one of the several arbitrary tests
which are accepted for measuring this "pmperty" of asphalt, i.e., the temperature
at which the fluidity of asphalt falls beyond a certain minimuIl!.
St1ch contaminations can be reduced, however, to a reasonable minimum, provided the conditions employed for separating these substances
are strictly controlled. Similar conditions are encountered with other
c1easpbalting solvents, which are also capable of acting as dewaxing
agents.
In commercial installations, deasphalting with propane is accomplished by mixing residt1al oil with propane at a predetermined temperature and under pressure, settling the precipitated asphalt, and removing
it fr0111 the oil.
Attempts are being made to increase the settling rate and improve the separation of the asphalt hy passing the mixture through an electric field of high ten
sion,~ etc., but none of such accelerated methods are apparently in commercial use.
100
A"'ollOl
Etilyl* ................ 45
Butyl ................. 71
Amyl................. 77
Hexyl ................ 89
Octyl ................. 100
~.
Cal"llllll
R(.'~itluc
2.1
1.9
1.7
2.6
3.1
Say}>"I!: Universal
Viscosily at. 210 0 F.
54.1
85
87
97
100
This a1cuhol \~as ilppHed at 275 0 F., aS I at 35 F., it i1'j practically illll11isdIJlc with oil.
The data show that for a given oil yield the quantity of the asphalt
precipitated from the residuum, as indicated by the decrease in the carbon
residue of the extracted oil, reaches its maximUlll with hutyl and amyl
alcohols. The higher alcohols also possess, however, some deasphalting
properties, but the low temperatures reqnired for displaying' them are
such tbat the viscosity of the alcohol~oil mixtures is usually too high to
101
permit an effective separation of the precipitated fractions, unless filteraids and pressure filtration are resorted to,
Another modifying factor is the isomeric structure of the alcohols.
Thus, under similar treating conditions, refining of a residual oil fro111
German crude with 5 volumes of alcohols at 20 F., gave the results listed
in the following table.
TADLE
% Volume
Cal'lJOu
Residue
100
CH,-CH -CH,-CH,OB
CRn
I
CH,- CH,- CR -CI-LO H
Yield
Saybolt
Universal
Pont"
Seconds
.}'oint
210" F.
"F.
6.6
232
>100
73
2.9
101
15
67
2.7
97
10
89
4.3
136
30
CH,-CH,-CH,-CHOH -CH,
77
2.9
104
20
CH,-CH,-CHOH-CH,-CH,
82
3.1
109
20
Alcohol
CH,
I
CHn
I
CH,-CH,-COB
I
CR,
102
residue and 90 0 F. pour test, with anhydrous amyl alcohol, and with the
same alcohol containing SIX) water; S volumes of alcohol at 20 F. were
employed.
90
80
SOLVENT
AV
.,..
It.J
"..
y:_.l(
:::..
~
b'!l.
....j
40
30
[7 I~
~.lj V [7
-;IA~
10
20
--
_._
NOTE
FIGURES IN
CIIfCLES REFER TO
CARBON RESIDUES.
HI
D1
o
1---
So
bW :/['yV
~
.?i [7l7
G
60
(5
:::::.
~
:::..:
1-- ....
RATIO
~~
~
VA>~ k
20: I
1----
70
10 OIL
:10
40
50
60
70
--
80
Fll.iURE
The yields referred to ill the above tabJes and in Figure 10 were
obtained by single batch extractions. They can usually be increased by
employing multi-stage countercurrent ancI recycling operations, but only
under exceptionally favorable conditions can they be made equal to those
103
Anhydrous
A myI Alcohol
Yield, % volume
Pour, 'F.
Carbon residuc
Saybolt Universal Seconds 210' F.
Alcohol Containing
5 % \Vater
77
52
20
20
1.4
70
0.9
62
obtained with propane for an equal reduction in the carbon residue content
of the oil. In general, alcohols are applied with best results on oils
containing large proportions of hard asphalts which are removed with
relative ease, but they become progressively less effective dcasphalting
agents after the carbon residue of an oil is reduced below a certain
1111t11111Ul11.
Since no expensive high pressure installations are needed
and the fire hazard involved in handling alcohols as compared with
propane is relatively small, the alcohols may be of value as deasphalting
agents in refining some specific refinery products. For this reason, it
might be expected that they will gradually become of some commercial
importance in refining residlJaI stocks from certa.in types of crudes.
There are recorded for commercial utilization of aliphatic alcohols as
deasphalting agents numerous patent applications which frequently
specify the use of aqueous alcohols or addition of water during the
extraction process for altering the solubility characteristics of the
solvent mixtures.
Werschen-Weissenfelser Braunkohlen A.-G.'" treats petroleum residual oils
containing wax and asphalt with fusel oil or similar mixtures, adds to the mixture
from 0.5% to 50/0 of water, and after chilling to the desired temperature, separates
the precipitated asphalt and wax by decantation; N. V. de Bataafsche Petroleum
Maatschappij 30 uses a mixture of a secondary or tertiary aliphatic alcohol and a
polar substancc, such as water, lower aliphatic alcohols or ketones, etc. Widdecke ""
describes a rather elaborated scheme for refining oils with aqueous amyl alcohol for
removal of wax and asphalt in which the water content of the a1col101 is varied in
the course of the extraction. Krauch, Pier, and Eisenhut,31 employ a mixture of
methyl alcohol and a hydroaromatic hydrocarbon Sl1ch as cyc10hexane for removing
resinous and asphaltic suhstances; etc.
The selective solvent action of methyl, ethyl, propyl, butyl and amyl
alcohols on asphalts from different origins has been also investig-ated. 32
Propyl alcohol is, apparently, slightly superior in this respect to other
alcohols, although, in general, the physical characteristics, ash content
and elementary analysis of the. separated fractions showed only m1nor
differences.
As already mentioned the deasphalting solvents are also capable of
separating the oil into fractions of some,vhat different physical and chemical characteristics. This has been recognized for a number of years as
alcohols were recommended for refining the light petroleum fractions at
the early beginning of the petroleum indnstry.*
* Tyler
33
1[)4
Deasphalting Plants
Previous cliscl!~siol1 showed that the propane process is the only COlllmercial solvent deasphalting process in existence. The following tabulation gives the capacities of the propane cleasphaltillg anc! lleresilling plants
and their distribution between various oil companies.
TABLE
Ilbls./Day
19:~6 ........
Bibliography
1.
Gotlbvicz. M., and von Pilat, S., PrscIIl)'sl C/t.em., 18, 376-85 (1934). See, however, U. S.
l)atent Office decision n: lvIctan 's German Patent 362 1 45R.
2. Bray, U. n" Swift, C. E., and Carr, D. E., Oil Gas J., 32, No. 24, 14-6, 20-2 (1933).
3. Dahlke,
n., Sullivan, F. W., Jr., and Wilson, R. E., Canadian Patent 360.J97 (Sept. S,
1936); :Bray, U. B. U. S, l'"lent 1,944,491 (Jan. 23, 1934), U. S. Patent 1,949,989 (Mar.
6, 1934). u. S. Patent., 2,041.275-7 (May 10. 1936), u. S, Patents 1,988,71.1-5 (Jan. 22,
1935), U. S. Ptttent~ 2.010,007-8 (Aug. 6, 1935). Illl(l U. S. Patont 2,1).\9,046 (Jllly 28,
1936); :Bray, U. n., and Swift, C. E., U. S. Patent, 1,988.711-2 (Jan. 22. 1935); Ferris,
S. W., Canadian P"tent 360,630 (Sept. 22, 1936); Ganl, E. W., \J. S. Patent 2,002,004
(May 21, 1935); Haylctt, R E., U. S. Patent 1,9G8,on (July 31, 1934); I. G. Farbcnindustrlc A.-G., British Patent 389,113 (Mur. 6, 1933), Ilritish Patent 450,107 (July 10,
,v.
4.
5,
6.
7.
8.
9.
10.
11.
12.
13.
14,
15.
16.
17.
18.
19.
20.
21.
22,
23.
24.
25.
26,
27.
2R.
29.
30.
31.
32.
10.
,4,
105
1936), l'rench Patent 716,703 (l>by 7, 1931), French Patent 774,421 (Dec. 6, 1934) ane!
French Patent 775,450 (Dec. 28, 1934); Pier. 1,. and Eisenhut. A., U. S. Patent 2,055,135
(Sept. 22, 1936); Standard Oil Development Co., French Patent 791,605 (Dec. 14, 1935);
Tears, C. F., U. S. Patent 2,049,277 (July 28, 1936), and U. S, Patent 2,067,802 (Jan. 12.
1937); Union Oil Co. of California, BJ"itish Patents 408,9478 (Apr. 11, 1934), and British
Patent 410,103 (May 4, 1934); etc.
Godlewicz, M., and von Pilat, S., Przentysl Cite",., 18, 37685 (1934); Oil Gas J., 34, No.
32, 76, 78, 81-2 (1935); Godlewicz, M., Oil Gas J., 34, No. 41), 28 (1936); von Pilat, S.,
Oil Gas J., 35, No. 10, 54-5 58-9 (1936); Standard Oil Development Co., British Patent
449,717 (July 2, 1936); nnd'von Pilat, S" and Godiewicz, M" Canadian Patent 363,364
(Jan. 12, 1937).
I. G. Farbeninclustrie A.-G., French Patent 763,190 (Apr. 25, 1934).
I. G. Farbenindustrie A,-G., British Patent 430,080 (June 6, 1935).
Bray, U. Boo and Swift, C. E., U. S. Patent 2,040,239 (May 12, 1936).
Standard Oil Development Co., French Patent 770,903 (Sept. 24, 1934).
Bray, U, B., U. S. Patent 1,988,714 (Jan. 22, 1934).
N. V. de Batnafsche Petroleum Maat,c1Hl.ppij, Ftcn"h Patents 791,326-7 (Dec. 7, 1935).
Bray, U. B., U. S. Patent 1,988,713 (Jan. 22, 1935).
Whitley, J. M" and Beiswenger, G. A., Canadi:ll1 1'"tont 354,567 (Dec. 3, W35).
N. V. Machinerieen-en Apparaten Fahrieken, "Meaf," French Patent 777,520 (Feb. 22.
1935); Britisll Patent 427.843 (Nov, 6, 1935).
Bray, U, B., and Beckwith, L. B., U. S. Patent 1,988,715 (Jan. 22, 1934),
Wilson. R. E., Keith, p, C., Jr., and IItlylett, R. E., Inri. ElIg. Chew., 28, 106578 (1936);
Wilson, R. 1':., and Keith, P. C., Jr" Proc. Am. Petrol",,,, 1""t. lIT, 15, 10619 (1934);
see also Bray, U. n., Swift. C. E., and Carr, D, E., PTOC. Am. P,troleullt b"'t. Ill,
96-105 (1933), and Refiner Natura! Gasoline Mfr, , 13, 333-5 (1934); Livingston, M, J.,
and Dickinson, J. T., Natl. Petro/c"", News, Ti, No, 27, 25-9 (19.35), discuss deasphaitlUg Pennsylvania. residuums.
Wilson, R. E., Keith, P. C., Jr., and Haylelt, R. Eoo Inri. Eug, Cll.m" 28, 1065-78 (1936).
Gmefe, E. E., Aspltalt Teeri"d. Zeit., 26, 798-802 (1926).
Lochmann, C., Petroleum Z., 31, No. 38. 135 (1935).
I. G. Farbenindustrie A.-G., French PRIen! 790,615 (N,,>,. 25. 1935).
I. G. Farbenindustrie A,G., French Patent 775,450 (Dcc, 18, 1934).
Bray, U. B., Canadian Patent 352,059 (July 30, 19.15).
Bray, U. B., U. S, Patent 2,031,204 (Feb. 18, 1936).
Bray, U. n" u. S. Patents 2,041,275-7 (May 10, 1936).
Ako Products Inc., French P"tent 790,634 (Nov. 25, 1935).
Aldrld~e, B, G., and Hopper, B., U. S. Pilton! 2,041.278 (May 19, 1936).
I. G. Farbenindustrie A-G . German Patent 615,455 (July S, 1935).
Bahlke. W. H" Thiele, E. W., Adams, C. E., and Ginsberg, B., World Petraicl"" CDIl!!I'.,
1'o.l'is (1937).
Widdecke, Z. a1lgew. Cit ell!. , 48, 110-2 (1935),
Werschen-Weissenfelser Braunkohlen A,-G., German P"tent 549,451 (Nov. 21. 1930).
N. V, de Bataafsche Petroleum Maatschappij, British Patent 450,511 Uuly 20, 1936).
Krauch, C., Pier, M" and Eisenhut, A., U. S. Patent 1,960,974 (May 29, 1934).
Zwergal, A., Oel Kohle Erdael Teer, 11, 608-9 (1935).
Tyler, S. N., U. S. Patent 38,015 (Mar. 24, 1863).
Werkenthill, T, A., U. S. 'P>ltents 1,680.352-3 (Aug. 14, 1928); Swift. C. E .. U. S. Patent
2,031,234 (Feh. 18, 1936); B"hcux, c, A. F., French Patent 792,946 (Jan. U, 1936),
employs for this purpose ethyl alcohol.
Chapter X
General Principles of Solvent Refining Processes
oil
* For a
'f For further discussion of the process as applied to refining of light petroleum
106
107
108
1.
- - - = K , or
J'o - Y1
'V'(
2.
'Ill =
KP )
KP+W
KP )"
:v" = Yo ( KP+W.
3.
Counter-current extractions .
.1:,C(e" -1) +}'oC"(C -1)
j'/I==:'--
C - 1+C(C" - 1)
C.
_
il1lpuriti~s in tI~e oil .a!ld ~olv~nt phase respectively,
Yo - concentratIon of Imp unties 111 011 before extraction
Yn = concentration of impurities in oil after nth extracti~n
P = volume of oil free of impurities,
'
vV =
109
KP
C=-.
W
These equations show that single batch extraction is the least efficient
and that counter-current extraction is the 1110st efficient. Counter-flow
towers can be regarded as counter-current batch extractors considering a
given height of the column to be equivalent to one ideal extraction stage.
Attempts are also made to draw parallels hetween solvent extraction and distillation processes Imt the vallie of such comparisons appears to be open to question.
Solvent Analysis
In practice, however, it is frequently necessary to obtain quick information about the available yield of oils of various qualities from a given
charging stock, or the quantity of satisfactory oil rejected into extract,
or the approximate composition of the refined product. Such approximations can be ohtained by the method of Bray, Pollock, and lVlerrill,18
which is a modification of the "Albreaetion" recommendecl hy Lee,19
for identification of variolls crudes by plotting' the gravities of resiclues
uhtained from a given crude in a series of acid tt-eatments.
According to this method the oil is repeatedly extracted by employing
a constant volume of fresh solvent at temperatures required to maintain
a substantially const,mt concentration of oil in the extract phase. The
resulting extracts are analyzed fo!' gravity. ]efractivc index. viscotlity
or some other significant property and the results are plotted against the
total amount of material removed up to the mid-point of the cut in' question.
An example of such curves is given in Figure 11, where Bray, Pollock and
lVlcrrill show the differences obtained in extracting an oil in the above
described manner when the increments of the extracted oil fractions are
small (Curve 1) or large (. Curve 2). These results are compared with
110
jO
30 1 ~
V
_/ ~
/lO~M~L METHOD
exPW/IIlllrA OPUArlOIl /'11TH IIEJ{c1IOt1
2 Il
JHORl
MCTIIOJ)
ZG
3 0 NORMAL METHOD
!;.P
1,,(
.V
~V
v-
Ix V
C "7
II IY
I
v
1--'"
10
../
I. l/'
w
l--o--'
;J
(...9-
/V
-D-
P--'
I--V
V
o
10
.20
.30
4-0
$0
f'ERCl'17AGE 8Y
60
70
lJO
5'0
100
VDLUME
111
solvents have also a certain selective action towards the paraffinic type
of hydrocarbons of lower molecular ,veights, which, in some instances,
may be more soluble in the solvent than the arolllatic compounds of
higher molecular weight. This is substantiated by the observation that
in the multi-stage extractions mentioned above the plot of the amount
of the oil extracted against some of the physical properties of the extracted
fractions, such as gravity, may show an inversion.
When the oil is separated into fractions by means of solvents the
raffinate phase has a higher API gravity, a higher viscosity index, a
lower viscosity-gravity constant, a lower carbon residue, a lower acidity
and a lighter color than the charging stock and, particularly, than the
extract phase. The boiling point range and the flash and fire points
undergo comparatively minor changes, if any. In comparing efficiencies
of extraction by the various methods it is frequently customary to draw
conclusions on the basis of the change of one constant only. Although
this may often be permissible, it should be noted that identical products
are obtained only when all of such constants are in complete agreement,
as otherwise the products cannot be considered as strictly comparable and
the value of the resulting conclusions is, therefore, greatly minimized.
112
January 1930
,----A-----..
January 1934
Process
800
100.00
800
100.00
13.01
1,600
47.06
l'l'_jS
1'.800
52:94
29.27
Nitrohenzelw ~ .... ,.
Nitrobenzene,sLtlfuric acid ....
I
Tot"l
.............
Dno-Sol .................
Furfural ...........
Phenol . . . . . . . .. ... . . .. . .
S ttl fur-diox iele-henzol' ..... .
'1'otal
j'l
6.72
E1trope
. .
2,0'00
100.00
3,;.48
2,000
100.00
34.48
5,500
100.00
94.83
2,000
100.00
9.62
2,000
100.00
9.62
5,500
100.00
26.46
Plants in
Duo-Sol ...............
Furfural .................
Phenol ..................
Chlorex .................. .
Sulfur-dioxidebcnzol* ..... .
Nitrohenzene ............
Nitrol1en1.enc.. sul furic ncid ....
Total
.............
i,ooo
100.00
2,000
100.00
12.27
2.88
S.66
2,000
800
71.43
28.S7
12:27
13.01
1,600
5,500
1,800
17.98
61.80
20.22
33.74
29.27
2,800
100.00
4.04
8,900
100.00
12.83
..
2,000
800
2,000
* 'Plauts using straigbt liquid stlUur dioxide bave a total capacity of 92,260 bbl. per day;
petroleum prodl1cts such as kerosene.
11.3
Jamtary 1936
January 1935
Janl1ary 1938
(Estimated)
1937
U"ited States
800
100.00
100.00
100.00
100.00
100.00
100.00
100.00
13,022
14,100
10,500
6,150
1,500
~ 501l
'800
26.81
29.02
21.62
12.66
3.09
5.15
1.65
100.00
lllO.O()
100.00
100.00
100.00
100.00
100.00
48,572
100.00
100.00
48,572
100.00
100.00
,1,590
1,710
5.800
1,150
34.6412.91
43.77
8.68
<\8.<1'
39.17
100.00
100.00
9,470
94.83
39.13
4,366
5,800
1,150
45.56
21.01
27.90
5.53
100.00
100.00
100.00
100.00
100.00
78.72
100.00
100.00
100.00
100.OU
100.00
13,023
14,100
10,500
0,150
1,500
2,500
100.00
28.57
24.36
23.0-1
13.50
3.29
5.49
1.75
37.04
45,572
100.00
94.07
2,030
25.44
21.44
5',iiOO
55.18
8.54
IiS.71
11.35
4:566
24.01
8.00
73.17
100.00
800
'4.27
18,742
100.00
1,500
26.81
29.02
21.62
12.66
3.09
5.15
1.65
13,022
11,100
10,500
6,150
1,500
2,500
800
10,342
1,600
anti Canada
5',500
100.00
450
68.Y2
5.M
5,500
100.00
26.46
7,980
100.00
38.39
13,250
100.00
63.74
20,786
100.00
100.00
the World
10,342
42.66
1,600
6.60
5,500
22.69
4,500
18.56
1,500
6.19
45.98
8.66
33.74
73.17
56.60
28.1!
20.73
29.8S
11.48
3.64
4.67
1.49
(>n.92
60.11
98.16
100.00
73.58
100.00
100.00
17,612
15,810
16,300
6,150
2,650
2,500
800
28.49
25.57
26.37
9.95
4.29
4.04
1.29
78.30
85.62
100.00
100.00
100.00
100.00
100.00
22,492
18,466
16,300
6,150
2,650
2,500
800
.l2.4J
26.63
23.50
8.87
3.82
3.60
LIS
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
77.21
61,822
100.00
89.13
Ii9,:lS8
100.00
100.00
800
3.30
100.00
15,052
11,100
16,000
6,150
1,950
2,500
800
24,242
100.00
34.95
53,552
77.31
22.69
37.04
26.46
45,572
7,980
85.10
14.90
9-1.07
38.39
48.572
13,250
78.57
21.43
100.00
63.74
48,572
20,786
70.03
29.97
100.00
100.00
24,242
100.00
34.95
53,552
100.00
77.21
61,822
100.00
89.13
69,358
100.00
100.00
but they are not included in this summary, because they are used mostly for refining light
11-1
Chaq:,(il1g
Capacity
YeaI' of
Rhl./D"y
Construction
Pa ulshOl-O, N. J.
Beaumont, Tex.
4.182
2,3.10
1934
l..)hiladelphia, Pa.
\Yood River, 111.
3.330
L(Jcation
Company
DII(J~Sol r-'I'OCCSS
Hull, England
Port
Brclllen, GermallY
Jcromc,
France
Naples, Italy
Grozny, U. S. S. R.
Tnt,,1
2,G80
2,03D
1,280
1,280
1,280
3.600
1934
19H
1935
l,)~S
1936
1936
constt'.
const1".
22,492
Pm'faral Process
Lawrenceville, III.
Port Arthur, Tex.
Roumanin.
BeaUlllont, Tex.
S11cll Haven, Engl~m(l
l\fishurg, Germany
lJulJlin, ireland
Total
Pl,o"ol P"acess
Snrnia, Ont., Canada
Port JerOl1lC, France
Baton Rouge, La.
Bayonne, N. J.
California
Barranca Denneja,
Colombia
Total
1,600
5.000
4,500
60
3,000
1.650
1,3S(i
1.400
1933
19.15
1935
1936
1936
1937
1937
constr-.
18,466
2,000
3,500
5.000
2,000
3.500
1929
1933
1935
300
1936
1935
1935'
1(J . .lOO
ClIlme . P"oress
Casper J "'lyo.
Tulsa, Okla.
'Nood River, Ill.
Oil City, Pa.
Olean, N. Y.
Clarendon, l)a.
Freedom, Pa.
Total
600
200
1,000
1,000
1,700
450
1.200
1932
1932
19.13
1934
1934
1935
19.L'
6.150
Oleulll, Cal.
Courchelettes, France
Trieste, Italy
Tlltal
Nitrobell::eHe Process
Philadelphia, ,Pa.
1,500
450
700*~"*
1934"
1935
1937
2,1150
2,500
19:15
2.500
* Originally
800
1934
~oo
and naphtha have a total capacity of 92,260 bbI./day. The capacity of solvent refining plants
nt the present time far all types of petroleum products is, therefore, 161,618 bbl.fday. -
115
Bibliography
1. Ralichcvsky! V. A., Jnd Stagner, B. A., "Chemical Refining of Petroleum,. n The Chclllical
Cal<llog Cu., 111.('" tRt:inho\d l'u\Jlh;hing emp.), New \'urk. 1933.
2. RakusinJ !vI. A" "Dit:. Ulltcnmchung des Erdi.iles ulld seiner Pl'odukte. '1 l906; Englert C.,
and Hofer, H. V., "D"s EnlOl," Vol. I, 39, 1913.
3. Aisinman, Di"gl~r's jlOlyt. J., 44, 297 (1895),
1. Zaloziecki, "Nelita," 394, 1900.
5. Charitschkoff, Chell'. Rev., 1903, 251,281. For brief historical oUllines of solvent refining
see Manley, R. E., McCarty, B. Y., and Gross, H. H .. Ret,,,er N"t1<ral GIlSOU1I' Mfr.,
12, 420-31 (1933); Wilson, R. E., and Keith, P. C., Notl. PetrolclI'" News, 26, No. 29,
200, 21-6 (1934); Burstin, H., Petroleum Z., 31, No. 15 (1935); Foster, A. L. NIlII.
Pctralemll News, 25, No. 32, 29-31, No. 33, 35-6, No. 34, 34-5, No. 35, 21-2 (1933); etc.
G. Et!eleanu, L., British Patent 11,140 (May 22, 1908).
7. Ferris, S. W" Birkl,imer, E. R., and Henderson, L. M., Ind. Eng. Chel1l., 23, 753-61 (1931).
8. Nash, A. W., Oil Gas J., 31, No. 45, 52-4 (1933).
9. Hunter, T. G., and Nash, A. W., Ind. Eng. Cite",., 27, 8.16-45 (1936).
10. Hunter, T. G., and Nasll, A. W., Trans. World Power Co"f., 3rt! Coni., Washington, 1936.
11. Evans, T. W., bId. Eng. Cltem" 26, 860 (1934).
12. Kurtz, S. S., Jr., b"l. Eng. ChCIII., 27, 845-6 (1935).
13. Thiele, E. W., Ind. Eng. ell.",., 27, 392-6 (1935).
14. Varteressian, K. A., and Fenske, M. R., Ind. Eng. Challt., 2B, 92R-33, 1353-60 (1936).
15. Underwood, A. J. V., Ind. Chemist, 10, 128-30 (1934).
16. Francis, C. K, Oil Gas J., 35, No. 45, 87 (1937).
17. Thompson, F. E. A., J. Inst. Petrolellnt Tech., 22, 189-92 (1936).
lB. Bray, U. B., Pollock, R. C., and Merrill, D. R., Oil Gas J., 34, No.2, 18, 21), 22 (1935).
