Feb. 11, 1964 K.

THORMANN ETAL 3,120,993

GAS PURIFICATION PROCESS
Filed May 9, 196l

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 United States Patent Office 3,120,993
Patented Feb. 11, 1964
1. 2
3,120,993 for example, methanol or acetone at temperatures below
GAS PURFICATION PROCESS -20 C. and under increased pressure. A concentrated
Kurt Thormann and Wilhelm Herbert, Frankfurt am mixture of all of the impurities is desorbed during the re
Maia, and Hans-Ulrich Kohrt, Bad Homburg vor der generation of the solvent and further treated in known
Hohe, Germany, assignors to Metallgesellschaft Aktien 3) a.
gesellschaft, Frankfurt am Main, Germany, a corpora Conditions for carrying out the above process have
tion of Germany also been found whereby the organic solvents of the afore
Filed May 9, 1961, Ser. No. 108,837 said type have a certain selectivity for hydrogen sulfide
Clains priority, application Germany May 1, 1960 in preference to all of the other gas impurities. Thus,
1i Caims. (C. 23-2) O as compared with methanol, acetone has a marked selec
The invention is a process for purifying gases, and tivity for hydrogen sulfide. However, during the regen
especially for removing sulfur compounds from industrial eration, it forms with the latter, compounds which can
gases. More particularly the invention relates to a prac Oniy be separated from the acetone with difficulty and as
tical and economical process for the removal and re a result pass finally into the stripped gas as impurities.
covery of Sulfur-containing and acidic components from 5 When using, as absorbents, aromatic hydrocarbons in the
industrial gases. low-temperature washing processes, it is necessary to first
iPractically all industrial combustible gases, such as dry the gas as the aromatic hydrocarbons are not mis
coke oven gas, water gas, carburetted water gas, coal gas, cible with Water. A comparatively high selectivity was
refinery waste gas, natural gas contain impurities such as found in the case of the use of dimethyl formamide as ab
hydrogen sulfide, carbon dioxide, cyanogen, as well as 20 Sorbent. In the continuous operation of a technical
low hydrocarbons, sulfur compounds, etc., which must plant, however, the dimethyl formamide undergoes hy
be removed before the gases are suitable for certain uses. drolysis which results in continuous losses and, further
Organic and inorganic Sulfur compounds are commonly more, gives rise to the formation of free formic acid
present in all such gases and most gas purification sys which has a corrosive effect on the equipment and neces
tems are designed for the removal of these impurities, be 25 sitates the use of high-grade steel.
cause they have a corroding effect and/or act as catalyst The primary object of the invention is to provide a
poisons. process for purifying industrial gases whereby economy
The known processes for the absorption of the acidic of operation is obtained.
components from gas mixtures generally consists of Another object of the invention is to provide a process
Scrubbing out of the gases with alkaline reacting liquids, 30 for purifying industrial gases permitting separation and
Such as aqueous solutions of inorganic bases or alkali recovery of hydrogen sulfide without its being contami
salts of weak inorganic or organic acids. The disad nated with gas impurities e.g. hydrocarbons, solvents,
Vantages of the known process are that in order to effect etc.
a complete removal of hydrogen sulfide from the gas to Still another object of the invention is to provide a
be purified, the absorbent liquid loaded with absorbed process for purifying industrial gases whereby there is ob
impurities must be entirely regenerated with high expendi tained a gas which is an important source of synthesis
ture of steam which is mostly prohibitive for reasons of gas, i.e., a high purity carbon dioxide gas from waste
economy and, further, when using an alkaline absorbent gaSeS.
solution, for removal of hydrogen sulfide, there is simul 40
Other and further objects and advantages of the inven
taneously absorbed large quantities of carbon dioxide. tion will become more apparent from a consideration of
This is very detrimental for several reasons, for one, the the following description:
further working up of the hydrogen sulfide into non The present invention consists in a process for remov
volatile sulfur compounds which is necessary to avoid a ing impurities from gases which comprises scrubbing the
pollution of atmosphere is interfered with and, further, 45
gas with an organic water-soluble absorbent constituting
when the hydrogen sulfide containing gas stripped from a heterocyclic compound containing in addition to a car
the absorbent is to be used in the manufacture of chemical bonyl group, a vicinal alkylated tertiary nitrogen atom.
compounds. It is necessary, therefore, to separate the In general, the substances applicable as absorbents for
carbon dioxide from the hydrogen sulfide before proceed carrying out the gas scrubbing process according to the
ing further. The use of such basic acting solvents is in 50 invention and which are selective for sulfur compounds
many cases therefore inefficient due to the limited extent are N-alkylated lactams of the y or 8 amino acids deriv
to which regeneration of the solvent can be effected, the able from butyric acid, valeric acid and caproic acid,
great expenditure of thermal energy necessary to effect namely, the N-alkylated pyrrollidones or piperidones which
regeneration and destruction of the equipment due to may be substituted with one or two lower alkyl groups,
excessive corrosion attendant on their use. e.g. methyl groups, on the heterocyclic nucleus.
Processes employing physically acting organic solvents in the method of the invention which provides an eco
allow, by using sufficiently high absorption towers and nomically executed and highly efficient process for the
maintaining lower adsorption temperatures, for example, selective absorption of sulfur compounds from industrial
in the region of -20 to -70 C., the obtaining of coin gases which also contain carbon dioxide and hydrocar
plete absorption of the hydrogen sulfide with low con 60
bons as well as other gas components, the N-alkylated
sumption of energy for the regeneration. The organic pyrrollidones or piperidones are passed in circulation
solvents, which however possess a good capacity for ab through the absorption under elevated pressure and the
sorbing hydrogen sulfide, dissolve simultaneously however regeneration stages under atmospheric pressure.
also other gas components which are not acid, as, for While the ratio of the absorption coefficients according
example, saturated and unsaturated hydrocarbons. 65 to Bunsen, as expressed in liters of absorbed gas per liter
Processes for purifying industrial gases are known in of absorbent at a pressure of 1 atm. and at a temperature
which all the impurities contained in the gas, such as hy of 20° C. for hydrogen sulfide and carbon dioxide are in
drogen sulfide and sulfur compounds, carbon dioxide, the case of acetone and methanol about equivalent to 5:1,
resinforming substances, such as unsaturated hydrocar and in the case of dimethyl formamide, about 9:1, the
bons and other hydrocarbons, metal carbonyls and like, 70 ratio of the coefficients in the case of the lactams in ac
are absorbed simultaneously from the industrial gas mix cordance with the invention is about 12:1 to 15:1.
tures by means of a simple organic polar substance as, The absorption coefficients for the lower saturated hy
 3,120,993
es 4.
drocarbons are considerably lower than those for carbon absorption temperatures of about 0 to 20 C., for exam
dioxide. ple, between 5 and 15° C. If the other gas impurities,
The absorbents are water-soluble. Their boiling points and especially the carbon dioxide, are to be scrubbed out
are between 200 and 250 C. in a subsequent low-temperature washing at about 20
Absorbents according to the invention are to -50° C. as described in the specification of the U.S.A.
N-methyl pyrrolidone boiling point 206 Patent 2,863,527 the low temperature of the pure gas is
N-methyl-2-methylpyrrolidone boiling point 215-217 sufficient to maintain the absorption temperature in the
N-methyl piperidone boiling point 205 process according to the invention, independently of the
surrounding temperature.
To effect a selective absorption of the hydrogen Sul 0. In the accompanying drawing forming a part of the
fide and of the organic compounds, a special purifying specification and showing for purposes of examplification
stage with its own regeneration is necessary, which stage a typical method and form of apparatuts in which the in
is preferably located as usual at the first point of the gas vention may be embodied and practised but without limit
passage through the whole gas purification procedure. In ing the claimed invention specifically to such illustration,
scrubbing, a gas cooled in the usual manner to ambient 5 the simple figure is a flow diagram of an installation
temperature and freed from tar under pressure, with an which has as first stage the selective absorption of the
N-alkylated lactam, as absorbent in accordance with the sulfur compounds according to the invention and as Sec
invention, the charged absorbent contains not only the ond stage a methanol low-temperature Washing for sepa
sulfur compounds but also water and the hydrocarbons rating the carbon dioxide.