19. Lee, W., J. Soc. Chem. ]nd., 46, 667-8 (1927).
20. Anon., GlLelll. Ml't. Eng., 27, No. 15, 751 (lY22).
21. Landsberg, L., German Patent 166,452 (1904).
22. Schwartz, F., German Patent 232.794 (Oct. 2, 1909).
23. Nottage, M., J. rust. 1'ctro/c"11> Tech., 18, 943-53 (1933); Rllssini, F. D., Oil GIlS J., 35,
No. 2G, 146-52 (1936), and Refiner Natltral GIl.l'oiille Mfr., 15, '199-506 (l93til; Mail',
n. J., and Schicktanz, S. T., American Chemical Society Meeting, Sept. 7-11, 1936,
Petroleum Division; etc.
24. Mair, B, J., and Willingham, C. n., r"d. E"<q. ClI,em., 28, 1452-60 (1936).
25. Fuc11s, G. H., and Anderson, A. P., American Chemical Society Meeting, Sept. 711,
1936, Petroleum Division.
~6. 'Vatel'man, H. T., Kl'Uijff, P. C., Schon!au, W. J. K., and Tulleners, A. J" .T. Illst.
Petroleum Tech .. 20, 159-6\ (1934),
37. Kalicilevsky, V, A., Simpson, T. P., and Story, B. W . Oil Gas J .. 36, No.3, 88-9"1 (1937);
Natl. Petrolell1lt News, 29, No. 26, 113-9 (1937), llnd Re.uner Natllral Gasolin" Mfr., 16,
Chapter XI
Variables Involved in Refining Oils with
Selective Solvents
(In collaboration 'with Th. A. Petry)
Theoretical foundations of the selective solvent refining processes
discussed in the previous chapter show that a great number of variables
are encountered in practical applications of these processes which are discussed in detail in this chapter. These variables may be segregated in
the following groups:
1. N atttre of the solvent used,
117
Solvent
% byVo[ume
of Extraction
Yield
Viscosity Index
100% aniline
50% nitrobenzene
200ro aniline
45% nitrobenzene
100% aniline
100% nitrobenzene
75 F.
35 F.
75 F.
35 F.
75 F.
35 F.
880/0
780/0
850/0
85%
s8ro
660/0
35
35
39
33
3S
47
11g
Another comparison between selectivity and solvent power characteristics of the different solvents is presented in the following table. 21
TAIILB
Oil
Chlate"
Rallin"te
Chlorex
Ext.ract
Nitrobe\lZene
Raffina!e
Nitrobenzene
Extract
Acetone
Raffino!.
Acetone
Extrap.t
Viscosity at
210" F.
49.
49.
55.
48.
53.
48.
52.
100 F.
272.
233.
582.
216.
406.
236.
390.
Viscosity index
77.5
104.0
5A
1Ot5
54.1
89A
49.8
V. G. C.
0.845
0.828
0.898
0.819
0.817
0.8.33
0.891
Gravity A.P.I.
25.8
28.5
18.0
29.8
21.8
27.7
19.8
A.S.T.M. pour point 0 F.
5' F. -10 F.
5' F. -10 F.
on F. -15 0 F.
Yield, volume % 100.0
74.8
25.2
51.1
48.9
79.2
20.8
* Miscible at 120' F.; extraction at 77' J?
t Miscible at 93' F.; extraction at .10' F.
119
volume of oil, produced a raffinate of 61.0 V. I. and an extract of - 200 V. r. Hencethe quality of the raffinatc, even after this excessive extl"action, is still unsatisfactory, although the V. 1. difference, or "selectivity" is 261.0.
Quantity of Solvent
The quantity of solvent used has, obviously, a direct bearing 011 the
yield and properties of the resulting raffinates. Thus in refining by single
T AllLE 28--Effect of Quantity of Solvent Used in Refining
~H_affinatc
Gravity
o A.P.I.
S.U.V. at
% Yield
210' F.
Viscosity
JIlde.
Ca ..hn~
Residue
100.0
21.4
130.0
65.0
2.9
75.2
62.6
47.1
25.7
26.6
27.1
27.3
108.6
107.8
107.0
106,4
84.7
88.6
91.0
93.2
1.1
0.9
0.8
0.7
70.0
59.1
50.4
44.8
26.0
26.9
27.5
27.6
108.8
106.2
104.6
104.2
85.4
89.5
93.6
95.7
1.0
0.8
0.7
0.6
6G.3
50.0
40.8
34.0
25.9
27.8
28.0
28.2
108.2
107.0
104.2
lO4.0
87.5
92.8
95.4
97.5
1.0
0.8
0.7
0.6
Solvent
% by Volume
Original stock
0
53.3
120
Temperature of Extraction
The effect of temperature is likewise very pronounced. It affects both
the selectivity characteristics and the solvent power of the solvents. The
solvent pow~r always increases with the increase in temperature until the
oil and solvent bec(~11le completely miscible. Selectivity. however, usual1y
decreases gradually, or else remains relatively constant over a certain
temperature range, and then decreases rapidly as the miscibility region
is approached. This is illustrated by the following elata, obtained in
extracting a Coastal distillate with 100% of aniline-benzol mixtures containing 10% benzol, at various extraction tempel'atnres.
TABLIl
29-Effect of Temperature
aD
Temperature of Extraction
Yiel,]
320 F.
75 F.
90%
Vi::;cosity Index
33
85%
80%
100 F.
40
36
The data show that while the yield decreases continually as the extraction temperature is raised, the viscosity index of the raffinate first shows
an increase and then a decrease. This maximum indicates an optimum
balance between selectivity and solvent power of the solvent as applied
to the above stock.
The table below gives similar data ohtained by extracting an undewaxed residt\al stock from 1\{id-Continent cmele of 93 Saybolt Universal
seconds at 210 F., with chloranilinc employing the single batch method
of extraction. The clewaxed charging stock had 105 Saybolt Universal
seconds at 210 F., and a viscosity index of 74. The data below refer
to the oil extracted in the unclcwaxed state, but afterwards dewaxed to
approximately -I- 10 F. pour test. The yields refer to the undewaxecl
oil.
TABLE
3D-Effect
Soh'cnt
by Vo1ume
400%
240%
300'/0
150%
150%
150%
400%
400%
900%
of
Temperature
TCIlIIICrnlul"c
of Extraction
75 F.
100 0 F.
75' F.
100 F.
75 F.
100 F.
75 F.
100 0 F.
75 F.
all
Yield
Viscosity Indcle
37%
23%
43%
43%
64%
43%
37%
9%
31%
97
97
95
90
89
90
97
104
100
121
Time of Contact
The time of contacting the oil with the l:iolvent should be sufficient for
obtaining equilibrium conditions. The time required for this purpose is
evidently inversely proportional to the degree of agitation employed, or,
if contacting is effected by passing counter-currently the solvent ancl the
oil in thin films, by the relative thickness and viscosity of such films.
These variables depend entirely on the nature of the equipment employed
and should be determined experimenta1ly. In general, however, only
moderate agitation is usually sufficient for obtaining equilibrium conditions in a relatively short time.
Time of Settling
The time of settling is likewise dependent 011 the nature of the oil
ancl the solvent and on the degree of agitation employed. For these
reasons it also can be determined only experimentally for each particular
type of equipment and for conditions of extraction. In general, the time
of settling is considerably longer for oils containing wax or asphaltic
substances in suspensions as they tend to act as emulsifying agents.
Some of the solvents appear to emulsify less readily than others. Increased temperatures usually improve settling rates due to lowered
viscosities, provided the degree of dispersion of solvent and oil are the
same.
If the separation between the raffinate and extract phases is not
sufficiently rapid by gravity settling, centrifuging may be also resorted
to.22
In
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128
extracting' the oil with auy of the three solvents and at practically the
same refining yields provided the conditions of extraction are properly
adjusted for the individual solvents. The cost of the solvent and the
size of the extracting and solvent recovery equipment required for
operation t1l1(ier these conditions would then become the deciding economic factors.
The above comparisons are made on the basis of the viscosity indexes
of the raffillates. Similar results are observed also in treating oils to
carbon residue or color specifications, although in exceptional instances
some solvents may show better selectivity than others with respect to
these types of oil constituents. This is, apparently, associated not so
much with the preferential solubility characteristics of such solvents as
with their ability to act as mild precipitating agents, as discussed in the
chapter on deasphalting.
The aLove comparisons between the number of extraction stages
employed or the nature of the solvent used are based primarily 011 the
viscosity indexes of the resulting products which were taken as being
representative of the oil quality. Although this is frequently permissible,
it should be noted that an oil of the same viscosity index might be
obtained by either single or multi-stage extraction methods, but in the
first instance the separation between the desirable and undesirable constituents is less sharp than in multi-stage extractions. For these reasons,
in referring to raffinates of equal quality on the basis of a single test,
some confusion frequently results as other properties of the raffil1ates
are considered to be the same also, which is not necessarily true. Single
stage extractions will always give a somewhat different product than
multi-stage extractions. and the uniformity of the product is obtained
only after the number of extraction stages reaches a certain minimum
beyond which further increase in the number of stages results only in
a negligible improvement in the efficiency of separation.
The minimum quantity of solvent which can be used for extraction
is defined by the solubility of the solvent in the oil, and the maximum
quantity by the solubility of the oil in the solvent, as otherwise the separation i11to two phases is impossible. By raising the extraction temperature the mutual solubilities of solvent and oil increase until they
become miscible in all proportions. In general, however, by increasing
the temperature below the miscibility region the relative quantity of the
oil dissolved in the extract phase is usually higher than that of the solvent
in the raffinate phase, which for a relatively large temperature interval
may be considered as being more or less constant. In counter-current
extraction systems, miscibility conditions are first reached at the point
where the partially spent extract is brought in contact with the fresh
portion of oil, as under these conditions the relative proportion of the
oil constituents highly soluble in the solvent reaches a maximum. Occasionally, also, when using very small quantities of solvents, the separa-
129
tion of the two phases is difficult, but this can be often remedied by
recirculating the extract rejected from the system through the extraction
stages where this difficulty is observed.
Nature of Oil Extracted
Oils to be extracted \vith solvents vary considerably in their physical
characteristics and in the relative contents of the desirable and 1.ll1desirable constituents. Oils of Pennsylvania type contain more high viscosity
index constituents than oils of Mid-Continent and particularly of Coastal
type and, if products of equal viscosity index should be made, the Pentlsylvania oils will yield the largest and the Coastal oils the smallest
amounts of such products. In refining Mid-Continent stocks, the quantity of low viscosity index constituents which sho1.l1cl be rejected for
obtaining a product of viscosity index specifications similar to those of
Pennsylvania oils is not commercially prohibitive, but in refining Coastal
100 V.I.
ASPHALT
WAX.
V.I.
stocks to the same specifications the yield of such quality oils may be
reduced to an impractical minimum. For this reason, selection of stocks
for solvent refining operations is important, as not all of them are able
to give commercial yields of desired products. This is illustrated graphically in Figure 17, which compares approximate contents of various
viscosity index fractions in some of the crudes. 3G Althongh different
oil stocks may be regarded as all containing certain quantities of the
130
131
132
* Kurtz, Headington and Zicbcr,'1 describe the use of such methods as applied
to nitrobenzene.
1" Kurtz, Headington, and Zieber," constructed a chart for estimating the quantity of ni trobenzene present in an oil from the lowering of the closed-cup flash point
of such mixtures.
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38. N. V. de Batattfsche Petroleum Maatschappij, Frent:h Patent 795,107 (1lar. 4, 19.,6).
39. van Dijk, W. J. D., U. S. Palent 2,023,375 (Dcc. 3, 1935).
40. Edeleanu Gos. 111. b. II., French Patent 798,098 (M"y 8, 1936).
4l. Texaco Development Corp., British Patent 445,317 (Apr. 7, 1936).
42. Merrill, D. R, and SubkolV, P., U. S. Patent 2,OQ2,702 (May 28, 1936).
43. Merrill, D. R., U. S. Patent 2,043,389 (June 9, 1936).
44. Gavel's, F. X., U. S. Patent 2,054,052 (Sept. 8, 1936), and British Patent 454,690 (Oct. 6,
1936).
45. v;m der Waorden, H., Ca""iian 'Patent 360,538 (Sept. 15. 1936).
46. Texaco DeVelopment Co., French Patent 795,357 (Mar. 12, 1936); N. V. de Balaafsche
Petroleum Maatschappij, French Patent 797,666 (May I, 1936).
47. Kurtz, S. S., Jr., Headington, C. E., and Zieber, n., Ind. E"g. CIte",., Anal. Ed., 8, 1-5
(1936).
Chapter XII
Single Solvents
Recent investigations have shown that a very large number of chemical
compounds are capable of exhibiting a preferential solvent action towards
the various constituents of petroleum. Of these compounds, liquid sulfur
dioxide, chlorex, furfural, nitrobenzene and phenol have achieved C0111mercial importance in single solvent processes, while aniline, in spite of
its poisonous nature, may also become of future interest.
Besides the above solvents. a series of others have been covered by
patents as being capable of displaying the required selective solvent properties. These solvents include benzonitrile,1 furfuralcloxime,2 benzaldehyde,:! aliphatic aldehydes, particularly propionaldehycle,4 lower aliphatic
acids, such as acetic, propionic, butyric or iso-butyric, 5 'iso-propyl alcohol, (l
furfuryl a1cohol,1 tetrahyclrofurfuryl alcohol,S nitro alcohols such as
nitrobellzyl alcohol,o ethylene glycol ethers and their acyl derivatives,lO
aromatic acetates, such as phenyl acetate,n or benzyl acetate,12 methyl
acetate,13 esters of furoic acid, stich as ,iso-propyl or butyl fU1'oates,H
methyl, ethyl or propyl amino benzoates,15 aliphatic keto-esters such as
ethylacetoacetate,lG lower alkyl hydrogen sulfates,11 ciiketones, such as
acetyl acetone, IS chlorinated substances, such as chlorohydrins,19 chloroacetates,20 etc., quinoline,:!1 amines,22 nitrilcs or organic thiocyanates,!!B
acetonitrile,U aromatic cyanides, such as phenyl cyanide,2u nitro or nitrile
derivatives of aliphatic hydrocarbons, such as nitromcthanc,2!l tetrahydrofuran,21 benzoyl-, tolyl-, or xyloylturan,'.I.S aliphatic acyl derivatives
of furan, such as acetyifuran,20 chloraniline,30 acetophenone,31 carvacrol,32
liquid trimethylenc,33 liquid ammonia,34 liquid carbon dioxide,sa liquid
hyclrog-ell sulfide,36 dibutyl sulfone,37 and lllany others.* This list is
increasing continually, as the numbel' of substances which may be employed
as selective solvents for petroleum oils, is by no means small. It appears
possible that at least some of the substances enumerated above may, with
time, become commercially important, particularly, if they can be obtained
at a low cost.
Liquid Sulfur Dioxide Process
The success of the Edeleanu process in refining kerosenes resulted in
a series of attempts to apply this solvent to the refining of lubricating oil.
* Some of the patents, such as those of Standard Oil Co. of Indiana,""u Edeleanu
Ges. m.b.H."a,,, or N. V. de Bataaf;,che Petroleum Maatschappij,." cover many
hundreds of compounds which, according to their claim!l, can be used as selective
solvents either alone or in mixtures with other solvents:
134
SINGLE SOLVE,YTS
135
distillates. Brandt 13 and Kain 44 * investigated the possibility of manufacturing 111otor, transformer and turbine oils by extraction with liquid
sulfur dioxide. They found that the extracted oils have a flatter viscositytemperature curve and produce less sludge and acidity in nse ; transformer
oils become more resistant to oxidation; turbine oils emulsify less readily,
etc. It has been also claimed that under certain conditions lubricating or
other oils containing paraffin wax can be treated with liquid sulfur dioxide
and the separated upper layer of wax can be filtered at the same 10,,"
temperature to remove the crystallized paraffin.
N. V. de Bataasche Petroleum Maatschappij;17 and Frank;'" descrihe results of
refining transformer and turbine oils; Egloff "u describes the preparatioil oi lubricating oils from cracked residuum by sulfur dioxide extractions.
]\Iolecular weight
Boiling point
Freezing point
Specific gravity at 68/68 F.
SlJecific heat
Heat of vaporization
Vapor pressure at - 54 F.
Vapor pressure at 100 F.
Solubility in water at 32 F,
Solubility in water at 104 F.
Critical temperature
Critical pressure
64.12
140 F.
- 105 F,
1.45
0.32 B. t. u./lb.j F.
167 B. t. u./lb.
100 mm.Hg.
4370 mm.Hg.
19~\'
5%
3WF.
79 aim
Due to its low boiling point, pressure equipment is reCJllirecl in CO\11mercial plant installations.
Many patents have been issued at various times covering the specific
application o[ liquid sulfur dioxide to the refining of luhricating oils,uti
hut the degree of improvement in the properties of 1110t01' oils which can
he obtained by this reagent is, within the commercial limits, not sufficient to
warrant its tlse even when the extraction temperatnres are raised to the
See also the interesting reviews by Erkle:tllll," and Foster:'" alld slicceeding"
articles giving an extensive disclission and a review of literature on the Edeleanu
process.
tN. V: de Bataafsche Peh~ole\1m Maatschappij,'" describes a similar method but
employs low extraction temperatures.
136
Chlorex Process
This process was developed by the Standard Oil Co. of Indiana,un
and is particularly adapted to the refining of Pennsylvania type of oils.
By 1936 seven commercial plants were using chlorex as a selective solvent.
Four of these plants were designed for processing Pennsylvania stocks and are
used by the Pennzoil Co., Freedom Oil Works Co., The Bradford Pennsylvania
Refining Corpn., and So cony- Vacuum Oil Co., Inc.
TABLE
Molecular weight
Boiling point (760 mm.Hg.)
Freezing point
Viscosity:
Centipoises at 25.5 C.
Saybolt Universal 77 0 F. (25 C.)
Saybolt Universal 32 0 F. (0 0 C.)
Vapor pressure, mm.Hg.
Vapor pressure, mm.Hg.
Latent heat of vaporization
Specific heat at 85 F. (29.4 0 C.)
Flash point (closed cup)
Solubility in water:
68~ F. (20 C.)
1940 F. (90 C.)
Specific gravity
142.98
352.40 F. (178 0 C.)
- 61 0 F. ( - 51,70 C)
2.0653
32
39
2 at 100 0 F. (37.8 C.)
100 at 242 0 F. (116.7 C.)
115.4 B. t. u./lb. or
64.1 cal./gm.
0.369
168 F.
0
1.01%
1.71%
1.222 at 68 F. (20 C.)
SINGLE SOLVENTS
137
138
The solvent is, therefore, of the type which is mostly suitable to the
refining of paraffinic type of oils due to the relatively high solvent power
displayed at fairly low temperature extractions,
Chlorex is an abbreviated name for (3' ,B'-dichloroethyl ether (CH 2 CICH 2 -O-CH 2 -Cll.!C1) and has the phy~ical properties given in Table 32.
Acidity of commercial chlorex is approximately 5.5 mg. of HCI per
100 cc. of chlorex. After hydrochloric acid is removed the recoverec1
chlorex is claimed to he more stable than the fresh product. Traces
of hydrochloric acid formed on distilling chlorex should be neutralized
in order to prevent corrosion of the equipment. The solubility of water
in chlorex is about 3% at room temperature.
The relatively high solvent power of chlorex requires somewhat low
extraction temperatnres which may require dewaxillg the oil before solvent
refining and make the solvent particularly useful in refining Pennsylvania
or similar types of oils.
One commercial installation extracts waxy Mid-Continent type distillates below
the wax melting point as regular practice. This can only be done, of course, by
stage counter-current methods, not by tower counter flow, as wax tends to plug
column packing materials.
SINGLE SOLVENTS
139
Furfural Process
The process has been developed by the Texas Oil Co. and the Royal
Dutch Shell Co.,oo and is used primarily in refining Mid-Continent stocks,
although it might also be usee! conveniently with Coastal stocks at somewhat lower extraction temperatures, as ,veil as with Pennsylvania stocks
bnt at higher temperatures.
Due to its high miscibility temperature furfural is well suited for extractiull
at ordinary temperatures of light oils, which with othl'l' solvents Illay he miscihk
at these temperatures. Gross '" thus applies furfural for refining of straight-rt1n
eno
CH=C<
Structural formula
Molecular weight
Boiling point
Freezing point
Specific gravity
Vapor pressure at lOa' F.
Vapor pressure at 216 F.
Latent heat of vaporization
Specific heat (68-2120 F. range)
Flash point (Closed cup)
Kinematic viscosity at 100 F.
Critical temperature
Critical pressnre
Solubility in water at 100 F.
0
CH=CH....-
96.03
0
323 F.
- 34 F.
1.1622 at 20 C. ((iSo F.)
7 111m.Hg..
100 nun.Eg.
193.5 B. t. l1./lb.
0.416
138 F.
0.907 c('ntistokcs
746 0 F.
798 lbs./sq. in. abs.
9.0%
140
SINGLE SOLVENTS
141
Phenol Process
This process has been investigated for a number of years by various
oil companies,* but has been 1110st extensively developed by the Standard
Oil Co. (N.J.), through its subsidiary the Imperial Oil Co. of Canada,
which employs anhydrous phenol instead of phenol containing a few per
cent of water, as specified in most of the earlier patents. U7
Phenol has the properties given below.
TABLE
34-Properties of Phenol
94.05
Molecular weight (CoHoOH)
361 F. (183 C.)
Boiling point
105.6 F. (44.9 C.)
Melting point
100 mm.Hg.
Vapor pressure at 251 F.
1.072
Specific gravity at 68/68 F.
0.56 B. t. u./lbP F.
Specific heat
206 B. t. u./lb.
Heat of vaporization
174 F.
Flash point (closed cup)
9%
Solubility in water at 77" 0F.
infinite
Solubility in water at 151 F.
* Chem. Fabrik Lindenhof C. Weyl and Co.;1l.'l Kuczynski;'" Frazer!l5 uses phenol
with 5-15% water; etc. Schick uses phenol with many dil1,1ents,
0
142
Nitrobenzene Process
The nitrobenzene process ,vas developed hy the Atlantic Refining
Company,(lS which is operating it HOW 011 a commercial scale.
Nitrobenzene (Cr;Br.N0 2 ) has the properties given below.
TABLE
35-Pl'lI]lcrtics of Nitrobenzene
Molecular weight
Boiling- point
Melting point
Vapor pressure at lOO F.
Vapor pressllre at 286" F.
Specific gravity at 68/68 F.
Specific heat
T.atent heat of vaporization
Flash point (closcd cup)
Its solubility in water is very slight
0
123.5
1.207
0.34 B. t. tl./lb,f" F.
142 0 B. t. tt./lb.
208 F.
SINGLE SOLVENTS
113
the separated layers flow fr0111 them to the mixing pumps which transh:r
the mixtures to the next settling chal11b<.~rs. :\ five stage treating system
is adopted at the plant.
The nitrobenzene plant operates 011 oils which arc not necessarily
deasphalted before solvent refining. As has been already mentioned.
however, this is compensated by the use of additional quantities of clay
or sulfuric acid and clay'" for further improvement of the color and carbon
residue of the stocks.
A modification of the nitrobenzene process was developed by the
Sinclair Relining Co. for refining lubricating oils, particularly of Pennsylvania type, by a simultaneolls application of nitrohenzene and sulfuric
acicl.7 Apparently, however, this modification of the process did not
meet with a c0111mercial success.
Aniline Process
The aniline process has been developed by the Standard Oil Co.
of California,71 but has not been put into commercial operation clue to the
poisonous nature of the solvent. The physical properties of aniline,
(C)-Ir,NH~), are given below.
TABUl
:Moleclllar weight
Boiling point
Melting point
Specific gravity
93.06
184.4 e.
-Ge.
1.U22 at 20 e.
Ferris "" uses sulfuric acid ami day after nitrobellzene extractions for manufacturing- white oils.
Bibliography
1. I(urlz, S. S., U. S. Palcnt 1,899,969 (Mar. 7, 1933), and Canadian Patent 333,851 (May 30,
1933); Atlantic l{efllling Co., British Patent 383,801 (Nuv. 24, 19:12) , and French Patent
730,431 (Jan. 22, 1932).
2. l{cncl .. n, M. T., U. S. !'alcnt 1,973,683 (Sepl. 11, 1934) .
.1. 11irkhimer, E. R., U. S. PRtent 1,904,402 (Apr. 18, 1933), and Canadian Patent 333,027
(June 6, 1933).
4. TIirldlimer, E. R., U. S. Patent 1,910,:22 (1\1ay 23, 1933), and Canadian Patent 335,392
(Sept. 5, 1933).
5. N. V. de Bataafsche Petroleum Maatschappij, French Patent 795,107 (Mar. 4, 1936).
6. Taveau, R. de M., U. S. Patent 1,825,762 (Oct. 6, 1931).
7. Hill, J. B., U. S. Patent 1,883,374 (Oct. 18, 1932), and Canadian Patent 334,463 (Aug, 1,
1933); Birkhimer, E. R., Canadian Patent 362,222 (Dec. l, 1936), speciJies aromatic
,tlcohoIs.
S. Detwiler, J. G., Canadian Patent 347,767 (Jan. 22, 1935), and Texaco Devc\opment Corp.,
French Patent 761,270 (Mar. 15, 1934).
9. Clarke, L. A., U. S. Patent 2,020,290 (J.'1ov. 12, 19.15).
lO. Henderson, L., U. S. Patent 1,908,018 Udal' 9, 1933).
11. Frrris. S. W., U. S. Patent 1,874,946 (Aug. 30, 1932), and Canadian P"lent 334,!O3 (July 18,
1933).
144
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
SINGLE SOLVENTS
145
No. 18, 2ti~R. 30, 32 (1~.)5), and RCjillcI' J,Vafu.,al G(J.WUIIC jU/r.,
(1~.35)J giv~s operating; l"usts as applied to l'ennsylvania lubricaling oils; \\run,nns, lJ. H., Oil Gus .T., 33, No. 53, 54-56, 59 0935). ~U1d ~a. 18, 13-4, lt~ (19~,4);
Haylctt, R. E., U. S. Patent 1,988,793 (jan. 22, 193?); removal of hl5it traces of solvent from the oil is spccilied by pa.ulus, ~I. G., U. S. Patent 1,994,i27 (1\l;\r. 19, 1935).