which are absorbable from or can be condensed out of 20 Referring to the drawing, the first stage comprises a
the gas under the absorption conditions. With an ab counter-flow absorbing tower 2 and an absorbent regen
sorption pressure of between 20 and 30 atms. and an ab erating tower 3 composed of a lower stripping zone and
sorption temperature of between 5 and 25 C., these are an upper concentrating zone. i he second stage incor
hydrocarbons having a boiling point of about i50 C. porates a low-temperature washing tower 16 and a re
In the regeneration of the absorbent according to the in generation device consisting of two pressure release towers
vention, the presence of these hydrocarbons must always 27, 8.
be taken into consideration even when a special preceding The gas cooled to the surrounding temperature and
scrubbing stage is provided for them. freed from tar, flows through a conduit i and a heat ex
The regeneration of the absorbent is effected under at changer 3 into the lower end portion of the scrubbing
mospheric pressure by heating the absorbent containing 30 tower 2. It is first cooled to about --10 C. in heat ex
impurities and stripping by direct contact with Stean in a changer 3 by the cold pure gas flowing out of the low
regenerating tower which consists of a lower stripping temperature washing tower 6 through conduit 36 and
zone and an upper concentrating zone. The charged con from heat exchanger 5. In accordance with the inven
taminated absorbent is fed into the regenerating tower tion, hydrogen sulfide and organic sulfur compounds as
at about half its height into direct contact with rising 35 well as hydrocarbons and also water are absorbed by the
countercurrently flowing steam. The regenerated ab selective solvents in the Washing tower 2, the gas rising
sorbent is removed from the sump of the regenerating in counter-current contact with continuously descending
tower and fed back through heat exchangers and coolers absorbent. The gas thus partially purified flows from
to the head of the absorption tower. The height of the the head of the washing tower 2 through conduit 3 and
regenerating tower and the relationship of the heights of 40 heat exchanger 5 and possibly another cooler 14 to the
the stripping zone and the concentrating Zone is so chosen low-temperature washing tower 6 in which the carbon
that the reflux at the head of the concentration zone is dioxide is scrubbed out with methanol at a temperature
free from absorbent. Due to the high boiling point of of about -40°C. The cold pure gas is led off from the
the absorbents, i.e., low volatility, all absorbed gas com head of washing tower 16 in conduit 36 through heat ex
ponents are stripped therefrom without any absorbent 45 changers 15, 13 and again heated to the surrounding tem
vapor being carried out with the gas-steaIn mixture. perature and fed through the conduit 22 for further use.
The exiting gas-steam mixture is cooled in a condenser r The regeneration of the absorbent loaded with absorbed
and separated into liquid and gaseous portions. The impurities in scrubbing tower 2 is effected in the regener
liquid portion is further separated into an upper hydro ating tower 3 by pressure release, heating and stripping
carbon phase and a lower aqueous phase by stratification 50 with steam. The loaded absorbent flows out from scrub
in a separator. The lower phase, after conducting off a bing tower 2 through conduit 33, a heat exchanger 6, a
quantity of water corresponding to the quantity of steam heater 7 and a relief valve 7a into the middle zone of
introduced into the stripping zone, is recycled to the con the regenerating tower 3 from which it is passed into a
centrating zone. distributing device 34. The lower part 5 of the regenerat
According to the invention, the operation of the regen ing tower 3 is operated as a stripping zone. A circulating
erating tower is so regulated that the regenerated absorb steam-fed evaporator 9 and a distributor 35 for direct
ent leaves the column sump with a water content of 1 to steam are arranged in the sump. The upper part of the
10%, preferably 2 to 5%, and the water content in the egenerating tower 3 is constructed as a concentrating
column increases towards the top in Such a manner that column. The water content of the liquid-steam mixtures
at the head of the concentrating zone there is no longer 60 is increased in upward direction to such an extent that
any absorbent. In the upper part of the stripping zone the head product flowing off through the conduit 36 no
and in the concentrating zone the desorption of the ab longer contains any absorbent. The gas-steam mixture
sorbed gas components is accompanied by a water-vapor passing out from the regenerating tower through the con
distillation whereby all of the hydrocarbons (light ends) duit 36 is precipitated in the condenser 10. The gaseous
are also expelled overhead. 65 residue contains the hydrogen sulfide and about 10% of
The absorption of the sulfur compounds by the N the carbon dioxide contained in the crude gas as well
alkylated lactams is due solely to physical solubility. For as Small quantities of lower hydrocarbons. This gas frac
the very selective absorption of hydrogen sulfide a loose tion is collected from the discharge 24 of the following
coordinate bond on the tertiary nitrogen atom may be as separator. The condensate is composed of water, and
sumed to be probable. 70 the hydrocarbons which separate in upward direction in
The absorbing capacity of physically acting solvents in the separator 12 as a lighter layer are drawn off over a
creases, as is known, with decreasing temperature. In weir 37 through the conduit 23. The portion of the con
order to obtain high absorption values and consequently densate forming the lower aqueous layer is recycled to the
also the use of a very much smaller volume of absorbent, head of the column through the conduit 38 by means of
the process according to the invention is conducted at 75 a pump 12. The excess water accumulating in the course
 3,120,993
5
of the process is conducted off through the branch con
duit 39. The regeneration is preferably carried out in Vol. percent Nm.3/hr.