Eic.hw~\d. E., U. S. l)<tt~nt 1,550,523 (Aug. 1(-\, 192.5); Texaco Dc\'clopn"l.l2ut Corp., F1'('.n.(11
14, 283-8
60.
I'atent 752,104 (Sept. 16, IYJ3); Gross, 11. H., C,lI1adian Patent :l50,928 (june 11, 1935),
uses furfural which cnntaills frum lif'o to 12% of \vater at extraction klllpcraturc!'i of
IS0-220' F.; Gross, H. B., U. S. l'a\ent 1,962.103 (June 5, 19.14), specinc; tile use
of 3-furfural. The _lJl"(}CCSS is dcsl:ribcd by :Manlcy. R. E., :l\.IcCarty, B. Y., und Gross,
H. II., Natl. PctrolculI! Ncws, 25, Ko. 43, 26-31 (1933), Oil Gas J., 32, No. 23, 78-82
(1933), Refin" Nat"ral GasoJ.inc Mj,., 12, +20-31 (1933), NIIH. Pe/"'oleulH News, 27,
No. 20, 24, 26, 28, 30, 32-3 (1935), and Oil GIlS J., 33, .Ko. 50, 53, 78, SO (1935); Bryant,
G. R., Manley, R. K, amI McCarty, B. Y., RC]incr Natuml Gaso/ille Mfr., 14, 299-305
(1935); and Ziegenlmln, W. T., Oil GIlS J., 32, No. 45,44 (1934). Livingston,1\1. J., and
Dickinson, J. '1'., Nail. l'etrolcllll! News, 27, No. 27, 25-9 (1935), describe the use of
packed towers ill furfufi:tl relining: whiclt is also spcciticd in Texaco Dcv. Corp., French
Patent 790,369 (Nov. 20, 1935). Weber, G., Oil Gas J., 35, No.7, 30-2 (19.16).
61. Gross, B. H., U. S. P"tent 1,962.10,1 (June 5, 1934).
6''> :Manley, R. E., U. S. Patent 2,000,707 (May 7, 19.J5), and Can"dian Patent 351,398 (July 2,
1935).
63. Cluml. Fabrik Lindenho[ C. Wcyl and Co., German PRtent 213.507 (July 31, 1908).
64. Kuczynski, ,Polish POLtents 2,695 and 3,279 (1922).
65.
66.
67.
j;'razel",
1!J2(j).
68.
i~
O[
employed.
Ferris, S. W., U. S. l'atent 1,788.562 (Jan. 13, 1931); Roberts, O. L.. Crrnariian Patent
359,401 (Jul)' 28, 1936); Atlantic Refinillfl Co .. French Patent 702,967 (Se!)t. 13. 193{)) ,
German Patent 593,827 (Jan. 7, 1934), and British Patent 394,404 (June 29, 193;1). Ferris. S. W., U. S. Patent 1,928.832 (Oct. 3, 1933), rrpplie., the proce," tn the refininfl
of white oils. For the descriptiull of the process sec Fnris, S. \V., J. Franklin; Inst.,
217, 591-615 (1934); Ferris. S. \V., anrl Houflhton, W. F . lIe/illrr Notural Gasolin" Mfr.,
11, 560-7, 581-3 (1932), Proc. Alii. Prtrnltll1ll IIlSI., III, 82-9.> (19.12), Oil GflS J., ll,
No. 26, 65-71, 96 (1932), Ro.lin", Natural (;"solille Mrr.. 12, 328 (193.1), and Natl.
Petroleum News. 24, No. 48, 25-32 (1932); Ferris. S. W .. Myel". ,Yo A., anrl Peterkin.
A. G . Rofi"er Nalural Casolillc Mfr., 12, 435-44 (19,13); ::I1),ors, W. A., Oil Gas J., 34,
No. 44, 81. 8.1-4. 8(,. 88, 91 (1936).
69. Ferris. S. W., U. S. Patent 1,928,R:12 (Oct. 3. 1903).
70. Sinclair Refining Co., British l'atent 390.697 (llpr. 13. 1933), and Frendl Patent 740,831
(July 28. 19321.
71. Chappell. M. L .. and Zis"r. r:. ,T., U. S. Patent 1,741,555 (Dec. :11, 1929). Henderson, L. M.,
U. S. Patent 2,024,221 (Dec. 17, 1935), specifies a mixed aliphatic-aromatic amine such
as phenylmethyJamine. Sec ai,,, Ehle,'s C. R., British Patent 184.991 (July 29. 1921).
Chapter XIII
Mixed Solvents
The lack of solvent power or of the desired degree of selectivity in
some of the selective solvents, as well as a realization of the advantages
to be gained by increasing the flexibility of solvent extraction operations,
resulted in the development of mixed solvents. In such mixtures, the
component present in greatest amounts is usually referred to as "primary
solvent," while the component employed to modify the characteristics of
this primary solvent is referred to as "secondary" solvent. By properly
selecting such components it is, evidently, possible to adjust the selectivity
and the solvent power of the mixture to any desired temperature of
extraction or to make necessary compensations for variations in the nature
of the stock treated. For these reasons, it may be considered within
certain limitations that the use of mixed solvents tends to eliminate the
temperature variable in solvent refining operations.
Although mixed solvents generally contain only two components of
the above mentioned type, ill a few instances additional components may
also he useci for depressing some of the other undesirable characteristics
of solvents such as high melting points, etc. As chemically pure compounds are frequently lacking in some of the properties required of ideal
solvents, the use of solvent mixtures of one or of another type is by no
means ullcommon. The discllssion below is restricted, however, to
solvent mixtures which were developed for the purpose of improving the
solvent characteristics of individual components as the improvement of
their other properties makes the prohlem of specific and not of general
importance.
Component Solvents
As previously stated, the primary solvent in such mixtures is considered the one present in greatest amollnt and possessing low selectivity
or low solvent power within the desired range of extraction temperatures.
The improvement of selectivity or solvent power is obtained by adding
a secondary solvent which must possess high selectivity or high solvent
power. It is always desirable when the solvent having high solvent power
has also a good selectivity, which may be sometimes concealed by its high
solvent power, although this is not always an absolute requirement, provided the selectivity of the other solvent is very high and is not excessively
deteriorated by addition of the high solvent power solvent. In some
146
MIXED SOLVENTS
147
instances, the primary solvent may possess both high selectivity and high
solvent power, and addition of the secondary solvent may have as its
purpose the lowering of the solvent power of the primary solvent. This
is illustrated by the use of phenol containing certain quantities of water
or of lower alcohols, and by other similar combinations. Secondary
solvents may be, therefore. also defined as substances added to the primary
solvents for modifying their solvent power without deteriorating appreciahly their selective solvent properties.
In using mixed solvents. it is frequently observed that for a given oil
and temperature of extraction there exists an optimum quantity of the
secondary solvent which may be employed for obtaining the most satisfactory results. This is obvious from the above discussion. as insufficient
quantity of the secondary solvent results in the lack of solvent vower of
such mixtures, while excessive amo11nts may result in the loss of their
selective solvent properties.
By varying the relative quantities of the components in a mixed solvent
the miscibility region is sometimes reached by addition of a secondary
solvent to the primary solvent at a constant temperature of extraction
at the expense of the extract and not of the raffinate phase. The observed
phenomenon is due to the gradual increase in the concentration of the
secondaiy solvent in the l'affinate phase which disturbs the equilibrium
and increascs the solubility of the primary solvent as well as of the
previously extracted impurities in the raffinate phase.
148
MIXED SOLVENTS
149
150
MIXED SOLVENTS
151
The quantity of benzol added to liquid sulfur dioxide for increasing its
solvent power depends on the nature of the stock and the desired quality
of the finished product. As the two solvents are recovered separately, 110
particular difficulty is encountered in adjusting the mixtures used in suhsequent extractions. The plant resembles in general the plants used for
152
MIXED SOLVENTS
153
Crotonaldehyde Process
The process was developed by the Foster-V/heeler Co.Y hut apparently has not yet been tried on it commercial scale. Originally, flexibility
was obtained by employing mixtures of crotonaldehycle and acrolein
adjusted so as to obtain the desired solvent effect on the oil. The properties of these two solvents are as follows:
TAIlLE
Chemical formula
C"H"CHO
Molecular weight
70.07
Boiling" point
218 F. (103.3' C.)
Free7.ing point
- 103 F. (-75 C.)
Specific gravity at 68 0 F. (20 0 C.)
0.859
0
Viscosity, celltipoises at 85 F.
0.539
0
Viscosity, SUV 100 F.
31.5
Vapor pressure, mm.Hg. at 100 F.
80
Specific heat
0.50 B. t. l1./lb./" F.
Latent heat of vaporization
214 B. t. 11./1b.
Flash (closed cup)
44 F.
0
Acrolein
CH"CHO
S(i.05
12(i.3 F. (52.-10 C.)
Bibliography
I. Standard Oil Co. of Indiana. British Patent 413,307 (July 11, 19.14).
2. IGein, R., U. S. Patent 1,936,453 (Nov. 21, 1933); Klein. H., K1i.hler, R., and Zorn. rI.,
U. S. Patent 1,936,453 (Nov. 21, 1933), and German Patent 532,686 (Dcc. 3, 1931): I. n.
Farbenindllstrie A.-G., French Patent 3Y,459 (Dcc. 5. 1930). These mixtures arc used
primarily for purification of waxes.
3. Diggs, J. H., and Page, J. M., Jr . U. S. Patent 1,976,544 (Oct. 9, 1934).
4. Merrill. D. R.. and Subkow, P., H. S. Patent 1,948,048 (Feh. 20. 1934).
5. Krauch, C., Pier, M., and Eisenhut, A.. U. S. Patent 1,960.974 (May 29, 1934).
o. Hjerpe. E. B.. and GrUBe. W. A., U. S Patent 2.042,995 (June 2, 1936).
i. Bennett, H. T., (T. S. Patent 2,044,603 (June 16. 1936).
8. Manley, R. E .. and Gross, II. II .. U. S. Patent 1,971,75~ (Aug. 28, 1934).
9. Stratford. R. K. U .. S. Palent 1.960,461 (May 29. 1934), and Canadian Patent 334.377 (July 25.
]9.13);
~tanr]nrcl
Oil Development
Co.~
154
15. Diwoky, F. F., and Brown, ;\ B., Canadian Patent 346,406 (Noy. 27, 1934); St~ndard
Oil De"eloPlllent Co., French Patent 748,925 (July 13, 1933), and French Patent 43,393
(1\1ay 11, 1934).
16. van Djjck, \V. ]. D., Canadiilll Patent 357,332 (ApI'. 21, 1936); N. V. ue Rataafschc
I'ctroleUlll 1Iaa.tschi.tppij, lkitisl~ Patent ~~3.1,323 \July 4. 1935).
17. Texaco De\tl"plllcnt Corp., British I'atent 445,317 ( ..-pr. 7, 1936).
18. Manley, R. E., and Gross, H. II., U. S. Patent 2,037,385 (Apr. 14, 1936).
19. Starr, J. Y., and Beiswenger, G. A, COTIadian l'alcnt 356,174 (Feb. 25, 1936).
20. Edele:mu Ges. m. h. II., German Patent 546,123 (Jan. 26, 1928).
21. Parkhurst, G. L., C.nadian I'atent 351,5(>9 (July 9, 1935).
22. Gary, W. W., U. S. Patent 1,89.1,1.18 (Jan. 3, 1933).
23. 1. G. Farhenin,lustrie A.-G., Jlritish Patent 439,621 (Dcc. 11, 1935).
24. I. G. Farhenindustrie A.-G., British Patent 439,674 (Dec. 11, 19:15).
25. Lindcke, H. F., ane] Green'felder, n. 5., British Patent 444,535 (Mar. 23, 1936); N. V.
de B:ttaafschc Petroleum 11aalschappij, French Patent 793,825 (Feb. 1, 1936).
26. Stauffer, J. C., u. S. Patent 3,063,564 (Dec. 8, 1936).
27. N. V. de Bataafsche Petroleum Maatschappij, French Patent 803,486 (Oct. 1, 1936).
~_,S9'. Brown, A. B., and Diwoky, F, F., Canadian P'lto.nt 363,521 Oo.n. 19, 1937).
Valek, W. H., U. S. l'atent 2,076,105 (Apr. 6, 1937).
00. Brooks, B. T., and Humphrey, 1., J, Alii. Clwl>!. Soc., 40, 822-56 (1918).
~l. Mann, F. W., and Chappell, M. L., U. S. Patent 1,163,025 (Dec. 7, 1915).
J~. Rehs, 1:1., British I'atent 113,098 (Jan. 30, 1918).
33. Treneer, J. M., and Benjamitl, C. S., Ilritish rettcn! 164,325 (May 31, 1931), and U. S.
Patent 1,392,370 (Oct. 4, 1931).
34. Sc1mlitt, G., lVis.l"e1lsc/,. m,d Illd" 1, 8-10 (1922), and Petrole"", Times, 8, 249-50 (1922).
35. Buchel, J. A., and Saal, R. N. J., u. S. Patent 1.945,516 (Feb. 6, 1934): Edeleann Ges.
m. b. Jr., German Paten! 580,875 (July 17, 1933), specifies USe of organic subslanres
soluble in s\llfur dioxide; Edeleallu Ges. m. b. H., British Patent 398,992 (Sept. 1933),
and German Patent 571,712 (Apr. 8, 1933); Bray, U. B., U. S. Patent 2,031,205 (Feb. 18,
1936); lIIerrill. D. R., U. S. Patent 1,988,8()3 (Jail. 22, 1935), and U. S. Patent 2,043,388
(June 9, 1936). Fnr tile description of the process see l("in, W., Refiner Nat"ral
Gasoline Mfr., 11, 553-7 (1932); Cottrell, O. P .. Refiner Nat1lral Gasoline Mfr., 12,
4.12-4 (193.1), Oil Gas .1., 31, No. 28, 10-12 (1932); Albright, J. C., Natl. PetrolcII'"
News, 27, No. 10, 25 (1935): Stockman. L. P., Oil Gas J., 33, No. 13, 6 (1934).
~I\. Rutherford, J. T., U. S. Patent 2,024,476 (Dec. 17, 1935).
:'7. Starr, J. V., and Phillips, G. E., Canadian Patcnt 334,380 (July 25, 1933).
38. StandfLrd Oil Development Co., French Patent 728,289 (Dec. 15, 1931).
:'\9. Parklml'st, G. L., U. S. Patent 2,029,689 (Feh. 4, 1936).
40. FitzSimons. 0., aorl Croxton, F. C., U. S. Patent 2,053,000 (Sept. 1, 1936).
41. Poole, J. W.,
S. Patent 1,965,392 (July 3. 1934), amI U. S. Patent 2,017,730 (Oct. 15.
1935). Ferris, S. W., U. S. Patent 2,033.932 (Mar. 17, 1936), recommends the usc of
unsntlll'at~d. aliphatic alcohols, such as allyl. crotonyl. 01' dimethyl allyl alcohol.
For
the descnptlOn of the proce.,. see Poole. J. W., and W"dswortll, J. M .. Oil Gas J., 32,
No. 2-" 19-52 (19.13), and ReJinrr No/ural Gasoli", Mfr., 12, 412-9 (1933); and Poole.
J. W" Natl. 1'etrolellm News, 25, No. :13, 28, 30-5 (1933\.
u.
Chapter XIV
Double Solvents
The double solvent processes employ two solvents which have relatively
low mutual solubilities and one of which has preferential solubility characteristics towards the undesirable oil constituents, while the other is
claimed to have similar characteristics but towards the desirable oil
constituents. These processes can be visualized as single solvent processes with the raffinate phase in solution in another solvent. This paralleb, therefore, to a certain extent, refming of oib in naphtha solution
with sulfuric acid, a process well known to petroleum refiners.
Paraffinic Solvents
The choice of a proper "paraffinic" solvent for the raffinate phase is
somewhat difficult as not many solvents are availahle which, when mixed
with oil, are capable of forming two phases within the desired temperature
ranges after such solutions are brought in contact with the second or
so-called "naphthenic" solvent. In practice. the paraffinic solvents are
restricted to light aliphatic hydl"Ocarbons as represented by propane and
allied substances, while napi1thenic solvents are likewise limited to a
relatively few cOl11pounds satisfactory for extraction at atmospheric temperatures.
Although paraffinic solvents are generally considered to have preferential solvent action towards the desirable oil constituents, this is, apparently. open to question, particularly in the absence of asphalt. Thus,
by extracting a Coastal distillate oil in naphtha solution with aniline, in
which the naphtha was substantially immiscible, the yield and properties
of the raffinate were found to be the same as those of the raffinatc obtained
by extracting the distillate with the same quantity of aniline in absence of
naphtha. This does not preclude the possibility that by employing other
solvents or other non-asphalt bearing- oil stocks, dilution of the extracted
oil with naphtha or allied substances may be beneficial. However, such a
beneficial effect may also he explained by the effects associated with the
extraction of impurities from more dilute solutions, to the reduction ill
the viscosity of the oil phase resulting in improved settling rates, etc.,
rather than to actual preferential solubility characteristics of the paraffinic
solvents.
Bray, Swift, and Carr,' observed that the amount of selective solvent required
to give a raffinate of a definite quality may be slightly greater when propane is
155
156
used, bUl that the benefits of increased yield alll! saving on subsequent treatmcnt
are afteu more than sufficient to justify the use of propane with a suitablc solvent.
This also indicates that the presence of the paraffinic solvent changes the selectivity
and solvent power characteristics of the naphthenic solvent, which can be expected
from general considerations based on the distrihution law principles, rather than
from additional assl1l11[ltions about the special selectivity characteristics of paraffinic solvents.
* Shell
DOUBLE SOLVENTS
157
deasphalted anel dewaxeel with propane anel the resulting propane solution
is then brought in contact with the l1aphthenic solvent.
Cresylic acid-phenol mixture, similar to that employed by the Duo-Sol
process, described further below. is being- used. Edeleanu Ges. m.b.H.," specifies
refining of oils tirst with light hydrocarbons, such as ethane, propane, butane or
pentane, and then contacting the solution counter-currently with liquid sulfur
dioxide, chlorex, nitrobenzene, furfural, or their mixtures with benzol or chloroform. See also Tuttle," who treats the distiIlate oil with nitrobenzol or other solvents in presence of propane employing recycling operations.
Duo-Sol Process
The process was developed by M. H. Tuttle of the :Max. B. II/riller Co.,
and is now successfully operated by several large oil companies_21
Tuttle '". '" spccities the use of wood tal' acids, and the use of crcsylic acid
in combination with propane. The Max B. Miller Co. patents,'" '" covel' the use
of a combination of a paraffinic solvent (ethane, propane, butane, petroleum ether,
gasoline, etc.) and a naphthenic solvent (cresol, guaiacol. or beechwood creosote) ;
another British Patent 10 specifies extractioll with a mixture of a liquefied normally
gaseolls hydrocarbon and a naphthenic solvent. Max B. Miller Co.," specifies a
paraffinic solvent stich as propane and a naphthenic solvent slIch as nitl'obenzene.
nitrotoll\cn~. b~nzyl alcohol. liquid sulfur dioxide, furfural, pyridine, or aniline.
~fax B. lId iller Co." specifies cresylic acid and a paraffinic solvent sllch as ethane.
propane. butane, etc. Tuttle lll. '0 covers various operating details for double solvent
processes.
158
Chemical formula
Molecular weight
Boiling point
Specific gravity at 68/68 F.
Specific heat, B. t. u.l1b./o F.
Latent heat of vaporization, B. t. u./lb.
Flash point (closed cup)
Boiling point at 100 mm.Hg.
Cresol
(mixture of
meta- and para)
C6H.CCHa) COH)
365-400 F.
1.045
0.53
180
108.10
396 0 F.
1.035
0.525
178 0
186 F.
281 F.
0
DOUBLE SOLVENTS
159
[1Ic.
16()
of SDlvenb
~Ellllllo.reu .~
Cl'e~yHc
Acid
Propane
R"ffinate
Yield
(% Volume)
150
150
400
200
400
60
0.72
90
77
58
0.51
85
400
40(]
GO
82
83
0.10
0.07
17
5
(iOO
85
67
135
129
102
99
% Weight
of Solvents
,..-- E,nployed---...
Cre;;;yIic
Ac id
Propane
100
100
200
600.
200
600
30()
300
R"ftinate
Yield
(~{) Volume)
86
90
74
81
84
1.1
1.0
91
0.5
0.5
77
96
525
260
.'325
Hi5
115
124
104
103
* Mixtures
containing (,0% crrsylic acid and 40% phenol were actually used.
DOUBLE SOLVENTS
161
162
Bibliography
I. llray, U. n., Swift, C. E., anu C:J.lT, D. E., Oil Gas J., 32, No. 24, 14-6, 20 (1933).
2. Euelc,mu G~s. m. b. II., l're11l;h l'atent 775,434 lDec. 28, 1934).
J. Tuttle, ,"1. H., U. S. I'atent 2,041,308 (lIl:J.Y 19, 1936).
4. Bahlke, W. H' I U. S. Patent 2,017,432 (Oct. 15, 1935), and Canadian Patent J60,983 (Oct. 6,
1936), and Page, J. M., Jr., CallOuiall Patent 344,609 (Sept. 11, 1934).
5. Standanl Oil Co., Frendl l'atent 44,219 (Dec. I, 1934); Bray, U. B., Canauian Patent 3'16,412
(i':ov. 27, 1934).
6. Bray, U. 11., and Swill, C. E., U. S. Patents 2,006,092-3 (June 25, 1935); N. V. de Bataalsehe
Petroleum Maatschappij, British I'atent 355,294 (June 3, 1929).
7. lkal', U. B., and Swift, C. K, U. S. Patent 2,026,729 (Jan. 7, 1936).
~. Whiteley, J. M., Jr., U. S. Patellt 2,025,965 (Dec. 31, 1935).
9. Standard Oil Co., French P"lent 44,220 (Dec. I, 1934); Texaco Development Co., French
I'atent 763,455 (May 1, 1934); N. V. c.le llataafsche Petroleum .rvr""t.chappij, French
Patent 776,043 U"". 15, 1935), and van Dijck, W. J. D., Mayer, A. W. J., anc.l Sa"l,
R. N. J., Canadian l'atent 364,322 (Feb. 23, 1937).
lLl. Standard Oil Development Co., French Patent 795,444 (Mar. 13, 1936).
11. Yall Dijck, W. J. D., U. S. Patent 2,023,109 (Dec. 3, 1935), and N. V. de Bataafsche
PClroleuIll IHaa.lschappijJ British IJatcnt 355,294 (June .3, 1929), recommend melhyl
<tkuhol LUld caruon disulfide for pal'affmic and naphthcllic solvents, l-espectivcly.
P
Tuttle, M. R., U. S. Patent 1,912,348 (May 3D, 1933).
13. Tuttle, 111. R., U. S. Patent 1,912,349 (i).;1:Ly 3D, 1933).
l-l. .Max JI. MilicI' Co., British Patent 421,123 (Dcc. 10, 1934).
IS. :Max B. Miller Co., British Patent 445,942 (Apr. 22, 1936).
Iv. ,"lax B . .Miller Co., British P"tent 424,000 (Feb. 1.1, 1935).
17. Max II. Miller Cu., French Patent 759,633 (Feb. 6, 1934).
IS. ,"lax n. MilicI' Co., french Patent 756,218 (Dec. 6, 19.13).
19. Tuttle, M. B., U. S. Patents 2,070,383-5 (Feb. 9, 1937).
20. Tutllc, ill. B., U. S. Patent 2,077,287 (Apr. 13, 1937).
21. 1"or tile more detailed description of the process see rvliller, IVl, n., ]\1atl. Petroleum J.Vews, 25,
1\:0. 41, 26-8 (1933); Hightower, J. V., ell"lIt. Met. En!!., 42, 82"5 (1935); Foster, A. L.,
Nail. Petrol,,,,,, News, 26, No. 40, 35-42 (1934); Allon., Rejiller Nfl/mal Gasolille Mfr.,
13, .169-74 (1934); Anon., Petrolclt'" Eng., 5, No. I, 2.7-8 (1933); Wilson, C. 0,., Oil
G'as J., 33, No. 20, 12-3 (1934); Tuttle, M. H., anu :Miller, :M. B., Reli"er Nat"",l
Gasoline Mlr., 12, 453 (1933), and 14, 289-98 (1935), and PrOG. Am. Petrolcltill Illst., III,
859 (1933); Miller, 1>1. B., World Petrol"""" 6, 285-91 (1935), Oil Gas J., 32, No. 21,
ll, 62 (1933), Natl. PetrolcuII' News, 25, No. 41, 26-8 (193.1), "World's Petroleum COIlgress," Paris, June, 1937.
22. K"tz, E., Polish Patents 16,738-9 (1926).
23. Clarke, L. A., U. S. Patent 1,974,805 (Sept. 25, 1934).
21. llurstin, II., l'rzem. Ciwn., 1934, 341-7.
25. Kalichevsky, V. A., and Stagner, B. A., "Chemical Rcfming; of Petroleum,lI The Chemical
Catalog Co., Inc. (Reinhold Publishing Corp.), 19.1.1.
26. Wilson, R. E., Keith, P. C., Jr., and H"ylett, R. E., Ind. Eng. C/WlII., 2B, 1056-78 (1Y36);
.'i~e also Bray, U. B., Swift. C. E., and Carr, D. E., Oil Ga.s ],. 32, No. 24, H'(l, 20
(193.1); and B~LhlkcJ W. H., Thiele, E. \V" Adams, C. E., ::tnt! Ginsberg, n., "\Vorld
I'clrolcum Congress," Paris, June, 1937, and Natl. 1'etI'0/,,,,,, News, Aug. 25, 1937, R-l13.
27. Bray. U. B., and Swift, C. E., U. S. Patent 2,006,098 (June 25, 1935), and Union Oil Co.
of Cali[orni" French Patent 74(J,80J (July 20, 1932).
2K Bl'O.)" U. n., and Swilt, C. E., U. S. Patent 2.006,096 (June 25, 19.35).
29. Bray, U. B.. and Swift, C. E., Canadian Patent 344,453 (Sept. 4, 193<1).
30. Bros. U. n., "nd Swift, C. E .. U. S. Patent 2.006,097 (June 25, 1935).
31. (;arol"lo. R. J., u. S. Patent 1,9i8,346 (Feb. 20, 1934).
Chapter XV
Disposal of Solvent Extracts
In view of the rapid growth of the solvent extraction processes the
problem of disposing of the solvent extracts becomes of increasing
commercial importance. The extracts from solvent refining obviously
contain those constituents of the raw petrolenm fractions, \vhich are
characterized by a low viscosity index, high carbon residue, and considerable chemicalleactivity. The extracts are free, however, of paraf-fi.n
~\Vax, except for small quantities of it which are often introduced into
the extracts by mechanical entrainment in treating the wax jJcaring
stucks. The extracts differ from the sulfuric acid sludges, the C01111110n
waste material from the conventional sulfuric acid treating processes,
in being free fr0111 sulfonated materials, and this fact greatly facilitates
their handling and their utilization around the plant.
Chemically, the extracts may be regarded as being composed of
asphaltic and resinuus hodies, substances of predominantly aromatic
nature, and compounds of sulfur and nitrogen. The nature and appearance of these extracts vary with the nature of the processed crude, its
preliminary refining, viscosity ot the treated fraction, ancl the severit),
cmd completeness of the solvent treat. In contrast with sulfuric acid,
solvents have no chemical action on the oil, and extracts are, therefore,
free of compounds formed in the course of refining, unless traces of
sllch compounds are introduced by employing solvents which slightly
decompose on distillation. This occurs. however. only when the conditions for distilling off the solvents from the oil are not sufficiently well
worked out or when the distillation system becomes unbalanced.
In general, three types of extracts are available at the refineries:
those from the cleasphalting processes which contain primarily the
asphaltic constituents, those from the solvent refining of deasphalted
stocks which are practically free of asphalt but contain the low viscosity
index constituents that are usually very reactive, and those from the
double solvent processes, which contain both asphalt and low viscosity
index constituents. The first two types of extracts are simpler to dispose
of than the latter type which, unless used as fuel or as an admixture
to asphalt. ll1t1st he first separated into the asphaltic bodies and oil
before they can be used as raw materials for further reworking into
valuable by-products.
As all of the extracts depend, with respect to their actual chemical
163
164
composition, on the type of crude from which the oil is obtained, their
utilization is like'vvise an individual refinery problem. While all of them
obviously can be utilized as fuel, some of the more valuable extracts
can be employed as raw materials for manufacturing more valuable
by-products thereby increasing the returns of the refinery. Considerable
amount of research has been conducted along these lines and, apparently,
with better success than with the sulfuric acid sludges which, with a
few exceptions, continue to remain a nuisance of the petroleum industry.
The huge quantities of solvent extracts now being obtained by the
refineries involve the problem of their disposal in bulk quantities. The
chemical nature of many of these extracts, however, suggests their
utilization in a 1110re efficient way as raw materials for various synthetic
chemicals, but only a negligible portion of the extracts can be disposed.
in such profitable way. For this reason the discttssion below is separated into two portions: disposal of the solvent extracts in bulle quantities and their reworking into various by-products of a more limited type.
\Naste products fr0111 the deasphalting processes or the extracts
from the double solvent refining processes which contain large qttantities
of asphalt might he frequently utilized in the manufacture of asphalts
and road oils.1 This frequently results in improved products with respect
to ductility although the presence of excessive quantities of oil in the
extracts may sometimes be harmful. For this reason, the quantity of
extracts to be utilized in this way depends 011 the particular use for which
such products are intended.
In refining lubricating oils to high grade products the extracts frequently contain fairly large quantities of relatively high viscosity index
oils, which can be removed fr0111 the extracts by reextracting them again
with solvents,~ or by removing some of the solvent, or by chilling, or
by adding an oil anti-solvent such as water or alcohol.
Reextractions with solvents should be, evidently, made under different
treating conditions from the original extractions from which these extracts were obtained. The resulting products usually possess a fair
degree of chemical stability while their viscosity index may frequently
be equal to that of the oils formerly obtained from the Mid-Continent
crudes by the conventional acid treating methods. For this reason, they
can be disposed of as secondary grades of lubricating oils for which
there is always a good market.
The possibility of recovering such seconc! grade oils by reextracting
the solvent extracts with solvents under modified conditions of extraction
was discussed in Chapter XI where it was shown that considerable
quantities of reasonably satisfactory oils may he ohtained ill this manner.
As a modification of such methods it has been also proposed before separating the solvent to saturate the extract phase with water which displaces the oil from its solution in the solvent with a sufficient degree of
HiS
166
the extracts they are capable of yielding high octane numbcr cracked
gasolincs. However, as is observed on cracking crudes rich in aromatic
compounds, coke formation lllay be excessive while gasoline yield will
be relatively low. r
A large proportion of the solvent extracts is utilized as fuel oil. G It
is to be hoped, however, that this practice will gradually diminish as new
outlets are found for a more efficient utilization of these extracts. When
used as fuel, the extracts, due to theh' aromatic nature, are frequently
of value whcn used in blencls with fuel oils from cracking processes
which have a tendency to deposit sediment in storage. This sediment
is formed due to the relatively poor solubility of the polymerized bodies
in the more paraffinic oils, whereas solubility of such polymerized bodies
becomes fair in blends of extract oi1s, which contain aromatic types of
hydrocarbons. For this reason, addition of certain types of solvent
extracts to cracked residu1111ls may find commercial application for stabilizing the product. 8
Limited quantities of extl"acts can also be employed as froth-flotation
agents, for manufacturing certain types of gear oils, inclustriallubricants,
greases, etc., whenever the stability of the oil employed is of secondary
importance. This, evidently, can be decided only by knowing the particular application for which the products are intended.
Consillerable amount of work has been calTiecl out on the possible
utilization of solvent extracts for manufacturing different chemical byproducts. Many helpful suggestions in this respect can be found in the
fundamental work of Ellis 9 on the utilization of various petroleum
products for the manufacture of chemicals.
A complete description of these methods is beyond the scope of the
present work as it enters well il1to the field of organic chemistry. III
general. however, it has been proposed to utilize the solvent extracts for
the manufacture o[ resins, sulfonic acids,lO dyes and pour point depressants,11 etc. The manufacture of sulfonic acids appears in this respect
to be attractive because the supply of sulfonates from the conventional
sulfuric acid processes will diminish as the solvent refining processes
become more and more universally adopted to the various needs of the
petroleum industry.
It has been also proposed to use the solvent extracts for resolving
crude oil emulsions.* The chemical reactivity ot extracts suggests their
usc for manufacturing oxygenated compounds by careful oxiclation by
air or oxygen. or hy the sulfuric acid method.13
To recover the fluorescent matter from the extracts for artificial
coloring of motor oils,14 as well as to utilize the variol1s nitrogen C0111pounds if such are present in the extracts, has a1so been recommended,15
De Groote and Monson" recommend for this purpose the fraction of the
extract which boils between 360 F. to over 490 F., and which is, therefore,
obtailled from products of the type of kerosene.
0
167
2.
3.
4.
S.
6.
7.
S.
9.
10.
11.
12.
13.
14.
15.
LoeGel, A., U. S. Palent 1,881.753 (Oct. 11, 1932), and li. S. Patent 1.~H~ ..1fJ5 (NoL 39, 19.1],;
Standard Oil Development Co., I'relldl !'"lent 7S3,036 (Oct. 5, 1933); Allan, H. L.,
U. S. Patent 1,990,466 (Feb. 12, 1935); N. V. de B"taafsche I'etroleum Ma .. tschappii.
Dutch Patent 28,709 (Jan. 16, 19.13), uses high boiling fractions nf the Edeleanu extracts
for increaSing the toughness of the asphalt. Beard, L. C., Jr., Oil Gas j., 30 t 1\0. 46,
56-7 (1932). .
Bennett. H. T., Canadian l'alent 342,.~n (June 19, 1934); Fussteig, R., .-lUge",. Od", Felt
Ztg., 33, 441-9 (19,16).
Suida, H., pml, IT., and Nowak. A.. Austrian Patent 141,514 (Apr. 25, 1935l; Austri'ln
Patent 148,991 (Mar. 25, 1937); French I'atent 789,299 (Oct. 25, 19:;5): lIrilish Patent
436,194 (Oct. 7, 1935); Frondl Patent 781,473 (July 22, 19.15); and British Patent 432,24~
(July 23, 1935).
Suidn, H., and Poll, H., Petroleum Z., 30, No. 25, 47 (1934); see ;tlso Standard Oil Devolnp.
ment Co., French Patent 803,413 (Sept. 30. 1936).
Halloran, R. A., and Chappell, M. L., U. S. l'atent 1.893.774 (Jan. 10, 1933).
Ferris, S. \V., and Houghton, \V. F., Proc. Am. Petroleum. 11Ist.~ 89 (1932.).
Sachaneu, A. N., and Tilicheyev. '1-1. D., liThe Chelnistry and Technology of Crack.ing,"
Reinhold Publishing Corp., New York, 1932.
Edelcanu Gcs. fll. h. n., German Patent 512,020 (Oct. 8. 1927).
Ellis, C., ~jThe Chemh;try of Pctrnteum D{~rha.tives/' The Chcmh:ill Catalog Co., Inc. (Reinhold Publishing Corp.), 19,14.
Limburg, H., U. S. Patent 1,895.195 (Jan. 2t, 1933); Osborn, R. T.~ and Cnlig, R., U. S.
Patent 1.955,859 (Apr. N, 19,4).
SclJafier. S. S., an,l Fasce. J':. V., Canadian Patrnt :1'11,70B (May 1$, 19.14).
De. Groote, M., and Monson. L. T., U. S. P,llent 1,834,940 (Dec. 8, 19.31).
N. V. de Balaafsche Petroleum Maatschappii, British P'Ltent 393,152 (June 1. 19;12).
N. V. <Ie Bataafsche Petroleum ;YTaatschappij, German Patent 546,516 (July 24, 1930).
Ihrig, H, K., U. S. Patent 1,768,910 (Ju\y 1, 1930).
Chapter XVI
Pour Point Depressants
Improvement in lubricating oil quality may be accomplished not only
by removing the undesirable constituents but also by adding to the oil
various protective agents or other substances capable of improving
service characteristics of natural products. The most important substances of this type are pour point depressants, oiliness carriers and
extreme pressure materials, viscosity index improvers, oxidation inhibitors, and color improvers. Other similar materials are fillers, as
represented by aluminum soaps used for manufacturing chatter proof
lubricants. and diluents or light viscosity anc1low boiling point substances
addecl to lubricating oils in order to eliminate some of the difficulties
encountered in employing fresh oils before they become diluted with the
heavy gasoline ends and attain normal viscosity in service. At the
present time, however, the use of fillers is no longer warranted due to
mechanical improvements in engines, while the use of diluents is likewise falling into disuse because corresponding improvements in the
engine design and in the distillation characteristics of fuels have practically eliminated the dilution problem in operation of the modern
internal combustion engines.
Effect of Wax on Oil Properties
It has previously been shown that the presence of wax in lubricating
oils is undesirable for the main reason that wax bearing oils have a high
congealing temperature resulting in an unsatisfactory circulation of such
nils in the engine. If such circulation can be established, however, the
engine performance depends primarily on the true viscosity of the oil
and not on the pour poinU At temperatures at which the wax goes
completely into oil solution, its presence may be even beneficial as,
according to Davis and Blackwood,2,4 the presence of wax in oils
increases the viscosity index, lowers the carbon forming tendency, improves volatility and oiliness, and raises the stability of oils towards
oxidation.*
The improvement in the viscosity index of an oil due to presence
of wax is explained by the very low viscosity of the wax in a molten
state. The dfect of wax 011 the viscosity index is, therefore, the same
'" Standard Oil Development Co." recommend~ improvin!; service characteristics
of lubricating oils (\eficienL in waJ', by adding to such oils some of the wax with
the required amount of pour-point depressants to off-set the rise in the pour point.
168
169
as that associated with dilution of oils with low viscosity materials which
has been discussed in Chapter 1. Such improvement in the viscosity
index is observed, however, only when wax is completely soluble in
the oil at temperatures at which viscosities are measured, .e . at 100 0 F.
and 210 F. employed in calculating viscosity indexes. If, however,
wax dissolves completely in the oil at 210 F. while at 100 0 F. its solubility is incomplete, the viscosity index of such oil-wax blends is often
inferior to that of the clewaxed oil. The effect of the presence of wax
on the carbon residue of the oil has also been explained as being a dilution phenomenon because the carhon residue of wax might be considered
as being nil. The effect of wax on volatility of oils as measured by flash
and fire tests and on their oiliness is usually insignificant and may be even
open to question, while its effect all oxidation characteristics depends
to a great extent on the type of oxidation test employed and might be
shown to be in either direction.
The effect of adding a pour point depressant (Paraflow), to wax
bearing lubricating oils can he visualized from the following experimental
elata, given by Davis and Blackwood. 4
TARLE
,----S.A.E.I0 --.~
A~ is
+ 1% Pnraflow
Properties
Gravity, 0 AP.I.
S.U.V. at 100 0 F.
S.U.V. at 210 F.
Viscositv index
Pour point, 0 F.
Flash point, 0 F.
Carholl residuc
Color, Tag-Robinson
Cloud point, 0 F.
DC!1lulsibility at 130 F.
0
30.6
150
43.2
90
+30
380
0.014
11
52
1620
30.4
161
44.3
99
-10
395
0.055
10
46
1620
27.4
481
62.3
96
+30
415
0.815
2:\:
1620
27.5
474
62.0
97
-10
415
0.829
2
1620
Summarizing the above effects of wax on oil properties it is apparent that its presence in the oil is at least not objectionable if the fluidity
of the oil can be maintained at low temperatures. By leaving wax in the
oil, however, the considerable expense of dewaxing operations can be
elimi11ated to a certain extent while the yield of the oil is improved
by the amount of wax left in the oil.
170
Moser a,' separates pour point depressants from pyrogcnous condensation produc1s by precipita.tion with aliphatic solvents, and employs a similar method for
separating such substances from solvent extracts after heating the extracts to
350 C. (662' F.) for increasing their asphaltcne content. See also Winning and
Fulton.
t Sloane 0 concentrates pour point depressants by extraction with butyl or amyl
alcohols.
t Kaladzhal '8 finds that addition of aluminum stearate creates in some instances
a "maximum" and a "minim\lm" pour point which can be eliminated by addition
of triethanolamine. Barth and Corlew' specify aluminum salts of organic acids
produced by the oxidation of paraffin wax.
171
products derived fro111 a sligar having at least one cyclic nucleus and
not more than two mono-saccharide groups in its molecule and an aliphatic acid, such as those of sucrose and stearic acid,~7 esterified hydrostearic acid,28 aluminum soaps,~n polystyrol, polyilldene, hydrogenated
natural or synthetic rubber or similar hydrocarbon polymerization
products,30 oxygenated vinyl compollnds,~l ethylene glycol distearate,32
aluminum chloride condensation product of a higher fatty acid chloride,
such as stearyl chloride, and a coal tar material,a:~ mixed ketones, a!
condensation products of hydrocarbons rich in parafiin,:l5 tristearate of
pyrogallol and similar compounds,3U glycerol tristearate,31 esters formed
frol11 .an alcohol containing at least ten carbon atol11s,~8 rufigallic acid
hexastearate, pyrogallol tristearate, resorcinol distearate and allied substances,'lil soaps of carboxylic acid containing more than nine carbon
atoms and a metal of the titanium subgroup of Group IV of the Periodic
System, such as titanium stearate,40 nonparaffinic natural waxes, such as
beeswax, spermaceti, myrica, candelilla, carnauba, china or lignite wax,41
condensation products of a halide of an aliphatic organic compound
having a long paraffin chain, such as chlorinated paraffin wax, and a
monochloronaphthalene or bromophenol, followed by further condensation with sodium for removing the halogen atoms,4~ condensation
products of oleic aciel, a elichloroparaffin, such as ethylene dichloride,
and an unsubstitued aromatic hydrocarbon;!'1 condensation products of
high molecular aliphatic hydrocarbons and aromatic compounds C011taining oxygen, snch as condensation products of diphenylene oxide and
chlorinated paraffin,H products obtained by heating chlorinated aliphatic
hydrocarbons with an aromatic hydrocarbon,"';' organic compounds having one or more five or six membered rings with at least two side chains
of ten or more carbon atoms, sllch as tristearate of pyrogallic acid or
distearatc of alizarine,4!l condensation products of an aromatic hydrocarbon material, such as naphthalene, and aliphatic hydrocarbon material, such as paraffin or l110nochlorowax, further condensed with a resinifying agent stIch as trioxymethylene,47 etc.*
The above list does not include patents which were issued in connection with the two best known commercial ponr point depressants
"Paraflow" and "SantopoLlr" (liscLlssecl in more detail on sl1bsequent
pages.
Byers" gives a survey of the patent literature on pOllr l?oint h;hibitors s!?o:ving tIl at sllch substances had already been recommended for Ullprovmg the fhtHhty
of oils as early as in 18(Ji. A total of 77 patents is abstracted.
172
formation of the wax crystals which, in their turn, frequently depend all
the previous history of the sample. In order to eliminate the latter
variable the sample is preheated to a relatively high temperature before
starting the test in order to bring the wax crystals completely into oil
solution.
Sachanen 40 observed that the solidification temperature of oils varies with the
temperature to whic.h the; samples were heated, and that higher l)reh:-a~ing temt)'cr~
tures depress solidification point which rises, however, to its ongmal value0 III
storage. Cherllozhukov and Gutzait 50 recommend heating the oil to 212 F.
(100 0 C.), in order to eliminate the effect of previous treatments. W oog, Ganster,
and Coulon,51, 02 find that if the oil is initially cooled at a very slow rate to -121 f'
(- 85 C.), and then reheated the melting point is at its maximulll while rapid
cooling does not give sufficient time for formation of the wax crystals,
0
Heating the oil before testing may cause a change not only in the
pour test of the oil but also in its specific gravity ancl viscosity. These
three attributes may be raised or lowered by preheating the samples,
depending on whether cooling takes place with the oil at rest or in
motion. They are raised or remain unaltered if cooling is accompanied
by stirring and lowered if the cooled sample is held at rest. Investigation
of the crystal structure of separated ,vax particles substantiates the conclusion that these differences should be attributed to the differences in
the size and quantities of the wax crystals present,53 While the above
phenomena are not unusual with oils of Pennsylvania type,54 they are
also observed with Mid-Continent oils which contain both wax and
asphalt.
An interesting observation of Moerbeek and van Beest 55 on the
sensitivity of pour points to the thermal history of fuel oils showed that
addition of small percentages of asphaltenes, precipitated from residual
fuels by pentane, to a residual fuel oil, the pour point of which was
insensitive to the temperatme or pretrea.tment, improved the sensitivity
of this fuel to the pour test. On the other hand, removal of asphaltenes
from fuel oils, which are in themselves temperature sensitive as to their
pour points, made them insensitive to temperatures of pretreatment.
It is well known that distillate fuels are, in general, not temperature sensitive
with respect to their A, S, T, M. pour test, while residual fuels often give different
results when preheated to different temperatures,
The pam test of an oil with or without addition of a pour point depressant, may in certain instances show no difference when the samples are
tested by following the standard procedure,50 while on slow chilling,
samples containing the pour point depressant may show a considerably
lower pour test. 57 Likewise oil samples, particularly those containing
pour point depressants or very high melting point waxes, may show a
low cloud test when tested under standard conditions, while on slow
chilling or on standing at relatively low temperatures for a certain length
of time, they may develop a cloud due to separation of wax at higher
temperatures than those which can be predicted from the cloud test.
173
The use of pour point depressants in lubricating oils and the general
characteristics of such products are discllssed in detail in connection with
the description of Paraflow, one of the commercial products which is
now being marketed on a large scale. The discussion below is, therefore, applicable also to other pOlIl' point depressants besides Paraflow,
Paraflow
Paraflow is a condensation product of chlorinated wax and naphthalene in presence of aluminum chloride. 58 It is marketed in oil solution
which permits careful adjustment of the pour point depressant qualities
of current production by varying the amount of oil used as diluent.
When added in small quantities to the oil, such as 0.5% or less, it effectively lowers the pour point without imfavorable effect on other oil properties. If, however, Paraflow is added in large quantities, such as 2%
or more, it may increase the carbon residue of the oil and the rate of
carbon formation in the engine:io Its effectiveness can sometimes be
improved if the oil has heen previously well refined from asphaltic and
resinous impurities. GO This, however, is of secondary importance as
Paraflow is practically always added to oils after they have been subjected to the variolls treating procedures. It should he noted, also,
that oils containing Paraflow should not be further refined, because
Paraflow may be removed from the oil in these operations, for instance,
by percolation through clay.
Paraflow is usually added to oils which have been already clewaxed
to a relatively low pour test, such as 20-25 F. in order to lower the
pour test still further, to OF. Or less. The use of Paraflow t11lder these
conditions permits the refiner to eliminate the necessity of using low
refrigerating temperatures and to avoid two dewaxing operations which
are sometimes needed if conventional dewaxing methods are employed
for attaining stIch low POtU" tests.
Doladugill, Solodovnik, ane[ Englin fll observed that addition of Paraflow to
Grozny mixed-base products containing 2-5% of paraffin wax has 110 effect on
their pour points. They believe that the medium holding the wax in solution has
a considerable effect on the behavior of Para flow and that oils containing aromatic
compounds of high freezing point are least affected by such additions.
174
Faraflow
% Volume in Blend
3
5
10
~----Pour
Coastal Distillate
~7()
-uS
-60
SO
RO
- 55
-50
-40
-25
- 5
100
+ 20
20
30
90
+ 10
Point,
F.
MidContinent Distillate
+10
-25
-50
-40
-30
-20
- 5
+ 5
+ 10
+ 20
1i5
43-Properties of Santoponr
Gravity, 0 A.P.L
Flash, 0 F.
Pour, 0 F.
S.U.V. at 210 F.
Carbon residue
N cutralizatioll number
26.7
485
+10
15tiA
1.4
0.02
Properties
Gravity, A.P.I.
26.8
325
S.U.V. at 100 00 F.
53.3
S.U.V. at 210 F.
~~
Viscosity index
Pour [loint, F.
+20
(>
Color, AS.T.M.
0.4
Carbon residue
Sligh oxidation number
9
0
26.8
325
53.3
9~
25.8
5iO
25.8
570
65.2
65.2
89
- 30
+20
(>
0.4
0.8
89
- 15
0.8
The effectiveness uf the commercial pour point depressants in lowering the pOUl' point of an oil may be visualized from the following experimental data, obtained in. adding various quantities of the pottt' point
depressants to a Mid-Continent oil of S.A.E. 30 specifications, and a
+ 20 D F. pour point. The quantities of pom point depressants added
to this oil are calculated on the basis of the actual quantities of active
ingredients in commercial prodncts.
Commercial [lroducts contain certain quantities of oil, which may amount to
60-80% of the total.
TABLE
Pour 'Point
of the Mixture, 0 F.
20
10
-10
-15
011
Mid-Continent Oil
0.000%
0.020%
0.0460/0
0.0900/0
0.124%
0.0000/0
(J.()09%
0.020%
O.04!l%
0.056)1,
176
I'our PDblt
of the 1:Iixturc, 0 F.
20
10
-10
-15
0.0000/0
0.0120/0
0.0360/0
0.078%
0.114%
0.0000/0
0.0050/0
0.0150/0
0.Q380/0
0.0600/0
The above data show that the relative quantities of the two inhibitors
required to lower the pour point of the oils to a given level are slightly
different for the two oils and that the ratios also vary somewhat with
the pour point to be obtained.
It is of interest to note that with some oils the addition of pour point
depressants has at first no effect on their pour point which begins to
change only after the quantity of depressant added is raised above a
certaitl 111inill1UtU.
177
heavy hydrocarbon distillate. Texaco Development Corp.'" '" uses variolls condensation products obtained by heating aromatic hydrocarbons such as benzene,
naphthalcne, anthracene, fluorene, phenanthrene or their derivatives, with aluminum
chloride. Anderson" uses a residue from the distillation of a waxy mixture in
order to prevent formation of interlacing crystals; Standard Oil Development Co.co
employs for this purpose wax tailings; Anderson'" recommellds soaps of triethanolamine; Moser"' specifies various addition agents; etc.
See also a uescription of the use of para flow in c011l111ercial centrifuging.""
Bibliography
1.
Hall, F. C., Oil Gas J., 33, No. 45, 81-2, 96 (1935).
2. Davis, G. H. B., and BlaCkwood, A. J., Ind. Eng. Chem., 23, 1452-8 (1931); NUll. l'elrolel<lI!
178
Chcrnozhukov, N. I., and Gutzait, A. M., lzuest. Teplo/oId,. Inst., 1930, No.2, 36-40.
Woog, I'., Ganster. E., and Coulon, F., COlllpt. fend., 193, 850-2 (1931).
52. Woog, P., Ganster, E., and Coulon, F., A"". des cOlllbustibles liquides, 7, 279-81 (1932).
53. Gurwitch, L., 1'etrol""", Z., 19, 183-5 (1923).
54. Anon .. Oil Trade J., 16, No. 11, 16 (1925).
55. lIIocrbeck, B. H., and van Beest, A. C., Oil Gas J., 33, No. 42, 33-4 (1935) . .
56. Am. Soc. Testing Materia.ls, Standards, "Method of Test for Cloud and Pour PoUlts, D97-33."
50.