such a manner that the regenerated absorbent leaves the
sump of the regenerating tower with a water content of 27.8 13,350
about 3 to 5%. It is returned to the head of the washing 11, 4
0.6
5,472
287
tower 2 by means of a pump 51 through the conduit 5 0.2 9.
via heat exchanger 6 and a cooler 8. hi--CO--Na--- 60.0 28,800
The gas purified from sulphur compounds is further 100.0 48,000
treated for removal of carbon dioxide in the following
low-temperature scrubbing stage ió. In this second scrub 10 The carbon dioxide is washed out of this gas to a resi
bing stage the absorption heat is removed by an evaporator due concentration of about 2% in the low temperature
40 of a cooler arranged in the proximity of the washing scrubbing in the tower 6. This carbon dioxide is free
tower sump. The cold loaded absorbent containing from sulfurous admixtures and has the purity required,
the carbon dioxide passes through the conduit 41 and a for example, for urea synthesis.
relief valve 42 into the first pressure releasing vessel 7 15
and from this through the conduit 44 and the relief valve Example II
45 to the second releasing vessel 18. The absorbent re In the plant illustrated in the drawing, 50,000 Nm.3
generated and cooled by expansion is returned to the head per hour of a natural gas ore purified under a pressure
of the washing tower 16 by means of a pump 21 through of 35 atms. at a temperature of 40° C. by scrubbing with
the conduit 46. The cold content of the expansion gases 20 150 Nm.8 N-methyl-2-methyl-pyrrolidone per hour. The
flowing off through the conduits 19 and 29 can be utilized Sulfur compounds are scrubbed out of the gas to a residual
by heat exchange at suitable points of the process, for concentration of 0.3 vol. percent.
example, in the coolers 3, 4, so that the gases can be The composition of the natural gas entering the scrub
used at about the surrounding temperature. bing tower 2 (in volume percent and the throughput
Example I quantities per hour (Nm.8/hr.) are as follows:
In the plant illustrated in the drawing, 50,000 Nm.8/h. Vol.
percent
Nm.8/hr.
of crude gas are purified under a pressure of 25 atms.
The hydrogen sulfide is scrubbed out of the gas to a resi 30 HS------------------------------------------- 10 5,500
due concentration of 2 mg. per Nm.8. This concentration CO-
C.A.--
-- 270
57.0
13,500
28,500
is about the limit that can be proved in technical analysis. N2---- - 5.0 2,500
About 60 m.8/hr. N-methyl pyrrollidone at --10 C. are
used in the washing tower 2 and about 150 m.8/hr, meth
anol at -40° C. in the washing tower ió. The composition of the purified gas is as follows:
The composition of the gas in volume percent and the
corresponding hourly throughput quantities (Nm.8/hr.) Vol. percent
are as foilows: H2S --------------------------------------- 0.3
CO2 --------------------------------------- 16.8
40 CH4 --------------------------------------- 76.0
Wol. percent Nm.8/hr. N ----------------------------------------- 6.9
O 15, OCO
The volume of the purified gas is 36,500 Nm.3. The
6 3CO content of 16.8 vol. percent carbon dioxide may be
0
.. 6
5,500
300 scrubbed out in a low temperature washing stage with
2 100 methanol as described in the foregoing example.