51.
57. McCloud, J. L., "I're,ent Concepts of the Relation of A.S:r.l.,L Pour Test to Service
Requirements of Oils," Am. Soc. Testing Materials, Symposium on Molar Lubricants,
Mar. R, 1933.
58. Davis, G. H. B., U. S. Palent 1,815,022 (July 14, 1931): Standard Oil Development Co.,
British Patent 402,253 (Nov. 30, 1933), Dutch Patent 64,852 (Apr. 3, 1933), French
l'"tent 762002 (Apr. 3, 1934), British Patent 415,065 (Aug. 13, 1934), and Germl111
I'atent 603),69 (Sept. 26, 1934); MacLaren, F. n., U. S. Patents 1,963,917-8 (June 19,
1934), and U. S. Patent 2,030,307 (Feb. 11, 1936): Frolich, P, Ie, U. S. Pate11t 2,015,748
(Oct. 1, 1935); M"cL'Hcn, F. H., ""d S\od<d'~I., T. E., U. S. Vatent 2,057,104 (Oct. 13,
1936). I'arldlOlIlenko, V., Novosti Neftepercrabotld, 3, No.5, 2-3 (1936), describes
preparation of Ilarn.fiow on a commercial scale. Properties of Paraflow nrc described
0)' Davis, G. H. B., and Blackwood, A. J., Natl. 1'ctrolew" News, 23, No. 46, 41-4, 46-7,
49, 52 (1931), Ind. EIIIJ. Chew., 23, 1452-8 (1931), Oil Gas J., 3{), No. 26, 46-8, 128
(1931), and Refiller Natural Gasoline Mfr., 10, No. 11, 81 (1931): Ramayya, Ie S., and
Khaiman, S., Nejtyanoe Khoz., 26, No. 12, 37-44 (1934).
59. Suida, H., and Poll, n., Petro!c"", Z., 29, No, 23, Motorenbctricb Maschinen-Schm;emng, 6,
No.6, 2-4 (1933).
(JO. Winning, C., [Ll1d Young, r. 1., U. S. Palent 2,045,742 (June 30, 1936).
61. Doladugin, A. 1., Solodovnik, M. S., and Englin, B. A., Nejtyanoe Kohzyaistvo, 28, No.4,
68-78 (1935).
62. Tanak<i, Y., and Taki7,[Lwa, :M., J. Soc. Che",. Ind., Japan. 39, Supp!. binding, 235-6 (1936).
63. Davis, G.
M.
65.
66.
67.
68.
69.
70.
71.
72.
74.
75.
76.
77.
78.
79.
80.
8!2'.
8
83.
84.
85,
86.
87.
88.
n. n.,
G. H. B., and Frolich, P. K., 1'enna. State Coil., fr'lineral Illd. E"p. Sta., !Jull., 12,
57-63 (1933).
Reiff, O. M., and TIadertscher, D. E., U. S. Patents 2,048,465-6 (July 21, 1936).
Burma}! Oil Co., British I'ntcnt 394,414 (June 29, 1933).
Lyons, H. N., U. S. Patent 1,920,922 (Aug. I, 1933).
Osterstrom, R. C., and Wagner, C. R, U. S. Palent 1,967,099 (July 17, 1934).
Henriksen, A., U. S. Patent 1,901,240 (Mar. 14, 1933).
Johnson, J. Y., British l'atent 397,169 (Aug. 14, 1933).
Anderson, J. A" U. S. Patent 1,998,648 (April 23, 1935).
Manley, R. E., McCarly, B. Y., and Gross, H. H., U. S. Patent 2,045,305 (June 23, 1936).
Manley, R. E., Mcea~ty, B. Y., and Gross, H. H., Canadian Patent 359,464 (July 28, 1936).
Pevere, E. F., Canadian I',tlent 357,661 (May 5, 1936).
N. V. de lIataafsclle Petroleum Mantschappij, French Patent 79.1,133 (Jan. 16, 1936).
Montgomer)', S. A., U. S. Patent 2,053,812 (Sept. 8, 1936).
Funstcn, S. R., U. S. Patent 1,857,370 (MilY 10, 1932).
Schott, J. E., U. S. Piltent 1,857,4U4 (M.iCY 10, 1932).
Jones, L. D., U. S. Palent 1,881,643 (Oct. 11 1932).
Chase, G. F., and Anderson, J. A., U. S. Pa'tent 2,034175 (Mill'. 17, 1936).
Hopper, B .. U. S. Patent 2,031,108 (Feb. 1B, 1936). '
Quinn, T. W., U. S. 1'(ltent 1,963,175 (June 19, 1934).
Texaco Development Corp., British Patent 437,779 (Nov. 5, 1935).
Texaco Development Corp., Frencll Patent 790,440 (Nov. 21, 19.15).
Anderson, J; A" U. S. Patent 2,036,188 (Apr. 7, 1936).
Standard 011 Development Co., French Patent 780,999 (:i\oIay 7 1935).
Anderson, J. A" U. S. Patent 2,059,837 (Nov. 3, 1936).
'
Moser, F. R, Dutch Patent 38,207 (May 15, 1936).
Anon., Oil Gas ]" 35, No. 36, 41, 43 (1937).
Chapter XVII
Viscosity Index hnprovers
The high viscosity iudex characteristics of oils intended for lubricating engines operating over a wide temperature range are of considerable importance in order to insure satisfactory lubrication under a variety
of service conditions. As already pointed out in Chapter I, the viscosity
index is an empirical relationship based on the viscosity-temperature
susceptibility characteristics of two typical crudes, and, for this reason,
has no theoretical foundation. However, other proposed methods have
no distinct advantages over this empirical method of classifying natural
petroleum products, while the simplicity of the viscosity index concept
has favored its wiele adoption by the petroleum industry.
In refining natural petroleum oils it is economically possible to
improve their viscosity index up to a certain maximum as further
refining has only an additional negligible effect on viscosity index characteristics. Further marked improvement can be effected, however, by
adding to the oil various types of substances which are described below.
180
Exanol
The above principles have been applied in practice for improving
the viscosity index of commercial products by the 1. G. Farbenindustrie
181
A.-G.} and the Standard Oil Co. (N. J.),:! who developed a special
heavy resin-like synthetic material, obtained by polymerization of unsaturated hydrocarbons, which on a(ldition to lubricating oils raises considerably their viscosity index. The product is known by tile trade
name "Exanol" ane] can be bought separately for adding to lubricating
oils which are already in the automobile crankcase and which do not
contain it.~ Oils containing these types or substances are likewise
marketed under the trade name of "Univis." The effect on their viscosity indexes of adding "Exanol" to various lubricating oils is shown
in the following table. 4 , r,
TABLE
47-Effcct
011
Exanol
%
Ad,lcd
Dasc
Coastal distillate
,---Sayholt Viscosity--.....
100" F.
210 0 F.
0
0.5
1.5
3.0
5.0
90 V. I. distillate
Pennsylvania oil
49.2
2G
441
54.0
51
627
1,020
1,851
66.0
91.5
147.5
51.4
296
353
0
O.S
1.0
2.0
5.0
0
0.5
1.0
418
SCiI
U22
237
273
332
432
1,050
2.0
5.0
V.l.
358
80
99
111
91
100
106
55.4
60.6
73.0
136.0
49.0
52.0
58.4
68.6
124.0
11-1125
100
lOG
119
126
128
The effect of adding "Exanol," 011 various properties of the oil other
than viscosity index, is ShOW11 in the following table, r,
TABLE
48-Effect
A.P.1. gravity
Flash point (deg. F.)
Viscosity at 100 F.
Viscosity at 210 F.
Viscosity index
Color
Conradsol1 carbon
residue (per cent)
Pour point (deg. F.)
0
30.7
420
195
45.5
98
??~
--4
0.008
10
30.7
420
343
60
123
30.2
425
254
-t9.2
92
20~
17:l
0.014
10
10
0.018
29.6
425
598
77.8
119
17
0.021
10
28.6
445
488
64.6
100
I}
0.722
30
Base
Stock
He"
+"ExanoI"
28.5
440
882
92
117
1}
0.794
30
Univis Oils
The properties of the commercial Univis oils are claimed to be those
listed in the following table. u
182
Saybolt Universal
Viscosity at 0 F.
210
130
100
70
30
0
-20
Viscosity index
Univis
Naphthenic
Base Oil
40.7
64.5
95
167
500
1,500
3,900
39.4
68
113
242
1,100
5,500
22,000
Univis
47.9
93
150
282
880
2,750
7,000
153
Univis
Parafiinic
Base Oil
62.4
153
264
520
1,670
5,300
14,000
150
56.8
175
368
980
5,700
33,000
165,000
101
Ullivis
77.4
217
388
775
2,630
8,800
22,000
146
183
ester-ethers of cellulose or similar highly polymerized hydrocal"bolls, such as tristearyl cellulose; Ruhrchemie A.-G.' specifics polymerization products obtained by
treatmg gases containing ethylene and propylene with condensing agents such as
aluminnm chloride,
iron chloride, zinc chloride or boron fluoride; Standard Oil
Deyelopment Co. 21" , adds to the oil an oil soluble linear polymer of iso-butylene
whIch has a molecular weight higher than 30,000; Standard Oil Development CO.,~l
and Fulton and Mikeska," recommend condensation product of ethylene dichloride
and benzene or similar polymers of the nonasphaltic chain type comprising alternate aromatic rings and aliphatic chains; T. G. Farbenindustrie A.-G." adds to the
oil up to 10'70' of condensation products obtained by subjecting hard or white
paraffin to the action of a silent electric discharge; Standard Oil Development
Co.' employs high molecular weight, oil soluble, oxygen free polymerization products of acetylene or acetylene derivatives; etc.
Pre-Diluted Oils
As already briefly mentioned, viscosity index improvement is likewise
obtained by diluting the oil with light petroleum fractions, such as kerosene
or heavy naphtha. In cold weather the heavy gasoline fractions tend to
concentrate in the crankcase due to excessive choking and the necessity
of using relatively rich gasoline-air mixtures. \iVith engines having no
special provision for eliminating these dilution effects, the oil finally
becomes diluted with such light fractions until equilibrium conditions are
reached. The oil diluted in this way offers, however, less friction in
starting than the same oil before dilution occurred. In order to avoid
such difficulties with fresh oils it has been recommended to pre-dilute
them with light petroleum distillates to the extent corresponding to the
equilibriul11 conditions reached in the engine. Such oils 27 are being
used commercially, although their utility becomes of increasingly less
184
Bibliography
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3.
4.
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Davis, G. H. B., Canadian Patent 346,0:12 (Nov. 13, 1934).
Picr, lit, Christmann, F., and Donath, E., U. S. Patent 2,049,019 (Tuly 28, 1936).
1. G. Fal'henindustrie A.-G., French Patent 758,269 (Jan. 13, 1934).
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(Aug. 9, 1934).
Mikeska, L. A., and Fulton. S. C.. U. S. Patent 2,072,120 (Mar. 2, 1937).
Pier. 111.. U. S. Patent 2,018.871 (Oct. 29, 1935).
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Eichwald. E., C"m,\lan Patent 059.595 (AUR. 4. 1936).
Pevere, E. F., U. S. Patent 2,045,922 (June 30. 1936).
N. V. de Jlataafsche J'etroleum 1I1aatschappij. French Patent 798,722 (May 25, 1936).
Ruhrchemie, .'1..-0., Frem,h Patent 791,950 (Dec. 19. 1915).
Standard Oil Development Co., French Patent 800,144 (June 27, 1936).
Standard Oil Development Co., French Patent 801.715 (Aug. 14, 1936).
Standard Oll Development Co . French Patent 784,570 (July 22. 1935).
Fulton, S. C., and Mikesk:t, L. A.. U. S. Patent 2.072.107 (Mar. 2, 1937).
I. G. Farhenindustrie A.-G., German P"tent 635,671 (Sept. 22. 1936).
Standard Oil Development Co .. German Patent 634,511 (Aug. 29, 1936).
Wilson, R. E .. n. S. I'atent 1,831.Q53 (Nov. 10, 1931).
Barnard. D. P .. 4th, U. S. Patent 1,796,857 (Mar. 17, 1931), and Canadian Patent 317,695
(Dec. 1. 1931).
Standard Oil Development Co., llriti'h Patent 401.341 (Nov. 7, 1933), and French Patent
736.983 (May 11. 19.12).
Chapter XVIII
Oiliness Carriers
One of the major requirements of a good lubricant is its ability to
maintain a film between the moving metal surfaces and, thus, eliminate
direct metal to metal contacts. This problem is not of particular importance when the clearances between the moving parts are large. Under
the latter operating conditions the viscosity of the oil is of primary importance and determines the satisfactory behavior of this oil in the engine.
Oiliness
However, with increased bearing pressures the oil tends to be gradually
squeezed out of the bearings with the resulting increase in the friction
coefficient. At still higher pressmes the oil is completely displaced from
the bearings and metal to metal contacts are established. The tenacity
with which a given oil is capable of adhering to the metal at such high
bearing l)!"cssnres is commonly referred to as "oiliness." Oiliness is
usually defined as that property of the oil which can make a difference in
the friction when two lubricants, having the same viscosity at the temperature of the film and at atmospheric pressure, are used under identical
conditions.1 Experimental work has shown that oiliness of lubricants
may be improved by addition of the variolls types of substances which
are discussed below.
vVhen the pressure between the moving parts is increased, however,
to a point when none of the known lubricants is capable of maintaining
the film between the metal surfaces, direct metal to metal contacts become
inevitable. Such conditions are encountered, for instance, in lubrication
of automobile gears where pressures between the gear teeth may reach
values as high as 400,000 lbs. per square inch with rubtJing velocities
ranging frOI11 zero to ,300 feet per minutc. 2 Under such conditions the
main function of the lubricant is to prevent seizure between the moving
parts by properly preparing their surfaces so as to insure minimum friction
and lowest possible rate of deterioration when the surfaces are brought
into intimate contact while the engine is operating.
Omitting the discussion of the, as yet, rather insufficiently clarified
mechanism of the action of lubricants under high pressures, it is feasible
to assume, however, that at low bearing pressures the oil is capable of
protecting the bearings irrespective of the tenacity with which it adheres
to the metal. At increased pressures the ability of the oil to adhere to the
185
186
OILINESS CARRIERS
187
mineral oils is usually more than sufficient for all practical purposes, including motor lubrication, as in well lubricated bearings the loads rarely
exceed 2,000 lbs. per square inch and the rubbing speeds are usually high
enough to maintain a constant film of oil for separating the bearing and
the journal. \Vhen loads are high, however, such as in engines during
the break-in period or in special types of industrial machinery, it is frequently desirable to improve the oiliness of lubricating oils by the addition
of special oiliness carriers.
Oiliness Carriers
Of the substances used for improving oiliness of lubricating oils, oleic
acid was until recently of some commercial importance,S being used in
manufacturing the so-calJed "germ-processed" oils. Addition of this acid
to the oil in quantities as low as 0.50/0 is usually sufficient to insure the
desired degree of improvement in oil properties. Stearic: acid is claimed
to be even more effective in this respect than oleic acid but it is not
as suitable fOl" practical purposes due to its low solubility characteristics.
The use of stearic acid as well as other acids containing at least sixteen
carbon atoms in the molecule, such as arachidic or cerotic acids, is nevertheless recommended in some of the patents. 9
Mildly oxidized vegetable oi15,10 as well as various derivatives of
organic acids, particularly esters, are also recol11mended. l l
Other groups of substances used for improving oiliness characteristics
include halogenated organic derivatives, of which chlorinated esters of
stearic acid appear to be particularly promising and are being llsed COI11mercially.
Lincoln and Henriksen'" use halogenated ot'gank esters; Litlcoln and Henriksen,'3 and Henricksen and Hartzell," recommend chlorinated stearic acid or
similar compounds; Henriksen and Lincoln 1(' employ halogenated amides of aliphatic acids, such as chlorinated a-tolyl stearamide or sulfochlorinated o-toly! stearaluide; Continental Oil Co.'" specifies halogenated organic oxygen compounds
including ethers, alcohols, aldehydes, ketones, acids or esters; Henriksen and
Lincoln 17 use a condensation product of chlorinated stearic acid and diphenylem::
oxide or similar derivatives; Lincoln and Henriksen 1ll specify condensation products such as derived from chlorinated lard oil and naphthalene; Lincoln and Hen'
riksen ,. cover condensation products derived from two halogenated fatty acids or
halogenated esters; Lincoln and Henriksen "0 use halogenated wax and halogenated
organic acid condensation product, such as derived from chlorinated paraffin and
chlorinated stearic acid; Henriksen and Lincoln"l use a halogenated diphenylene
oxide; Henriksen and Lincoln ""."" recommend halogenated aromatic hydrocarbons
of the phenylbenzene group. Davis, Sibley, and Lincoln,""' and Lincoln and
Byrkit:J5 discl1sS the effects of chlorinated aliphatic acid esters on the oiliness
characteristics of oil to which they afe added, while Clafk, Sterrett, and Lincoln "0
present the results of their studies on similar substances by the X-ray diffraction
methods; Lincoln and Henriksen 27 recommend condensation products which contain
a small amOl1nt of halogens in organic combination; Moran'" patented the use of
Nicolet and de Mitt's acid; Steiner"" specifies .halogenated terpenes; Prutton and
Smith 3D. 91, .., 83,.' enumerate a large number of halogenated organic derivatives
suitable for improving oiliness of lubricants.
188
Nitriles,31; nitroaromatics and amines,3G and various sulfur componnds,37 are also included in different patents.
Ralston, Christensen, Hoffman, Selby, and Conquest,'S discuss the use of. fatty
acids nitriles amides ketones, thioamides and other substances wIth the particular
reer~nce to ~xtreme 'pressure lubricants. Byers '" gives a survey of patent literature on extreme pressure lubricants.
* Ralston and Christensen '" employ mixed kctones for improving both oiliness
and pour point of oils; Christensen and Selby'" employ for the same purpose
condensation product, of highcr fatty chlorides and the coal tar products.
Bibliography
Herschel, W. H,. Trans, Sac. Autamati1!e Eng .. 17, I, 282-320 (1922); Hersey. M. D., MeeT,.
ling., 55, 5[;1-6 (1933); Hersey, M. D . "TheorY of Lubrication," J. Wiley and Sons,
Inc" New York, 1936.
2, Mouger, H. C., "nd Almon, J. 0., Oil Gas J., 30, No. 26, 109 (1931).
3. Woolgar. C, W., Oil Gas J,. 34, No, 18. 34-9 (1935).
4, Breth, F, W., anrl IAberthson, L., Oil Gas J,. 34, No. 51, 42-5 (1936).
5. Barnarrl. D. p" and Barnard. E. R, Refiner Natural Gasoline Mfr,. 14, 324-8 (1935);
Anon .. Nail, Petroleum News, 27, No, 21, 42, 44 (1935). Sec also Everett, H. A., Oil
Gas J., 36, No.5, 53-6 (1937).
1.
OILINESS caRRIERS
189
Clark, G. L., Sterrett, R R., and Lincoln, B. H., h,d. EH!!. el"""., 28, 1318-28 (1936);
. and Rei,""r Naturnl Gasolille Mfr., 14, 512-22, 536 (1935).
Da,vls, L. L., Slbley, B. E., i:tnd Lincoln, n. H'J RC"Jlller Nut.nral GllsoliHC ,AIjy., 14, 523-35
(1935).
8. SuuU1combe, J. E., anti \Vdls, H. 111., U. S. Patent 1,319,129 (Oct. 21. 1919), amI British
l'atcnt 130,877 (Feb. 5, 1918).
9. Wells, H. 111., and SOllthcombe, J. E., French l'atent 689,289 (July 17, 1929); Southcombc,
J. Eo, and Shenton, M. A., British Patent 412,101 (June 21, 1934).
10. Standard on De"elopment Co., French Putent 789,862 (Nov. 7, 19.15).
11. Frolich, p. K, British Patent 402,262 (Nov. 30, 1933), and Canadian Patent 3'15,547 (Oct. 23,
1934); St<mdard Oil De1'eloplllent Co., French Patent 785.839 (Aug. 20, 1935); Wiezevich, I'. J., Canadian Patent 363,203 (Jan. 5, 1937); Ralston, A. W., and Christensen,
C. W., U. S. Patent 2,077,068 (Apr. 13, 1937), employ reaction products of a coal tar
fraction and stearic or other fatty acid. Ellis, C., U. S. Patent 2,018,758 (Ort. 2Y,
6.
7.
1935), uses reaction pl'oducts of stearic or oleic add with trieth.u.nolanlinc or similur
13.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
substances. Mikeska, L. A., ami Smith, C. F . Canadhm Patent 365,079 (11m. 30, 1937),
covers suhstances such as blown coconut oil. Clarkson, R. G., C:tllauian Patent 362,37(i
(Dec. 8, 1936), employs high molecular wei gIl( :.Lliphatic alwhols.
Lincoln, B. n., and Henriksen, A., U. S. Patent 1,944,941 (Jan. 30, 19,H).
Lincoln, B. H., and Henriksen, A., U. S. Patent 2,074,338 (lIIar. 2.1, 1937).
Henriksen, A., and Hartzell, B., Canadian Patent 335,760 (Feb. 4, 1936).
Henriksen, A., and Lincoln, B. lL, U. S. Palent 1,959,054 (May 15, 19.14).
ContinenhLi Oil Co., French Paterl! 761,243 (Mttl'. 14, 1934).
Henriksen, A., and Lincoln, B. H., U. S. Patent 1,9.19,979 (Dec. 19, 1933).
Lincoln, H. H., and Henriksen, A., U. S. I'atent 1,939,993 (Dec. 19, 1933-).
Lincoln, B. II., and Henriksen, A., U. S. Patent 1,939,99-1 (Dec. 19, 19.13).
Lincoln, B. H., 'lIld Henriksen, A., U. S. Patent 1,939,995 (Dec. 19, 193:1).
Henriksen, A., and Lincoln, B. H., U. S. I'aten! 1,936,670 (Nov. 28, 1933).
Henriksen, A., and Lincoln, 13. H., U. S. Palent 2,066,354 (Jan. 5, 193i).
Henriksen, A., and Lincoln, B. H., Canadian Patent 35'1,803 (Dcc. 17, W35).
Davis, L. L., Sibley, B. E., and Lincoln, B. 1I., Proc ..'1m. Pc/roll""u lust., III, 16, 81-103
(1935).
25,
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
07.
Lincoln, B. H., and Byrkit, G. D., "World Petroleum Con~ress," Paris, (1937).
Clark, G. L., Sterrett, R. R., and Lincoln, It H., Rc]iuer Natural Gasoline l1Ifr., 14, 512-22,
536 (1935).
Lincoln, B. H., and HCUl'iksen, A., U. S. Patenl 1,945,615 (Feb. 6, 1934).
Momn, R. C., U. S. Patent 1,850,561 (Mar. 22, 1932).
Steiner, W. L., U. S. l'atent 2,063,857 (Dec. 8, 1936).
Prutton, C. E., and Smith, ,fl. K., British Patents 451,'111-2 (July 29, 1936).
I'rutwn, C. E., and Smith, A. K, llritish Patent 452,914 (Aug. 31, 1936).
Prutton, C. E., and Smith, A. K., Hritish Patent 453,047 (Aug. 31, 1936),
Prutton, C. E., and Smith, A. K., British Patents 453,114-5 (Au!,:. 31, 1936).
Pruttoll, C. E., aTld Smith, A. K., British Patent 454,552 (Sept. 29, 1936).
Kalston, A. W., Pool, W.O., and Harwood, J., U. S. P"tent 2,053,(J45 (Sept. 1, 1936), recom
mend illiphatic nHriles containing at least six carbon iltums, such itS stcaro- or palm itonitriles.
Ca]cott, W. S .. and McHamess, R. C., U. S. Patent 2,066,17,1 (Dec. 29. 1936). Penniman,
W. n. D., U. S. Patent 2,061,:-128 (Nov. 17, 1936), useS (;lllow oil and diphenylamine.
Farrington, B. B., and HUl1lpl,reys, R. L., U. S. I'atent 2,020,021 (Nov. 5, 1935), specify
thiocarbonates; Wakefield, C. C., and Co., Ltd., and Evans, E. A., British Patent 455,
235 (Oct. 15, 1936), use thiocthcrs: Humphreys, R. L., and Farrington, B. n., U. R.
Patent 2,073,841 (Mar. 16, 1937), employ thiaadds; Downing, F. B., and Benning, A. F.,
C~nadian
mer{"Llp~
Chapter XIX
Oxidation Inhibitors
One of the most important characteristics of lubricating oils is their
stability in service. A motor oil is frequently required to last for at
least 2,000 miles or more of driving while some drivers even consider
that changing of the oil is superfluous, particularly, if their cars are
equipped with filters. Transformer and turbine oils remain in service
for a number of years, while the life of cable oils is estimated as being
20 years or even longer. These drastic operating conditions require an
unusual stability fr0111 oils released to the market and consequently a
careful attention to the refining methods employed in their production.
Oxidation Inhibitors
As already mentioned the original conception of oil stability has been
associated with the inherent resistance of the oil molecules towards
oxidation, and oil refining was supposed to eliminate from the finished
oil all of the unstable molecules present. This conception prevailed until
the classical work of Moureu and Dufraisse 1 revealed the existence of
oxidation inhibitors, or substances which are capable of protecting less
stable molecules from oxidation even when such substances are present
ill exceptionally small quantities,-a few tenths or even a lew thousands
of one per cent all the volume of the oil. A description of inhibitors has
been given by Kulichevsky and Stagner? and need not be repeated in
detail, except for the following generalizations:
1. The presence of minute quantities of certain substances in an
oilmuy either promote or retard the oxidation of the oil when exposed
to the action of air or free oxygen.
2. The same substance may act as a promoter or as a retarder of
the oxidation reactions depending on the concentration of this substance,
nature of substances present in the oil, and the conditions of oxidation.
From the above, it follows that in investigating the oxidation inhibitors it is important to determine the optimum quantity of the inhibitor
required for protecting the oil from oxidation and not to restrict its
amount to a certain arbitrary concentration, to carry out the experimental
work under conditions approaching as closely as possible those
encountered ill service, and to employ the inhibitors in the particular
oil which they are intended to protect.
190
OXIDATION INHIBITORS
191
192
Corrosion Inhibitors
The above conception leads to a further assumption that inhibitors
added to the oil oxidized in presence of metals may act not only as true
anti-oxidants but also as substances passivating the catalytic activity of
metals. Such types of anti-oxidants will form a coating on the surface
of the metal, this coating being formed either by deposition of a dense
film of sludge or by formatiol1 of thin layers of metallic compounds produced by direct action of the inhibitors on the metal.
Among the ne\v types of inhibitors which recently have achieved
commercial importance, compounds of phosphorus are of considerable
interest as their protective action seems to be best explained by the above
surface theory. Besides phosphorus and related elements, such as arsenic
or antimony, organic compounds of chromium, bismuth, mercury, and
other metals appear to have a similar action. Thus it is claimed that a
good lubricant should contain organic chromium compounds for preventing
catalytic action of iron in the engine, and organic tin compound for
preventing deposition of carbon, and an organic lead compound for
OXIDATION INHIBITORS
193
A.
c.c."
to Lubricating Oil
Grade of oil
Temperature of oil
Time of test
Weigbt loss in oil without inhibitor
Weight gain in oil containing 0.25% Santolube
S.A.E. 20
350 F.
0
c.c.
24 hours
117 milligrams
7 milligrams
c.c.
1450 milligrams
16 milligrams
194
As is
'yV eight
122
0.0001
5052
0.004
6706
not determined
not determined
0.004
011
Characteristics
~---S.A.E..
As is
Gravity,
A.P.I.
S.U.V. at 100.0 F.
S.U.V. at 210 0 P.
Viscosity index
Plash point, F.
Pire point, 0 F.
Pour point, 0 F.
Neutralization nll111bel'
Color, A.S.T.M.
Carbon residue
0
20 Oil,---~
+0.50% Santolube C.C.
310
55.S
IIi}
30.5
303
55.6
116
425
480
420
475
30.6
-10
0.0
6
0.3
-10
0.3
6
0.3
OXIDATION INHIBITORS
195
Bibliography
1. Moureu, C., and Dufraissc, C., CampI. rend., 174, 258-64 (1922); Chelll_ }i,,/icws, 3, 11362
(1926); Chemistry Iir Industry, 47, 819 (1926).
2. I~a.lichevskYJ V. A., and Stagner, n. A'J HChcmical Refining of Pt:troleum," The Chemical
Catitlog Co., Inc. (ll.einhold l'ublishing Corp.), 1933.
3. Eyers, J. B., Natl. Petrol."", News, 29, No.6, 67-70 (1937).
4. Johnson, J. Y., British Patent 379,717 (Aug. 29, 1932), stabilizes oils by additiol\ of high
molecular weight substal\ces. Moser, F. R., Canadian Patel\t 3&1,928 (Mar. 2.1, 19:17).
uses for this purpose voltolized oleic acid and similar compounds.
5. N. V. de Bata,Lfschc Petroleum Maatschappij, French Patent 770,289 (Sept. 11, 1931).
6. N. V. de Bataafsehe Petroleum Maatschappij, British Patent 424,380 (Feb. 20, 19.15).
7. van Dijck, W. J. D., Canadian Palent 357,650 (1\Iay 5, 1936).
8. E. I. dtt Pont de Nemours and Co., Frendl Palent 790,666 (Nov. 25, 1935).
9. Prulton, C. F., and Smith, A. ,C, British Patent 454,215 (Sept. 25, 1936).
10. Eyers, J. H., Natl. Petrole"", News, 28, No. 51, 79-84 (1936).
11. Wakefield, C. C. and Co., Ltd., French Patent 480,448 (Apr. 26, 1935)_
12. Towne, C. C., U. S. Patent 2,078,472 (Apr. 27, 1937).
13. Evans, E. A., U. S. Patent 2,059,567 (Nuv. 3, 1936).
14. Rosen, R., Canadian Patent 365,078 (Jl.fitr. 30, 1937).
15. Standard Oil Development Co., French Patent 789,595 (Oct. 31, 1935).
16. Desmarais frh-cs, French llatcnt 805 1809 (Dcc. 1, 1936).
17. Griffith, A. A., and Helmore, W., British Patent 423,441 (Feb. I, 1935).
18. Ducamp, A. J., British Patent 368,025 (Mar. 3, 1932).
19. Gilbert, W. V., British Patent 455,096 (OCI. 14, 1936).
20. Gilbert, W. V., British Patent 455,097 (Oct. 14, 1936).
21. Sullivan, F. W., Jr., Shoemaker, B. H., and Taylor, Ie., U. S. Patent 2,079,0;1 (May .1, 19.17).
22. Mardles, E. W. J., CIt"IIl. Tmdc I., 95, No. 2472, 256 (193-\).
23. Moran, R. C., Evers, W. L., and Fuller, E. W., U. S. Patent, 2,0.18,342-4 (Oct. 21), 1936).
Chapter XX
Fluorescence Improvers
As is well known, extensive refining of lubricating oils with sulfuric
acid or solvents results in a considerable loss of their fluorescent characteristics. This is, generally, undesirable except in manufacturing highly
specialized colorless oils, sllch as medicinal oils, becallse the majority of
customers still continue to believe that the green fluorescence of Pennsylvania oils is all indication of their high quality.
FLUORESCENCE IMPROVERS
1!J7
(1) The elye should have no detrimental effect all any of the oil
properties which determine satisfactory performance of the oil ill service.
(2) The dye must be stable uncler usual service conditions as, due to
reasons already explained, it is also intended to conceal the actual appearance of the oil when in service.
( 3) The presence of the dye ill the oil should not be detected by the
customer by an unnatural appearance of such oils because the customer
is not yet accustomed to the use of colored lubricating oils although he
has become familiar with dyed gasoline.
(4) The dye should he difficult to remove from the oil by simple
chemical methods, as, due to the present state of market requirements, it
may serve as a pretext for the competitor to expose the presence of dye
in an oil to the customer and thus to unfavorably influence his opinion.
(5) The dye should be reasonably cheap, although this requirement
is usually secondary due to the exceptionally small quantities of dye
employed for coloring the oil. These quantities are frequently not over
10-20 milligrams of dye per gallon of oil and may be considerecl as being
negligible.
It seems questionable, however, whether a dye answering all of the
above requirements has been yet developed, and the refiner is always
required to give the individual dyes, which are now available on the
market, a careful scrutiny before adopting them for commercial usc.
198
ization of the liquid sulfur dioxide extracts,S hydrocarbon oils containing green fluorescent substances extracted from a coal tar residuum,l), 11
condensation products of liquid monoolefins with 20-7070 of polynuclear organic substances obtained in the presence of aluminum
chloride,l etc. It is also recommended for imparting fluorescence to
the oils to contact snch oils with clay in presence of a coal-tar distillate,ll or with finely divided cracking still coke. 12 Synthetic dyes
include ari1inophenylbcnzylthiazole or other primuline bases,13 organic
dyes of a heterocyclic structure containing oxygen in the structure, such
as 6,12-dimethy]coeroxene, 6,12-dimethylcoeroxenol or one of its acetates,
triphenyldioxazine; triphenylbenzoful'an or substitution products thereof,l-! dyes obtained by heating a mixture of a water-insoluble soap, stearic
acid, and a dye of the acridine, rhodamine, eosine or eurhodin type,lr,
various aniline dyes,lG products obtained by heating naphthenic acids
with acridine orange bases,17 compounds of the ceranthrenic or cerbianthrcnic series, such as ceroxene (yellow with gl'eell fluorescence), 1,5diccramidonine (crimson with yellow-red fluorescence), 10-methylbellzoceroxenol (red yellow with greenish fluorescence), 14-l1lethylcerthienol-lO acetate (yellowish with green fluorescence) or acetyl compounds
of ceramindenol (red with yellow-red fluorescence) 18 hydrocarbons
obtained by heating pyrene in presence of aluminum chloride,l!l polymers
produced from normally gaseous hydrocarbons,20 compounds obtained by
heating anthraquinone, bcnzanthrone or similar substances or their clerivatives,21 and others. Addition to the oil of 0.01-0.3% of furfural before
subjecting the oil to a sulfuric acid treat may also improve fiuorescence. 22
For preventing organic dyes fro111 separating fr0111 oils the mixtures may
be stabilized by addition of water insoluble soaps, such as fatty or resinous soaps of zinc, calcium, magnesium, or aluminul11. 23 However, addition of fluorescence agents is not absolutely necessary for imparting to
oils the yellowish-green blo0111 characteristic of Pennsylvania oils. Sufficient improvement may be frequently obtained by contacting oils with
clay at elevated temperatures, by treating oils with sulfuric acid in propane solution, or by other conventional refining methods.
Bibliography
1. Anan., Petrole.,,,,, Times, 24, No. 599, 28 (1930).
2. Spencer, C. F., U. S. Patents 1,973,118-9 (Sept. 11, 1934); Har~er, D. K., U. S. Patent
2,051,255 (Aug. 18, 1936); Manley, R. E., and Gross, H. H., U. S. Patent 2,040,057
(May 5, 1936).
3. Lang, F. R., U. S. raten! 1,974,778 (Sep!. 25, 1934).
4. Clu1ow, F. S., U. S. Patent 2,017,529 (Oct. 15, 1935), and Canadian Paten! 351,719 (luI)'
16, 1935).
.
S. Smith, H. G., U. S. Patent 1,944,851 (Jan. 23, 1934), U. S. Patent 1,868,473 (July 19, 1932),
and Canadian ratent 343,584 (July 31, 1934).
6. Shaffer, S. A., and Fasce, E. V., U. S. Patent 1,988,753 (Jan 22, 1935).
7. Miller, C. C., U. S. Patent 1,S69,508 (Aug. 2, 1932).
..
8. Moser, F. R., U. S. Patent 2.010,606 (Aug. 6, 1935). Ln,ar, A., and Evans, J. M., U. S.
Patent ~.05~,696 (Oct. 2~, 1936). employ substances obtained by eXlracting liquhl
sulfu,' d,ox,de extracts wlth hydrocaruon solvents.
9. Smith, L. n., Funslcn, S. R., and Field, H. W., Cnnadian Patent 362.539 (Dec. 15, 1936).
FLUORESCENCE IMPROVERS
199
10. 1. G. Farbenindusll'ie, A.-G., Ddtisll Patent 409,696 (Apr. 30, 1934); I{abe. Ii., U. S. Patent
2,028,472 (Jan. 21, 1936); Hartmann, B., and Ralle, H., U. S. l'atent 2,071,521 (Feb.
23, 1937).
11. Black, J. C., Rial, W. D., and McConnel, J. R., U. S. I'atcnt 1,839,012 (Dcc. 29, 1931).
12. Camp, H. W., U. S. Patent 1,961.898 (June 5, 1934).
13. Kuhrmo.n, F., and Siebert, 0., U. S. Patent 1,962,564 (June 12, 1931).
14. Wilmot and Cassidy, Inc., French P"tent 778,660 (Mar. 22, 1935).
15. Orelup, J. W., French Patent 759,767 (Feb. 9, 193"), and British Patent 424,205 (Feb. IS,
1935).
16. Vellner, E., British Patent 359,590 (July 29, 1930). Small quantitie" nf SUell materials as
17.
18.
19.
20.
21.
22.
23.
oil of doves, wintergreen, peppermint or lavendcl', are also added for scenting the oil.
Cassidy, T. A., U. S. Patent I,S60,HSO (May 31, 1932).
I. G. Farbenindustrie, A.-G., French Patent 791,764 (Dcc. 17. 19.15).
Anglo.Iranian Oil Co. Ltd., and Birch, S. F., British l'atent 438,435 (Nav. 11, 1935).
Towne, C. C., Canadian Patent 363,528 (Jan. 19, 1937).
Tinker, J. M., and Wcinmayr, V. M., U. S. Patent 2,074.288 (Mar. 16, 1937).
Smith, E. J., u. S. Patent 1.998,292 (,\pr. 16, 1935).
Patent Fuels and Color Corp" British Patent 357,179 (June 17, 1930).
Appendix
TABLE
11.5
17.5
1B.O
18.5
19.0
19.5
20.0
20.5
21.0
21.5
22.0
23.5
23.0
2,1.5
21.0
2-1.5
25.0
25.5
26.0
26.5
27.0
27.5
28.0
28.5
29.0
29.5
30.0
30.5
31.0
~1.5
32.U
32.5
33.0
33.5
34.0
34.5
35.0
35.5
36.0
36.5
37.0
37.5
38.0
38.5
39.0
,19.5
0.1201
0.1205
0.1209
0.1213
0.1218
0.1222
0.1226
0.1230
0.1235
0.1239
0.1243
0.1248
0.1252
0.1256
0.1260
0.1264
0.1269
0.1273
0.1277
D.UR\
(i.4041
6.4265
6.4490
6.4717
6.4946
6.5176
6.5400
6.5625
6.5852
6.6080
6.6302
6.6534
6.6758
6.6985
6.721.1
6.74H
6.7665
6,7889
6.8114
6.8341
(i.3030
6.3250
6.3472
6.3695
6.3920
6.4146
6.4367
6.4588
6.4812
6.5037
6.5255
6.5483
6.5704
6.5937
6.61S1
6.6369
6.65<}6
6,6811i
6.70,,8
6.72G2
1.01729
1.02085
1.02443
1.02803
1.03166
1.0.1532
1.03887
7.778
7.752
7.727
7.701
7.676
7.651
7.627
7.602
7.578
7.554
7.529
7.505
7.481
7.458
7.4.>4
7.410
7.387
7.364
7.341
7.318
0.1286
0.1290
0.1294
0.1299
0.1303
0.1307
O.U11
0.1315
0.1320
0.1324
0.1328
0.1332
0.1337
0.1341
0.1345
0.1350
0.1354
0.1358
0.1362
0.1366
6.8569
6.8799
6.9022
6.9255
6.9481
6.9708
6.9927
7.0157
7.0379
7.0603
7.0837
7.1064
7.1292
7.1512
7.1742
7.1975
7.2199
7.2424
7.2651
7.2880
6.7487
6.7712
1i.793Z
6.8\61
6.838.1
6.3607
6,8823
6.9048
6.9268
6.9488
6.9718
6.9941
7.0166
7.0382
7.0609
7.0838
7.1059
7.1281
7.1504
7.1729
1.08923
1.09288
1.09642
7.296
7.273
7.251
7.228
7.206
7.184
7.163
7.141
7.119
7.098
7.076
7.055
7.034
7.013
6.993
6.972
6,951
6.930
6.910
6.890
0.1371
0.1375
0.1379
0.1384
0.1388
0.1392
0.13%
0.1400
0,1405
0.1409
0.1413
0.1417
0.1422
0.1426
0.1430
0.1434
0.1439
0.1443
0.1447
0.1451
7.3099
7.3331
7.3553
7.3787
7.4012
7.4239
7.4457
7.4686
7.4917
7.5139
7.5372
7.5597
7.5822
7.6049
7.6266
7,6496
7.6738
7.6960
7.7183
7.7407
7.1945
7.2172
7.2391
7.2622
7.284.1
7.3067
7.:;281
7.3507
1.16119
1.16486
1.16839
1.17211
1.17569
1.17929
1.18275
1.18639
1.19006
1.19359
1.19729
1.20085
1.20444
1.2080-1
1.21150
1.21515
1.21882
1.22251
1.22605
1.22961
0.9340
0.9309
0.9279
0.92,8
0.9218
0.9188
0.9159
0.9129
0.9100
0.9071
0.9042
0.9013
0.89B4
0.8956
0.8927
0.8899
0.8871
0.8844
0.8816
0.8789
0.8762
0.8735
0.8708
0.8681
0.8654
0,8628
0.8602
0.8576
0.8550
0.8524
0.8498
0.8473
0.8448
0.8423
0.8398
0,8348
0.8324
0.8299
0.8275
I'er
'1'011
8.328
8.299
8.270
8.241
8.212
8.183
8.155
8.127
8.099
8.071
8.044
8.016
7.989
7.962
7.935
7.909
7.882
7,856
7.830
7.804
O.R~73
Cubic
l\Icters
TOll
1.0000
0.9965
0.9930
0.9895
0.9861
0.9826
0.9792
0.9759
0.9725
0.9692
0.9659
0.9626
0.9593
0.9561
0.9529
0.9497
0.9465
0.9433
0.9402
0.9371
10.0
10.5
11.0
Barrels
Long
Gallflll
Specific
Gravity
Barrels
Per
Per
Melric
Gallons
Per
Pound
Degrees
A.P.I.
12.0
12.5
13.0
13.5
H.O
14.5
15.0
15.5
16.0
16.5
17.0
Pounds
Per
201
7.373-1
7.3952
7.4182
7.440~
7.4625
7.4848
7.5062
7.5288
7.5516
7.5745
7.5964
7.6184
LDng
Ton
l.O42~5"
1.04606
1.0-1969
1.05321
1.05689
1.06046
1.0fi406
1.0676&
1.07119
1.07486
1.07841
1.08199
1.0856D
1.10012
1.10370
1.10731
1.11079
1.11445
1.11797
1.13153
1.12525
1.12885
1.13247
1.l359fi
1.13963
L14332
1.14688
1.15046
1.15407
1.15770
Cubic
1\Ieters
Per
Metric
Ton
1.0012.1
1.00472
1.00825
1.01180
1.01537
1.01897
1.02246
1.02599
1.02954
1.03311
1.03657
1.04020
1.04371
1.04725
1.05081
1.05427
I.0578R
1.0613R
1.06490
1.06845
1.07202
1.07563
1.07910
1.08274
1.08627
1.08982
1.09325
1.09684
1.10032
1.10381
1.10748
1.11102
1.1145S
1.1I802
1.12163
1.12526
1. I 2877
1.13229
1.13584
1.13941
1.14285
1.14646
1.14994
1.15360
1.15712
1.16066
1.16407
1.16765
1.17126
1.17473
1.17838
1.18189
1.18541
1.18896
1.19237
1.19596
1.19957
1.20320
1.20669
1.21019
202
TABLE
Degrees
A.P,I.
Specific
Gravity
40,0
40,5
41.0
41.5
42.0
42.5
0.8251
0,8227
0.8203
0.8179
0.8155
0.8132
0.8109
0.8086
0.8063
0.8040
0.8017
0.7994
0.7972
0.7949
0.7927
0.7905
0.7883
0.78n 1
43,0
43.5
44.0
44.S
45.0
45.5
46,0
46,5
47.0
47 ..1
48.0
48.5
49,0
49.5
50.0
50.5
51.0
51.5
52.0
52.5
53,0
53.5
51.0
54.5
55.0
55,5
56.0
56,5
57.0
57.5
58.0
58.5
59.0
59.5
60.0
60.5
61.0
61.5
62.0
62.5
63,0
63,S
64,0
64.5
65.0
65.5
66,0
66.5
67.0
67.5
68,0
68.5
69.0
69.5
0,7~39
0,7318
n.7790
0.7775
0.7753
0.7732
0,7711
0.7690
0,7669
0.7649
0.7628
0.7608
0.75R7
0.7567
0.7547
0.7527
0.7507
0.7487
0.7467
0.7447
0.7428
0.7408
0.7389
0.7370
0.7351
0,7332
0.7313
0.7294
0.7275
0.7256
0,7238
0.7219
0.7201
0.7183
0.7165
0.7146
0.7128
0.7111
0.7093
0.707.,
0,7057
0.7040
Pounds
Per
Gallon
Gallol1s
Pel'
Pound
I-(ColltiIZ1ICd)
Bal'rels
Per
LOllg
Ton
Bnxrels
Per
Metric
Ton
Cuhic
Meters
PCI'
Cubic
Meters
Per
Long
Ton
Metric
Ton
6,870
0.1456
6,850
O.14fill
6.8.10
6,810
6.790
6.771
6.752
6.732
6.713
6,694
6,675
6.656
6.637
6.618
6,('00
6.582
0.563
6.545
6.526
6,509
0.1464
0.1468
0,1473
0.1477
0.1481
0.1485
0.1490
0.1494
0.1498
0.1502
0.1507
0.1511
0.1515
0.1519
0.1524
0.1528
0.1532
0.1536
7.7632
7.7859
7.8087
7,8316
7,8547
7,8767
7.8989
7.9224
7.9448
7.9673
7.9900
8.0128
8.0358
8,0588
8.0808
8.1029
8.1264
8.1487
8,1724
8.1938
7,6406
7.6629
7.6854
7.7079
7.7306
7.7523
7.7741
7,7972
7.8193
7,8415
7,8638
7,8863
7,90BR
7.9316
7.9532
7:9749
7.9980
8,0200
8.0434
8,0644
1.23319
1.20(179
1,24041
1.24405
1.24772
1. 25122
1.2.1474
1.2.1847
1,26203
1.26561
1.26921
1.27284
1.27M8
1.28015
1.28364
1.28715
1.29087
1.29443
1. 29819
1.30158
1.21371
1.21726
1.22082
1.22441
1.22801
1.23146
1.23492
1.23859
1.24210
1.24502
1.24917
1.25274
1.25032
1.25993
1.26336
1.26682
1.27049
1.2739B
1.27769
1.28103
6.490
0.47:1
6.455
6.437
6,420
0.1541
0.1545
0.1.149
0.1554
0.1558
0,1562
0.1566
0.1570
0.1575
0.1579
0.1583
0,1587
0.1592
0.1596
0.1600
0.1604
0.1609
0.1613
0,1617
0.1622
8,2178
8.2394
8.2(,23
8.2854
8.3074
8,3307
8,3529
8.3752
8.3990
8.4202
8.4442
8.4656
8.4885
8.5115
8.5347
8.5566
8,5800
8.6035
8.6244
8.6482
8.0880
8.1092
8.131R
8.1546
8.1762
8,1992
8,2210
8,2429
8,2663
8,2872
8.:1108
8,3319
8.3544
8.3771
B,3999
B.4215
8.4445
8.4677
8.4882
8.5116
U0539
1.30882
1.31247
1.:11614
1.31963
1.32334
1.32686
1.33040
1.33418
1.33755
1.34136
1.34476
1.34840
1,35206
1.35574
1. 3 5922
!.36294
1.36667
1.36999
1.37377
1.28478
1.28815
1.29174
1.29536
1.29879
1.30244
1.30591
1.30939
1.31310
1.J 1643
1.:l2017
1.32353
1.32711
1.33071
1.33433
1.33775
1.34141
1.34509
1.34835
1.35207
0.1626
0.1630
0.1634
0.1639
0.1643
0,1647
0.1651
0.1656
0.1660
0.1664
0.1668
0.1673
0.1677
0.1681
0.1685
0.1689
0.1694
0.1698
0.1702
0.1706
8,6707
8.6933
8.7160
8.7389
8.7618
8.7835
8.8067
8,8300
8.8520
8.8741
8.8978
8.9201
8.9425
8,9651
8.9878
9.0105
9.0334
9,0564
9.0796
9.1013
8.5:1:18
8,5560
8.578'1
8.6009
8.6235
8.6448
8.6676
8.6906
8.7122
8.7339
8,7573
8.7792
8,8013
8,8235
8.8458
8.8682
8.8908
8,9134
8.9362
8,9575
1.37734
1.3809:1
1.38454
1.38817
1.39182
1.39526
1.39895
1.40265
1.40614
1.40965
1.41342
1.41696
1.42053
1.42411
1.42771
1.43132
1.43496
1.43861
1.44229
1.44574
1.35559
1.35912
1.36268
1.36625
1.36984
1.37322
1.37685
1.38050
1.38394
1.38739
1.39109
1.39458
1.39809
1.40162
1,40516
1.40872
1.41230
1.41590
1.41951
1.42290
6,~O2
6.385
5.3G8
6.350
6.334
6.316
6,300
6.283
6.266
6.249
6,233
6.216
6.199
6.184
6.167
6.151
6,135
6,119
fI.I03
6.087
6.072
6,056
6.040
6.025
6.010
5,994
5.979
5.964
5.949
5.934
5.919
5.904
5,889
5,874
5,860
APPENDIX
TADLE
Pounds
Per
I-(C01ztilZued)
Barrels
Gallon
Gallons
Pcr
POllnr1
0.6819
0.6803
0.6787
0.6770
0.6754
0.6738
0.6722
0.6706
5.845
5.831
5.817
5.802
5.788
5.773
5.759
5.745
5.731
5.718
5.703
5.690
5.(,7(,
5.662
5.649
5.635
5.522
5.608
5.595
5.582
0.1711
0.1715
0.1719
0.1724
0.1728
0.1732
0.17.10
0.1741
0.1745
0.1749
0.1753
0.1757
0.1762
0.1766
0.1770
0.ln5
0.1779
0.1783
0.1787
0.1791
9.1246
9.1465
9.1685
9.1922
9.2145
9.2384
9.2609
9.2834
9.30(,1
9.3273
9.3518
9.3732
9.3%3
9.4195
9.4412
9.4647
9.4865
9.5102
9.5323
9.5545
5.5(,8
5.556
5.542
5.529
5.516
5.503
5.491
5.477
5.465
5.453
5.440
5.427
5.415
5.402
5.390
5.377
5.365
5.353
5.341
5.329
0.1796
0.1800
0.1804
0.1809
0.18D
0.1817
0.1821
0.1826
0.1830
0.1834
0.1838
0.1843
0.1847
0.1851
0.1855
89.5
0.(,(,90
0.6675
0.6659
0.664:1
0.6628
0.6612
0.6597
0.6581
0.6566
0.6551
0.6536
0.6521
0.6506
0.6491
0.6476
0.6461
0.6446
0.6432
0.6417
0.6403
0.1864
0.1868
0.1872
0.1877
9.5785
9.5992
9.1)235
9.6461
9.6688
9.1i917
9.7129
9.nn
9.7591
9.7805
9.8039
9.8274
9.8492
9.8729
9.8949
9.9188
9.9410
9.9633
9.9856
10.0081
90.0
90.5
91.0
91.5
93.0
93.5
93.0
93.5
94.0
94.5
95.0
95.5
96.0
96.5
97.0
97.5
98.0
98.5
99.0
99.5
100.0
0.6388
0.6374
0.6360
0.6345
0.6331
0.6317
0.6303
0.6289
0.6275
0.6261
0.6247
0.6233
0.6220
0.6206
0.6193
0.6179
0.6166
0.6152
0.6139
0.6126
0.6112
5.316
5..~OS
5.293
5.281
5.269
5.257
5.246
5.234
5.232
5.210
5.199
5.187
5.176
5.164
5.154
5.142
5.131
5.120
5.109
5.098
5.086
0.1881
0.1885
0.1889
0.1894
0.1898
0.1902
0.1906
0.1911
0.1915
0.1919
0.1924
0.1928
0.1932
0.1936
0.1940
0.1945
0.1949
0.1953
0.1957
0.1962
0.1966
10.0326
10.0534
10.0762
10.0991
10.1221
10.1452
10.1665
10.1898
10.2132
10.2367
10.2584
10.2821
10.3040
10.3279
10.3479
10.3721
10.3943
10.4167
10.4391
10.4616
10.4863
Degrees
Specific
A.P.I.
Gravity
70.0
70.5
71.0
71.5
72.0
72.5
73.0
7,).5
74.0
74.5
75.0
7S.5
76.0
76.5
77.0
77.5
78.0
7R.5
79.0
79.5
0.7022
0.7005
0.6988
0.6970
0.6953
0.6936
0.6919
0.6902
0.6886
0.6869
0.6852
80.0
RO.5
81.0
81.5
82.0
82.5
83.0
83.5
84.0
84.5
85.0
85.5
86.0
86.5
87.0
87.5
88.0
88.5
89.0
0.68.~6
0.18m
203
Per
Long
Ton
Barrels
Per
Metric
Ton
Cubic
1Ie:ters
Per
Long
Ton
Cubic
Aleter::;
Pcr
Metric
TOil
8.9805
9.0021
9.0237
9.0471
9.0689
9.0925
9.1146
9.1368
9.1591
9.1800
9.2041
9.2251
9.2479
9.270R
9.2921
9.3152
9.3367
9.3600
9.3818
9.4036
1. 44945
1.45293
1.45642
1.46019
1.46372
1.46752
1.47109
1.47468
1.47828
1.48164
1.48554
1.48893
1.49260
1.49629
1.49974
I. 50346
1.5069,1
1.5107()
1.51121
1.51774
9.4273
9.6491
9.6722
9.6936
9.7170
9.7386
9.7621
9.7840
9.8059
9.8279
9.8501
1..,2155
1.52484
U2869
1. 53229
1.53590
1.53953
1.54289
1.54683
1.55023
1.55364
1.55736
1.56109
1.56455
1. 56831
1.57180
1.57560
1.57913
1.58267
1.58622
1.58979
1.49i 52
1.50070
I. S0455
1.S0809
1.51164
1.51521
1.51852
1.52240
1.52575
1.52910
1.53276
1.53643
1.53984
1,543S'[
1.54698
1.55072
1.55419
1.55767
1.56117
1.56469
9.8742
9.8946
9.9171
9.9396
9.9622
9.9850
10.0059
10.0289
10.0519
10.0750
10.0964
10.1197
10.1412
10.1648
10.1845
10.2083
10.2302
10.2521
10.2743
10.2964
10.3207
1.59368
1.59699
1.60061
1.60424
1.60790
1.51157
1.61495
1.61865
1.62237
1.62611
1.62955
1.6.1332
1.63679
1.64059
1.64377
1.64761
1.65114
1.65469
1.65825
1.66183
1.66575
1.56851
1.57176
1.57533
1.57891
1.58250
1.58612
1.58944
1.59309
1.59675
1.60043
1.60381
1.60752
1.61094
1.61468
1.61781
1.62159
1.62506
1.62856
1.63206
1.63558
1.63944
9.4~7('
9.4715
9.4938
9.5161
9.5386
9.S595
9.5839
9.(,049
9.62fil
1.42655
1.42998
1.43342
1.43713
1.44060
1.44435
1.44786
1.45139
1.45493
1.45824
1.46207
lA6541
1.46903
1.47266
1.47605
1.47972
1.48314
1.486R4
1.49030
1.49377
204
TAllLE
-=aT--d
T
where;
{I
V = absolute viscosity,
d = density of the oil at the temperature at which the viscosity is
beiu g mcasured,
T = reading of commercial instruments,
and b = constants.
Viscomc.tcx
Range
Saybolt Universal
Saybolt Universal
Saybolt Furol
Saybolt Furo!
Redwood Standard
Redwood Standard
Admiralty Fuel Oil
Engler
Engler
32-145 seconds
above 145 seconds
25-40 seconds
abovc 40 seconds
below 100 seconds
above 100 seconds
above 100 seconds
1.35-3.2 degrees
above 3.2 degrees
:I.
0.00221i
0.0022D
OJ)224
0.021G
0.0026
0.00247
0.0247
0.08
0.076
1.95
D.S
1.S4
0.6
1.79
D.S
0.0 (1)
0.0864
0.04
(1) Admiralty Fuel Oil Viscometer sbould be used all oils having viscosities
greater than 1000 Redwood Stanclard seconds.
The conversions are only approximate and should not be usee! when considerable accuracy is required.
[From F. H. Garner and C. 1. Kelly, Physics 4, 97-112 (1933).]
APPENDIX
205
s.u.v.
S.U.V.
210' F.
31
41
52
63
76
89
102
116
131
147
80
81
82
83
84
85
86
87
88
89
1627
1674
1721
1769
1817
1865
1914
1964
2014
2064
836
864
892
920
949
977
IOO7
1037
1067
1098
120
121
122
123
124
125
126
127
128
129
3838
3902
3966
4031
4097
4163
4229
4296
4363
4430
2218
2259
2301
234.)
2387
2430
2473
2517
2561
2605
422
456
491
525
560
596
{)32
669
706
743
165
184
202
220
238
257
276
295
315
335
90
91
92
93
94
95
97
98
99
2115
2166
2217
2270
2322
2375
2428
2481
2536
2591
1129
1160
1191
1224
1256
1288
1321
1353
1388
1423
130
131
132
133
134
135
13(j
137
4498
4567
4636
4705
4775
4845
4915
4986
5053
5130
2650
2696
2742
2787
28342880
2927
2974
3022
3070
781
819
857
897
936
976
1016
1057
1098
1140
355
376
397
418
440
462
484
507
531
554
100
101
102
103
104
105
106
107
108
109
2646
270!
2757
2814
2870
2928
2985
3043
3102
3161
1457
1491
152G
1562
1597
1634
1670
1706
1744
1782
140
141
142
143
144
145
141i
147
148
149
5202
5275
5348
5422
5496
5570
5796
5873
3118
3167
3216
3266
3316
3365
3416
:1467
3518
3570
1182
1225
1268
1311
1355
1399
1444
1489
578
602
627
652
677
702
111
112
113
114
115
lIO
3220
3280
3340
3400
3462
3524
3585
3{)48
1819
1858
1896
1934
1974
2014
2053
2094
2135
2176
150
151
152
153
154
155
156
IS7
ISS
159
160
5949
6026
6104
6182
6260
6339
0418
6498
!i578
6659
1.i740
3621
.'1673
3726
3779
3832
3886
3940
3995
4049
4105
41liO
40
41
42
43
44
45
46
47
48
49
138
161
185
210
237
265
293
322
353
386
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
7R
79
s.u.v.
210' F.
210' F.
1534
1580
728
75S
781
ROS
go
116
117
l1R
119
:1711.
3774
Viscosity index =
138
139
sG45
5721
L-[]
- - - x 100
D
206
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
A
D
E
Lily White
Cream White
Extra Pale
Extra Lemon Pale
Lemon Pale
Extra Orange Pale
Orange Pale
Pale
Light Red
Dark Red
Claret Red
Extra Dark Red
Extra Light Filtered
Light Filtered
Medium Filtered
Union
Tag
Robinson
L
M
N
0
P
21
17.5
12.5
10.25
9.75
9.25
8.25
5.75
3.50
2.25
LSD
G
H
I
R
A
Lovibond
~" Ccli
0.4
1.5
5.5
10
14
20
32
42
55
90
135
200
True
Color
0.4
1.5
5.S
10
14
20
32
42
56
100
170
285
D
E
The data are only approximate as exact comparisons between the different
commercial colorimeters are impossible for the reasons explained in Chapter I.
"True" colors are, approximately, additive although very considerable deviations might be expected for the explained reasons.
APPENDIX
o
207
o
o
1
("
""'
.....
00
0
u')
'I
'9
("0
T
o
;=:
'"";=:
o
"1
.S
u.,
.. ,,,
:0
I
'''1
:~
'+
,-. ,,-
:::;,
I
.~
l_)
tr)
: vi tr:i
00
......
208
U")
o
a
o
,....,
o
a
1
o
'?
o
"i"
~~
~~
1'-.\0
cci
o
I
S;I""
N
II
:/''\'"
'"<:;
>;>
'",
.",.
'+<
o
o
o
'0
+
'0
U1
1\ 1\
l)
<a
'0
OJ
0-
en.
APPENlJIX
TABLE
Test
Anderson
Belgian
British Air Ministry
Brown-Boveri Transformer
Brown-Boveri Turbine
French
Gel'll1an Tar (Kissling)
Indiana
Italian
Life (Snyder)
Michie
Sligh
Socony
Swedish
Swiss
U. S. S. R.
VI-Oxidation Tests
Temperature
of,
"C.
100
170
200
112
110
150
120
172
110
120
150
200
177
120
115
120
209
212
338
392
234
230
302
2-18
341
230
248
302
392
350
248
239
248
Time
Hours
.\tIHOSIJlwrc
100
Oxyg-ell
Size of
Air
24Air
Air
72/168
Air
72
Ail5)50)125
Oxygen
70
Air
X'
Air
300
To sludge
Air
Air
45
Oxygen
21
168
Air
Oxygen
70
Air
168
Ait70
CiLti1lyst
Ramplc
uOg.
Cu+Fe
None
40 c.c.
None
40 c.c.
lOOO c.c.
Cn
200e.c.
Cll
None
109.
150 g.
NOlie
None
300 C.c.
40g.
Cll
1000 c.c.
Cu
100 g.
Cn
None
109.
Fe
300g.
None
150 c.c.
eu 1000 C.L.
Cu
100 c.c.
PATENT INDEX
Patent No.
Page No.
AUSTIUAN
72,295
144
141,514 ........ , ... 167
148,991 " ' , '0 . 167
.,
P,-Itcnt ~tl.
l-Iagc l\ u.
410,175 .. , ........
410,833 ......... ,.
411,8(J(i '" .........
412,Oli9 .,. , ........
412,101 0' . . . . . I,.
413,307 ... ........
413,637 ..... ......
415,065 ............
419,820 .... '" - ....
421,118 ..... - ......
421,123 ............
422,471 ............
423,303 . ...... - , ...
423,441 . ...........
424,000 , ..........
424,205
424,380 , .. , .......
426)21 ........ , ...
427,843 ............
430,080 . ...........
430,485 , ..........
431,323 . ...........
432,168 . ....... , ...
432,249 . . . 0 ,
436,194 , 0'
437,486 . ...........
437,779 . . , 0
438,425 . .. , .. , .....
439,621 0 . , , 144,
439,674
442,039 ... " ..... , .
442,429 ., ..........
442,921 .... , ..... ,
444,535 ............
445,172 ., ....... , ..
445,317 ., ... ". 133,
445,908 ............
445,942 .... , .......
446,716 . , ..........
447,415 ... ...... ...
44-9,717 . , ... , ... '"
450,107 . , ........ .
450,511 ...... ......
451,411-2 . ... ......
452,914 '" .........
453,047 . , ........ , .
453,114-5 ..........
454,176 . , ..........
454,215 .... ..... ...
454,552 ., .... , .....
454,690 ...... ,,, .. ,
455,096-7 ......... '
455,235 .......... ..
211
,
BRITISH
1,6M (1912)
1,688 (1909)
11,140 (1908)
23,125 (1910)
113,098 ............
130,877 ............
164,325 '" .........
184991 ............
259;553 ............
263,167 .0 . , . "
267,038 .......... "
273,351 ............
276,658 '" .........
316,271 ......... - ..
345,632 ., ..........
350,388 .......... , .
355,294 ............
357,179 0
359,590
362,600 ............
368,025 ............
369,737 .......... "
369,975 ...... ,.,. "
370,325 .......... ..
373,538 .......... ..
379,717 , ...........
381,308 .... , .......
383,801 .. t. , .......
389,113 .......... ..
390,222 , ...........
390,697
393,152 .......... ..
394,404 .. " . , .... '.
394,414 .......... ..
397,169 ........ _p-,
398,922 .... .... 144,
399,030
401,341
402,253 ... , ........
402,262 .... " ......
403,392 .......... ..
408,947-8 . , ........
409,110 ..... , .... "
409,696 .......... ..
410,103 .... " ......
o.
o.
'
71
71
115
71
154
189
154
145
42
144
71
1-1-5
71
42
70
42
l(i2
199
199
145
195
153
37
71
71
195
79
1-1-3
104
70
145
167
145
178
178
154
144
18-1178
189
42
105
70
199
105
to
II.,
'"
144
177
70
91
189
153
18-1178
177
184
1(i2
184
713
195
1()2
199
195
144
lU5
IUS
70
154
71
Hi7
167
72
178
199
154
154
132
42
177
154
70
154
71
162
177
71
105
104
105
189
189
189
189
71
195
189
133
195
189
!lage No.
P;lH'nt ':-;0.
,'
, .
to-
'"
0"
.,.
.0'
..........
212
Patent No.
Page Xu.
35~,130
............
354,567 ............
354,803 ............
355,522 ............
350,140 ............
356,174 ............
356,176 ............
356,179 ............
356,637 ............
356,955 ............
357,209 ........... ,
357,332 ............
357,477 ............
357,650 ............
357,661 ............
357,974 ............
357,983 ............
358,412 ............
358,541-2 ..........
358,685 , ....... ,.,.
359,401 , ...........
359,459 ., .. , .... ".
359,464 , ... " .. ,.,.
359,596 ............
360,397 ............
360,538 ............
360,567 ............
360,630 .. , ........ ,
360,666 ............
360,668 ............
360,983 ............
361,999 ............
362,000 ............
362,222 ............
362,376 ............
362,539 ............
363,203 ............
363,364 .......... ,.
363,521 ............
363,528 ............
363,725 ............
364,322 ............
364,928 ,,,,,,......
365,076 ............
365,078 ............
365,079 ............
365,199 ............
70
105
189
7()
72
154
92
1~5
177
70
70
154
70
195
178
70
177
133
177
145
145
71
178
184
104
133
70
104
71
70
162
144
133
143
189
198
189
105
154
199
177
162
195
153
195
189
1R9
FRENCH
39,459 ...... " ....
43,393 ............
43,703 ............
44,179 ............
44,219-20 .........
44,791 ............
480,448 ............
632,602 .. "........
637,229 ............
644,840 ",."., .. "
670,366 ......... ".
153
154
184
91
162
70
195
71
71
42
92
Patent No.
677,385
682,330
68\),289
702,967
704,333
708,821
712,068
712,580
7th,703
728,289
730,431
731,471
734254
Page No.
........... ,
.... , ...... ,
............
............
............
............
............
............
............
............
.. ,., ...... ,
............
............
734;'W2 ............
734,797
736,983
737,256
737,836
738,953
739,062
739,264
739,542
740,803
740,832
741,633
743,776
745,378
747,558
748,925
749,942
752,104
753,036
756,248
756,640
758,269
758,853
759,633
759,767
761,243
761,270
762,002
762,446
762,949
763,190
763,455
770,289
770,803
770,903
772,827
773,687
774,421
775,434
775.450
775,640
776,043
776.766
777,520
777,719
778,660
780,468
780,999
............
........ 177,
............
............
...... ,.....
............
, ... "......
............
... , ........
............
............
.... ,.......
............
........ ,...
........ 144,
............
.. , ........ ,
............
............
............
............
............
............
............
............
, ...........
............
,...........
", .. ,......
............
", .. , ... ,"
............
........... ,
.......... ,'
............
............
... ,., ......
., ... , .... ,.
.. , .. ,......
............
...... ,.....
............
............
............
......... , ..
, ........ ,..
............
42
70
189
1~5
145
144
71
153
105
154
143
153
70
70
70
184
71
92
42
42
70
144
162
145
70
42
91
177
154
184
145
167
162
177
184
70
162
199
189
143
178
145
71
105
162
195
184
105
153
92
105
162
105
42
162
71
105
145
199
70
178
Patent No.
Page No.
781,258 ............
781,501 ........ ,',.
781,649 ............
783,447 ............
784,473 ............
784,570 ... ,.... 71,
784,596 ............
784,813 ............
785,839 ........... ,
786,581 ............
7ll7,381 ............
788,328 , .... ,......
789,299 ............
789,595 ............
789,862 ........ ,'"
790,309 ....... ,,',.
790,440 ..... ,......
790,615 ............
790,634 ........ 70,
790,666 ............
790,786 ......... ".
790,852-3 ..........
791,257 ............
791,326-7 ... .. .. ...
791,605 , ... , .......
791,764 ............
791,950 ............
792,946 ............
793,133 ........ 177,
793,825 ......... ,..
795,IQ7 ., ... , .. 133,
795,357 ............
795,444 , ...........
795,779 ............
796,168 ............
797,666 ............
798.061 ............
798,098 ............
798,304 ............
798,722 ., .. ,.......
800,144 ........ 85,
801,583 ............
SOl,715 ............
801,930 ..... , ... ,..
S03,413 ............
S03,470 ..... , ... ,.,
8()3,486 , ...........
804.270 ............
804,771-3 "", .....
S05,512 ............
805,809 ............
71
42
72
72
167
184
71
71
189
72
145
71
167
195
189
145
178
105
105
195
70
71
71
105
105
199
184
105
178
154
143
133
162
177
70
133
71
133
144
184
184
71
184
71
11i7
37
154
144
144
70
195
GERMAN
161i,45~
........... '
213,507 ............
232.794 ............
236,050-1 ..........
238,489 ..... " ... ,.
310,653 ............
337,512 ............
115
145
115
71
71
144
144
PATENT INDEX
Patent No.
Page No.
2,630
28,709
28,767
32,112
33,224
37,5G7
38,207
114,852
(i6,655
HOLLAND
.............
.............
.............
.............
.............
.............
.............
.............
.............
144
167
144
144
177
189
178
178
91
JAPANESE
109,419 ............ 177
POLISH
2,695 ............. 145
3,279 ............. 145
16,738-9 ........... 162
UNITED STATES
38,015 .......... 105
919,506 .......... 177
Patent No.
Page No.
213
P~L1t:nt
No.
214
Patent No.
Page No.
Patent No.
P'IJ:(c No.
2,008,569 .......... 42
2,008,674 .......... 42
2,009,454 .......... 71
2,010,007-8 ........ 104
2,010,606 .......... 198
2,010,819 .......... 79
2,014,629 .......... 37
2,015,046 .......... 144
2,(H5,748 .......... 178
2,017,432 .......... 168
2,017,529 .......... 198
2,017,730 .......... 154
2,018,758 .......... 189
2,018,871 .......... 184
2,020,021 .......... 189
2,020,066 .......... 70
2,020,290 .......... 143
2,020,290 .......... 144
2,020,693 .......... 42
2,020,703-4 ....... , 177
2,020,714 .......... 184
2,022,990 .......... 177
2,023,109 .......... 162
2,023,181 .......... 42
2,023,369 .......... 177
2,023,375 .......... 133
2,024,106 .......... 177
2,024,107 .......... 70
2,024,221 .......... 145
2,024,476 .......... 154
2,025,965 .......... 162
2,026,012 .......... 144
2,026,265 .......... 144
2,026,336 .......... 70
2,026,729 .......... 162
2,027,346 .......... 71
2,028,361 .......... 92
2,028,472 .......... 199
2,028,944 .......... 42
2,029,689 .......... 154
2,030,284 .......... 144
2,030,307 .......... 178
2,030,870 .......... 144
2,031,095-6 . . . . . . .. 71
2,031,107 .......... 70
2,0.11,108 .......... 178
2,031,210 .......... 42
2,031,117.g ........ 70
2,031,204 .......... 105
2,031,205 .......... 154
2,031,214 .......... 42
2,031,227 .......... 177
2,031,234 .......... 105
2,033,543 ...... 177, 189
2,033,546 ...... 177, 189
2,033,932 .......... 154
2,034,175 .......... 178
2,035,102 .......... 145
2,035,490.1 .. . . . . .. 71
2,035,583 .......... 144
2,035,945 .......... 91
Patent No.
Page No.
PATflNTINDEX
Patcllt No.
Page No.
2,054,429 .......... 70
2,054,430 .......... 72
2,054,433 .......... 71
2,054,750 .......... 71
2,054,775 .......... 72
2,054,777 .......... 37
2,055,135 .......... lOS
2,055,417 .......... 177
2,055,428 .......... 72
2,055,482 .......... 177
2,056,723 .......... 72
2,057,104 .......... 178
2,057,113 .......... 133
2,058,342-4 ........ 195
2,058,696 .......... 198
2,059,192 .......... 177
2,059,567 .......... 195
2,059,837 .......... 178
2,060,517 .......... 70
2,060,805 ....... 70, 71
2,061,008 .......... 177
2,061,328 .......... 1~9
2,061,541 .......... 70
2,062,354 .......... 177
2,062,356 .......... 79
Pat~nt
215
No.
2,062,676-7 ........
2,062,87:2 ..........
2,063,3(J9 ..........
2,063,564 ..........
2,063,857 ..........
2,064,338 ..........
2,064,422 ..........
2.064,506 ..........
2,065,551 ..........
2,066,164 ..........
2,066,173 ,.........
2,066,354 ....... ,..
2,067,050 ..........
2,067,128 ..... ,....
2,067,137 ....... ,..
2,067,162 ..... "...
2,067,193 ." .. ",.,
2,067,198 ..........
2,067,802 ..........
2,069,170 ., ..... ,..
2,070,383-5 .. ,',....
2,07G,6ll ,.........
2,071,481 ,., .......
2,071,521 ..........
2,072,10-1 ., ........
177
14-1
69
15-1
189
144
133
69
144
42
189
189
71
70
144
.Q
71
70
105
70
162
69
177
199
1-14
Patent No.
P~lge
2,072,107
2,072,120
2,072,382
2,073,080
2,073,641
2,073,841
2,074,254
2,074,288
2,074,338
2,075,269
2,076,105
2,076,141
2,076,147
2,077,057
2,077,068
2,077,287
2,077,656
2,077,712
2,078,186
2,078,442
2,078,472
2,079,035
2,079,051
2,079,1S1
..........
., .... , ...
..........
..........
..........
..........
......... ,
..........
..........
.... ,.....
..........
, ... , .. ,..
",., ... ,.
., .. , ... ,.
..........
..........
..........
..........
..........
..........
, .........
....... , ..
, ... " .. ,.
..........
No.
184
18-1133
177
177
189
69
199
189
144
154
70
42
133
189
162
70
70
71
144
195
144
195
70
AUTHOR INDEX
Abezgauz, I., 63, 71, 76, 79
Abraham, H., 8U, 85
Adams, C. E., 42, 54, W, 7U, 100, 105, l(i2
Aisinman, 106, 115
Aktiebolaget Separator Nobel, 42, GO,
61, 71, 132, 145
Akzionernojc Obshchcstvo po Patcntowaniyu i Rcalizatzii lzobretcnij, 42
Albridge, J. C., 63, 71, 15<\Aldridge, B. G., 42, 7U, 9U, IUS
Aka Products Inc., 70, 87, 99, 105
Allan, H. L., 79, 167
Allgemeine Ges. fiir Chem. Ind. m.b.h.,
144
Almasi, L., 144
Almen, J. 0., 188
American Society for Testing Ivfaterials,
12, 14, 21
Anctcnon, A. I'., 16,21, 56, 70, llO, 115
Anderson, J. A., 70, 176, 177, 178
Anglo-Iranian Oil Co., Ltd., 199
Aquila, S.S. Tec1mico Industriale, 114
Arakawa, 1., 35, 37
Associated 011 Co., 136
Atlantic Refining Co., 60, 6R, 89, 11-1,
142, 143, 144, 145
Atwell, H. V., 60, 70, 71
Auel-bRch, E. B., 144
Auld, S. J. 11'1., 116, 132
71
Berne-Allen, A. Jr., 42
Bloomer, W_ J., 91
218
Gewerkschaft Elwerath, 68
Gilbert. W. V .. 70, 193. 195
Giles, R. N" 54, 69, 70
Ginsberg, B., 100, lOS, 162
Glavneft Oil Trust, 114
AUTHOR INDEX
219
I.
J acobsel1, SO, 85
Johnson, .T. Y., 70, 176, 177, 178, 195
Jones, L. D., 42, 60, Cil, 71, 176,178
Just, Z., 81, 85
Lacey, R. J., 72
Lacey, W. N., 54, 56, 69, 70
Landsberg, L., 115
Lane, R. S., 62, 71
220
Laug, F_ R, 195
Laugworth, M. L., 70
Lapeyrouse, M., 21
Latson, C. M., 12, 14, 21
Lazar, A., 144, 198
Lederer, E. L., 18, 21, 29, 37, 42, GO, 71
Lee, R., 78
Lee, W., 109, 115
Leigh, R. E., 201
Lerzcynska, 1., 92
Leslie, R. T., 70
Levin, H., 177
Levine, A. A., 60, 69, 71
Lewis, W. K., 69, 184
Liberthson, L., 177, 186, 188
Limburg, H., 167, 177
Lincoln, B. H., 187, 189
Lindeke, H. F., 154
Lindgren, H. 0 . .10, 37
Livingston, M . .T., 61, 71, lOS, 122, D3,
145
Lochmann, C, 105
Loebel, A., 167
Lovibond, F. E., 21
Lovibond, ]. W., 21
Lucatu, E., 82, 85
Ludeman, C. G., 177
Lummus, W. E., 69, 87
Lummus Co., 88, 91
Lyons, H. N., 176, 178
MacLaren, F. H., 178
Magnolia Petroleum Co., 6S, II.!
Mair, B. J., 110, 115
Maim, K. G., 3D, 37
Manley, R E., 42, 7D, 71, 91, 92, 115,
122, 133, 139, 145, 15.1, 154, mi, 178,
198
Mann, F. W., 154
Marcusson, J., 80. 81, lB. 84. liS
Mardles, E. W. J_, 193, 195
Marg'oIis, L., 63. 71
Marsh, 1.. G., 41i, 69
Martin, E. J., 72
Mauritz, F. E., 26, 28
Mayer, A. W. J., 162
McAfee, A. M., 92
McCarty, R. y', 58, 61, G0, 70. 71, 92,
11 S, 122, 1.13, 145, 176, 178
McCloud, ]. L., 178
McCluer, W. B., 13, 14, 15, 21, 122.
133, 144
McConnel. T. R, 199
McDonald. M. c., 42
McGill, W. J., 69, 70. 177
McHarness, R. C. 189
McIlvain, ]. M., 21
McKee, A. G. and Co., 87
McKittrick, D. S., 71
Meaf, N. V. Machil1erieen-en Allparaten
Fabriekcn, 105
AUTHOR INDEX
Pcullzoil Co., 114,. 136
Pester, C. F., 71
Peterkin, A. G., 42, 14S
Petry, T. A., 116 144
Petty, E., 42, 70 '
Pevere, E. F., 58, 70, 72 144, 1i(l, 177,
178, 182, 184
'
Pf~ff? ]. K., 41, 42
PhlllljlS, E. B., 42
Phillips, G. E., 151, 154
P~otogen Raftinel'ies de Pctrole, 114
Plctet, A., 92
Pier, M., 103, 105, 153, 182, 184
Plank, R, 144
Pokornym, S. 0., 20, 21, 145
PCill, H., 145, 167, 178
109 115
Pollock, R.
Pool, W.O., 189 '
Poole, J. W., 68, 69, 71, 72, II(i, 1~2,
132, 133, 154
Poznyak, 1. V., 136, 14+
Pruitt, I-I., 69
Prutton, C. F., 187, 189, 193, 19S
Pyhaclae, E., 75, 78, 79
c.,
c..
c.,
Co.,
221
J.'
c..
222
114
Travis, P. M., 42
Trellccr, J. M., 154
Tulleners, A. J., 110, 115
Tuttle, M. H., 157, 162
Tyler, S. N., 103, lOS
Uier, E., 177
Underwood, A. J. V .. 108, 115
Union Oil Co, of California, 42, 56, 68
94, 104, 105, 114, 153, 162
Upham, E. W., 12, 21
,,,I.,
r.,
AUTHOR INDEX
Williams, D. E., 144 145
W!11ingham, C. E., l'lD, 115
W~\mot and Cassidy Inc., 199
WlIlklcr, J., 37
Winning, c., 170, 177, 178
Woog, P., 172, 178
W oolgar, C. W., 186, 188
Wulff, C, 177, 182. 184
Wyant, L. D., 46, 69
Young, P. 1., 178
,,(_,
SUBJECT INDEX
A cceleralecl
69
dewaxing~ with, 61
Acetic ether, 72
Acetone,
c1cwaxing
with, 44, 46-8 J
57-61
65 J 6f\-r
72
'
miscibility with oil, 57-8, 110
properties, 49 58
selective soh:ent properties, '18 65,
llO, 118, 147, l49, 151, 157
'
solubilitv of wax in 40-7
toxicity: 44
'
Acetonitrile, 134. 149
Acetophenone, 134
Acetyl acetone, 134
Acctylene, 96
Acetylene derivatives, 183
Acctylene dichloride, (,D
Acetylfurall, 134
Acidic
111subs tances ' rCllloval fl' 0111
01'I?)
, -~,
dew:lxing with, 65
'
ethel'S, 134
Acridine t\ves, 198
Acrolein, f5.'l
Addition ag'cnts, 168
Aged oils, decolorization by solvent re-
fining, 27
Agitation, in c\CW<lxing, 56-7
Airplane enginc oils, oxidation tests 19
Alhreaction, 109
'
Alcohols (sl'r "Iso the individual alco-
hols)
deasphaltillg with, 67, 100-4
dehydration, 50
dewaxing' with, 41, 01 05-8
oiliness characteristics: 189
selective solvent [lropertic~, lOS. Ul,
,143,. 14~, 149, 151, 154, 164. 170
VISCOSity 1!1dex improvers, 182
wax analysis with, 31
87
"":
12
oleate, 193
l\Jul11inUIll soaps,
llour point depres~ants, 170-1
stabilizing dyes with, 198
Aluminum stearate, -1-1, 17ll, 193
Amides (sa (//su the individual am-
ides),187-8
225
226
Anthraquinone, 198
Anti-oxidants (see oxidation inhibitors) ,
Arachidic acid, 187
Aromatic cyanides, 134
Aromatic nitro compounds, 149
Aromatic polycyclic hydrocarbons, 149
Aromatics from solvent extracts, 58, 65,
106, 165-6
Aromatic solvents in sweating wax, 75
Awma tic sulfonic acids, 76
Arsenic derivatives, 191-3
Ash content after deasphalting, 103
Asphalt (see also deasphalting),
composition, 82, 103
definition, 82-5, 97
effect on oil properties, 20, 80, 183
effect on settling rates, 121
electrical precipitation, 99
from solvent extracts, 163-4, 167
hard, 80, 99, 103
heat of licluefaction, 97-8
melting point, 97-8
potential, 83-4
pour point depressant qualities, 32, 176
precipitation in dewaxing oils, 56, 67
preparation by propane extraction, 96,
156
preformed, 83-4
soft, 80, 99
synthetic, 82
Asphaltenes, 81-3, 172, 197
Asphaltic snbstances,
analysis, 80
colloidal nature, 81-2
dewaxing aids, 57
effect on carbon residue, 80
nature, 80-2
Asphaltous acid anhydrides, 81
Asphaltous acids, 81
Bari-Sol Dewaxing Process, 63-5, 68
Bearings, protection of, 193-4
Beechwood creosote, 157
Beeswax, 171
Belgian oxidation test, 19, 209
Benzaldehyde, 65, 72, 134, 149
Benzabthrone, 198
Benzol,
deasphalting with, 96
dewaxing with, 47, 57-60, 63, 65, 69,
71-2
properties, 49, 58
selective solvent properties, 130, 147,
149, 157
toxicity, 44
Benzol-Acetone Process,
deoiling by, 13, 75
dewaxing by, 31, 39, 48, 57-60
fit ter rates, 48, 51
oil separation in, 57-58, 65
SUBJECT INDEX
Carbon disulfide, 65, 69, 147, 162
Carbonization index, 16
Carbon residue, 16-8, 34, 80, 83-4, 89,
90, 111, 128, 168-9, 196
Carbon tetrachloride, 31, 49, 60-1, 69,
147, 149, 184
Carnauba wax, 171
Carvacrol, 134
Cascade system, 142-3
Cellular filter aids, 39
Cellulose, 183
Cellulose acetate, 157
Cellulose, tri-stearyl, 183
Centrifuging,
deoilillg waxes by, 76
dewaxing by, 35-7, 41, 61, 63, 176
of solvent extracts, 122, 145, 165
Ceramindenol, 198
Ceranthrenic compounds, 198
Ccrbianthrenic compounds, 198
Ceresin wax (sea also petrolatum and
wax),
deoiling, 76-8
fractionation, 76-8
properties, 30, 173
utilization, 30, 79
Cerotic acid, 170, 187
Ceroxene, 198
Chilling differential in dewaxing, 44
Chilling rates in dewaxing, 26, 56, 60,
62-3
Chilling temperature in dewaxillg, 58,
60, 62-3
China wax, 171
Chloraniline, 120-1, 134, 157
Chlorex,
applicability, 138-9
corrosiveness, 139
detection in oils, 132
dehydration, 50
dewaxing with, 65
effect on flash point, 132
finishing oils after treating with, 90
plants, 112-4, 136
properties, 49, 136, 138
recovery, 50, 138-9, 145
selective solvent properties, 118-20,
134, 136-9, 145, 147, 157
sweating with, 75
toxicity, 44
Chlorinated hydrocarbons (see also the
individual hydrocarbons), 60-3
Chlorinated esters (s~e also the imlividual esters), 187
Chlorinated ethers (see also chlorex
and the individual ethers), 147, 149
Chlorinated paraffin wax, 171
Chlorinated solvents,
corrosiveness, 61
dewaxing with, 60-5
effect on oil properties, 61
227
111
measurement, 17-8
relation to oil properLies, 17, 128
Colorimeters, 17-8
Color intensity, 17
Columbian crude, 13
Combination processes, 24. 65-6
Component solvents, 146-7
Conclensation products from electric discharge, 170
Conrad son carhon (see carbon resid\le),
Constant boiling mixtures, 49, 50
Conversion tables, 201-6
Copper-lead bearings, 193
Corrosion inhibitors, 62, 192-5
228
171-2
Crystallization regulators, 56, 176
Crystal oil, 54
Cumene, 58
Cutting oils, 188
Cyanides (see also the individual cyanides), 134
Cyclic alcohols (sec also the indiviclual
alcohols), 149
Cyclic ketones (see also the individual
ketones), 58
Cyclohexane, 58, 65, 96, 103
Cyclohexanol, 149
Cyciohexanone, 149
Cyc1ohexene, 54
Deasphalting,
asphalt recovered, 96-7
by distillation, 82, 86-7
conventional methods, 86-92
eft ect on oil properties, 83 85
high molecular weight Sl1b~tallccs, removal by, 84, 93 .
in dewaxing, 24
in solvent refining, 24, 27, 82-5, 93105, 158
losses in, 83
recycling in, 102-3
relation to solvent refining, 83-4
sequence, 24
settling rates in, 99
wax separation in, 99
with alcohols, 10()4
with chemicals, 86
with day, 88-90, 143
with esters, 104
Deasphalting (Coni'd),
with ethen, 104
with ketones, 104
with liquefied hydrocarbons, 24, 93100
with metallic chlorides, 91
with sulfl1ric acid, 23, gO-I, 143
Deasphalting plants, distribution, 104
Dehydration of sol vents, 48-50
Demulsifying agents, 166
Deresining, 104
Dewaxing,
hy centrifuging, 36-7, 41, 51, 62-3
by cold settling, 35
by filter pressing;, 35-lj, 51
chilling rates, 36
choice of solvents for, 51
classification of methods, 38, 43
comparison of methmls. 37-8
electrical methods for, 38, 41
effect on oil properties, 33, 40
in deasphalting, 24
in solvC'llt refining. 24
low melti ng point waxes, effect ill, GO
oil loss, e,lim:ltiol1, 57
plants, 68-9
pOllr point depressants in, 176
pretreating oils before, 38, 41-2 60,
176
'
sequence, 24
with filter aids, 38-41, 170
with napiltha, 35-6, 39-40, 54
Dibro1l1o!lcl1zenc, 41
Dibw111opropyl alcohol, 144
Dibutyl oxalate, 72
Dibutyl sulfone, 134
Dichlorobenzene, 41, 58, 61, 65, 72
Dichlorodifluoromcthane, 60
Dichloroethane, 60-1
Dichloroelhylene, 61
Dichloroethyl ether (see chlorex)
Dichloromethyl P\-OP;l1lC, 60
Dichloropropanc, 61
Dietbyl carbinol, 4(j
Diethylene glycol, 61
Diisopropyl ethcr, 72
Diketoncs, 134
D!Iuents for lubricating oils, leiS
DIlution, effect on viscosity, 183
Dimethyl allyl alcohol, 154
D illlcthyl amine, 96
Dimethyl craekcne 197
Dimyricyl ether ~f 1,5-dioxvnaphthOllene, 170
Dinitrophenyl thiocyanate, 189
Diolefins, 182
Dioxane, 149
Diphenv1, 41
Diphenylamine, 189
Diphenylene oxide, 171, 187
229
Distillation, deasphalting by, 8(j-8
Distillation residue, 170
Distributiun coett1cicllt, 1O~
Disulfides (-rce also the illdi I'irlual di,
sulfides), 191
Double centrifuging', 61, 63-4
Double solvent processes, 27, 113, 155-62
Duo-Sol Process, 24, 91, 112-4, 156-62
Dyes, 18, 166, 196-9
Ethyl iorlllate, 72
Ethyl isol'alerate, (jy
Ethyl prupionate, W
Ethyl vakrate, 0~1
Emhodill dye:;, 1~)13
Exanol, 1::;0-1
ExtraL:tioll ",tages, 122-3, 128, 130-1
Extn:ll1e pressure lubricants, 1::;5, lSti,
1S8
230
Gas oil, 40
Iron, 192-3
Iron chlorides, 91
Isobutalle, 96
Isobutyl acetate, 72
Isobutyl alcohol, 66
lsobutylene, 183
Isobutyric acid, 134
Isodecane, 53
Isopentane, 65, 96
Isopropyl alcohol, 46, 65, 134
Isopropyl ether, 61, 65, 72
Isopropyl furoate, 134
Italian oxidation test, 209
Kinematic viscosity, 13
Kissling oxidation test, 209
Keto-esters, 134
Ketone oils, 46
Ketones (see (lIsa the individual ketones) ,
deasphalting with, 101, 103-4
dewaxing with, 58, 65
oiliness, 187-8
pour point depressants, 170-1, 188
separating oils from solvents with,
131
solvent refining with, 147, 149, 151
toxicity, 44
viscosity index improvers, 182
Kerosene, 54, 82, 103, 106
labontory tests, unreliability of, 11, 19,
20
Lampblack, 39
Lard oil, 187
Lavender oil, 199
Lead compounds, 192-3
Lead sulfate, 39
Lead sulfide, 39
Lead tetraethyl, 193
Levulinic acid, 96
Life oxidation test, 191-2, 209
Lignite oil, 110
Lignite wax, 171
Liquid sulfur dioxide process (see sulfur dioxide process)
Liquid sulfur dioxide-benzol process
(see sulfur dioxide-benzol process)
Litharge, 39
Losses, estimation in clewaxing, 57
Lovibond tintometer, 17
Low viscosity oils, demand for, 87
Lubricating oils from solvent extracts,
164-5
Magnesium chloride, 170
Magnesium hydrostearate, 170
Magnesium soaps, 170, 198
McKee Distillation Process, 87
SUBJECT INDEX
231
Naphtha,
cracked, 54, 151
dewaxing with, 39, 51, 53-4, 60-1, 65,
69
refining with furfural, 139
selective solvent properties, 151
solubility of waxes in, 46
solvent pressing waxes with, 75-6
Naphthalene, 40, 149, 170-1, 177, 182,
. 187, 197
Naphthenic solvent, 155,157-8, 162
Naphthols, 157, 191
Naphthylamines, 191
Narrow fractions, flash point of, 20
Natural pour point depressants, 169-70
Natural waxes, 171
Neutralization number, change on oxidation, 18
Nickel compounds, 193
Nicolet and deMitt's acid, 187
Nitriles (sec also the individual nitriles), 134, 188-9
Nitro alcohols (see also the individual
alcohols), 134
Nitro aromatics (s{'e also the individual compounds), 149, 188
Nitrobenzene,
applicability, 142
dehydration, 50
detection in oils, 132
dewaxing with, 65
plants, 112-4
properties, 49, 142
sepa ration from oil. 142
solubility of wax in, 46
solvent refining with, 89, 96, 117-8,
134, 142-3, 145, 149, 1S7, 165
toxicity, 44
Nitrobenzene-sulfuric acid process, 1124, 143
Nitrobcnzyl alcohol, 134
Nitrogen, 96
Nitrogen bases, 135, 144, 149, 166. .
Nitrogen compounds (see also the llld!vidual compounds), 191, 193
Nitromethane, 65, 130, 134
Nitroto1uene, 96, 149, 157
Octane solubility of wax in, 53
Octyl alcohol, 100
Oil,
consumption in engines, 20
effect of inhibitors on pour point of,
173-5
inhibitor response, 191
losses in dewaxing, 57
separation from solvents, 131-2, 139,
141, 145, 164-5
separation from wax, 73-9
solubility in solvents, 46, 67, 97, 110
wax content, 29, 31-4, 168-9
232
lSI
Phenol,
as filter aiel 41
r\ehydration; 142
lowcring' melting point of, 142
oxidation inhibitors from, 191
plants, 112-01]Jroperties, 49, 141
separation from oil, 145
~olvent refining' with. 31, %, 119-20,
13~ 142, 145, 14~ 14~ 151, 15~
157, 160
sweating in presence of, 41
toxicity, 44
Phenolic esters, (is
1)heno1ic ethers, 177
Phenyl acetates, 134, 149
Phenyicyanicle, 134
Pl1enylmethylamine, 145
Phosphates, organic, 157, 1YI-3
Phosphates, inorganic, 76
Phosphites, 193
Photoelectric colorimeters, 18
Piperidine, 149
Pitch, 197
Polycyclic hydrocarhons (sec also the
indiviclual hydrocarbons), 149
Polyhydric alcohols, 147
Polyindcne, 171
Polymerization of Furfural extracts,
1.39
Polymerized suhstances, 170
Polystyrene resins, 182
Polystyrol, 171
Putential asphalt, 83
POllr point,
change in solvent refining', 24
differential between chilling' temperature and, 36, 48. 58, 67 effect of asphalt on, 32, 85, 172
effect of wax 011. 31-2, 48
effect on oil performance, 19
limitations, 171-3
maximum, 170
measurement of 19
minimulll, 170 '
Ponr point depressants,
comparison of commercial, 175-(,
clewaxing in presence of, 176-7
effect on oil properties, 175, 183, 18R
from solvent extracts, 166
natUl'aJ, 32, 169-70
synthetic, 170-8
Precipitation solvents (srI? clcasphalting
solvents)
Predilutccl oils. 183-4
Preformed asphalt, 83
Pressing waxes, 34-5, 75-6
Primary solvents. 146-7
Pri111ulinc bases, 198
Propane.
deasphalting with, 24, 55, 83, 93-100,
156-7
SUBJ1iCT iNDEX
Propane (Cont'd),
c1eoiling with, 7ll
dew axing \vith, :.N, 39, 51-8, 61, 68,
72, 99, 156-7, 161
plants, 68, 104
properties, 49, 54-6
refining in presence of, 161
refrigerating with, 55
solubility of wax in, S4
solvent relining with, 149, 156-7
Propionaldehycle, 134
Propionates, 72
Propionic acid, 134
Propionitrile, 130
Propyl alcohol, 6ri, 103
Propyl amino benzoate, 134
Propylene, 96, 151, 183
Propylene dichloride, 39, 60-1, 149
Propyl ethel-, 61
Pseudo-waxes, 31
Pyrene, 198
Pyridine, 65, 69, 96, 149, 157
Pyrogallol tristearate, 171
Pyrogenous condensation products, 170
Q uilloline, 65,
134, 149
Ramsbottol1l carboll
234
Specific dispersion, 16
Specific gravity, 20, 33, 53-4, 85, 109-11
Spent clay, dyes from, 197
Spermaceti, 171
Spery-C~m111en Adheroscope, 186
Stammer s chromometer, 17
Stearamide, 187
Stearic acid, 171, 187, 189
Stearo-Ilitrile, 189
Stearyl chloride, 171
Storage, effect on refining, 27
Sulfur dioxide.
dewaxing with, 61, 65, 72
plants, 112-4
properties, 49, 135
separating oil from solvents with. 131
solutions in solvents refining with'
151
'
,
solvent refining with, 106, 118, 130,
134-6, 144, 147, 149, 151, 157, 161
toxicity, 44
Sulfur dioxide-benzol process, 24, 65-6
112-4, 148-53
'
Sucrose, 171
Suida Process, 165
Sulfides, 189
Sulfoch1orinated o-tolyl stearamide 187
Sulfonic acids, 76, 166
'
Sulfur compounds, 188-9, 191, 193
Sulfuric acid,
comparison with solvents, 22-3, 25-8,
106, 116
deasphalting with, 90-1, 143
dewaxing in presence of, 161
finishing solvent refined oils with, 90-1
pretreating oils before dewaxillg with,
29, 37, 42, 60
refining solvent extracts with, 165
treating in propane solution with, 18,
104, 161, 198
Sulfurized paraffins, 41
Sulfur trioxide, 149
Sweating, 34, 41, 73-5
Swedish oxidation test, 209
Swiss oxidation test, 209
Tag-Robill5on colorimeter, 17
Talang-Akar crude, 31
Tallium compounds, 193
Tallow oil, 189
Tar pitch, 170
Tellurium compounds, 191
Temperature gradient, 130-1, 141-2
Tensile strength of wax, 32
Terpenes, halogenated, 187
Tetrahydrofuran, 134
Tetrahydrofurfuryl alcohol, 134
Tetrahyclronaphthalene, 58
Tctralin, 65
Thermal properties of oils, 207-8
Thioacids, 189
Thioamides, 188
Thiocarbonates, 189
Thiocyanates, 134, 189
Thioetbers, 189
Thiophene, 149
Thiophosphoric acid esters, 193
Tin compounds, 192-3
Tin oleate, 193
Titanium compounds, 171
Titanium stearate, 171
Toluol,
in dewaxing, 47, 57-61, oS. 69, 72
in solvent refining, 130, 149
properties, 49, 58
Tolyl !itearamicle, 187
Towers, counter-flow, 122, 131 138,
141-2, 145
'
Toxicity of solvents, 30, 44. 134, 143
Transformer oils, 12, 19, 20. 135-0, 174,
191-2
Tri (see trichloroethylene)
Triang'ular diagrams, 46, 97-8
Trichloroethylene (see also Sepal'atorN ob,el Dewaxine; Process).
corrOSIVeness, 61
dehynration, 50
newaxing with. 48, 61-3. 68
properties, 49, li2
stabilization, 62
toxicity, 44
SUBJECT iNDEX
Triethanolamine, 149, 170, 177, 18\!
Trimethylene, 134
Trioxymetbylene, 171
Triphenylbenzofttran, 198
Triphenyldioxazine, 198
Tristearate of pyrogallol, 171
Tristearyl cellulose, 183
Turbine oils, 12, 19, 135-6, 174
Union colorimeter, 17
Ullivis oils, 181-2
Unsaturated compounds (see also the
individual compounds), (iO, 149, 154
U sed oils, oiliness of, 188
U.S.S.R. oxidation test, 209
Valerates, 72
"Vaseline," 73
Vegetable oils, 96, 176, 187
Vinyl compounds, 149, 170-1, 182
Viscosity,
effect of deasphalting, 20, 85
effect of dewaxing, 20, 33, 40
change in oxidation tests, 18
of hydrocarbon-oil solutions, 53-4
reduction on clay percolation, 89
conversion, 204
Viscosity breaking, 87
Viscosity gradient, 14
Viscosity-gravity constant, 14-5, 85, 107,
111
Viscosity index,
change on refining, 111
effect of asphalt on, 20, 85, 128
effect of wax on, 20, 37, 168-9, lR4
kinematic, 13
limiting, 180
measurement of, 12-3
mo lecular weights from, 14
of blends, 14, 180, 183
of motor oils, 25, 91
of solvent extracts, 116-7
of typical crudes, 13, 15
of waxy oils, 33
relation to viscosity-gravity constant,
15
tables, 205
Viscosity index improvers, 179-184
Viscosity-temperature chart, 12
Viscosity-temperature slope, 14
Viscosity-temperature susceptibility (sec
also viscosity index), 11-3
235
Il
Water,
in solvents, 101-3, 142, 145, 153, 164-5
regenerating filter-aids with, 40
separation from soh'ents, 48-50, 142
solubility in solvents, 49
solubility of solvents in, 49
'N ax (see also ceresin wax and parufiltl
wax),
amorphous, 29, 30, 35
content in oils, 30-2
crystallization, 34-5, 171-2, 174, 176
deoiling, 73-9
effect on oil properties, 20, 22, 29,
31-4, 184
effect in solvent refining, 121, 138, 142
inhibitors in, 29, 30
low melting point, 31, (;0
nature of, 29, 30
oil content, 31-2, 57
pressability, 29, 30, 34-5
refining, 79, 153
separation with asphalt, 99
solubility in solvents, 45-8, 53-4, 56
testing, 32, 79
types, 29, 30, 73
'I./ax tailings, 170, 177
VI[ eight-gravity-voJume co 11 v e r s ion
tables, 201-3
Weir Dewaxillg Process, 39, 40, 76
White oils, ]45
White Speed Flow, 40
'Nilson's chrolllometer, 17
Wintergreen oil, 199
Wood pulp, 39
Wood tar acids, 157
Wool fat, 170
X-ray diffraction method, 187
Xylene, 58, 61, 65, 96
Xylidines, 149
Xylylstearamide, 170
Zinc chloride, 41, 91
Zinc hyclrostearatc, 170
Zinc soaps, 170, 198
2.
3.
4.
5.
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30.
33.
34.
36.
37.
41.
42.
43.
44.
45.
46.
47.
48.
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53.
54.
55.
56.
JamieSOll.
S9.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
The Chemistry of Natural Products Re'lated to Phenanthrene (Second Edition with Appendix). By L. P'. Fieser.
71.
J.
72.
73.
74.
J. Weith
and
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Baila!'.
J.
J.
S. LOllg.
J.
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