6 28,800 The gas impurities, absorbed in the N-methyl-2-methyl
O 50,000 pyrrolidone are 13,500 Nm.8 and have a composition as
follows:
50
In the first absorption stage the N-methyl pyrrollidone WO. Nm,3
absorbs in Nm.8/hr. and vol. percent: percent

H2S----------------------------------------------- 40.0 53,786

CO2--- 54.4 73,304
Nm,3|hr. Vol. percent 5.6 7,910
300 15.0
1,650
28
82.5
1.4
The concentration of hydrogensulphide in the gas mix
3 0.65 ture desorbed from the loaded absorbent may be enriched
9 0.45
60 by a partial pressure release of the absorbent before en
2,000 100.00 tering the regeneration tower to a pressure of about 12
atms. The gas mixture, escaping by this partial pressure
release contains.
Whereas the crude gas contains hydrogen sulfide and Vol. percent
carbon dioxide in a volume ratio of 1:50, this ratio in H2S --------------------------------------- 0.6
the expelled gas of the N-methyl pyrrolidone regeneration CO2 --------------------------------------- 89.4
amounts to 1:5.5. That is an enrichment to almost 10 CH4 --------------------------------------- 10.0
times the amount. The gas which is obtained from the and has a volume of 4,900 Nm.3.
regeneration is suitable for working up to Sulfur or Sul After full pressure release to atmospheric pressure are
furic acid in a known manner. The steam consumption in stripped from the absorbent in the regeneration tower 3
the regeneration for removal of the Sulfur compounds and 8600 Nm.8 of a gas mixture containing
distiling off the hydrocarbons and the absorbed water Wol. percent
amounts to 5 to 6 t./hr. H2S ---------------------------------------- 62.2
The pre-purified gas from the washing tower 2 has the CO2 --------------------------------------- 34.3
following composition (in vol. percent and Nm.3/hr.): CH4 --------------------------------------- 3.5
 3,130,993
7 3.
Example III tivity for hydrogen sulfide in preference to C3 hydrocar
bons. This is important for the purification of natural
30,000 Nm.8/hr. of a gas, obtained by gasification of a gases and refinery gases, because it allows a separation of
heavy oil with oxygen and steam are purified in a plant hydrogen sulfide and propane by means of a physically
illustrated in the drawing by scrubbing with 40 Nm.8/hr. acting solvent absorbent. This separation presents diffi
N-methyl ox piperidone under a pressure of 31.5 atms. at culties in many cases in the low-temperature gas decom
a temperature of 30° C. position and in low-temperature gas scrubbing processes,
The composition (vol. percent) and the throughput because hydrogen sulfide and propane form an azeotropic
(Nm.8/hr.) of the gas to be purified are as follows: mixture. The process according to the invention can there
fore be applied with advantage to gases or gas fractions,
for example, desorbate fractions of low-temperature wash
Wol. Nm.8/hr.
ing processes, which contain hydrogen Sulfide and propane.
percent We claim:
1. Process for the separation of hydrogen sulfide from
4.3 1,290 5 industrial gases which additionally contain carbon di
0.9
46.9
270
14,070
oxide and hydrocarbons, which comprises scrubbing the
46. 13,830 industrial gases with a liquid organic water-soluble ab
0.4
1.4
20
420
sorbent selected from the group consisting of N-alkylated
pyrrolidones and piperidones in an absorption Zone to
100.0 30,000 20 thereby absorb hydrogen sulfide, conducting said absorbent
containing the absorbed hydrogen sulfide from said ab
sorption to a de-absorption zone, liberating the absorbed
The composition (vol. percent) and the throughoput the hydrogen sulfide from the absorbent to thereby regenerate
(Nm.8/hr.) of the purified gas are as follows: same and recycling the regenerated absorbent to the
absorption zone.
2. Process according to claim 1, wherein said libera
tion of hydrogen sulfide is effected by flowing the ab
Wol percent Nna3/hr.
sorbent containing the dissolved hydrogen sulfide in di
rect countercurrent contact with steam in the lower strip
30 ping part of the regeneration zone, the stripped gases
0.0 O
3.6 1,070 and vapors being rectified in the upper concentration part
48.3
47.7
14,040
13,303
of said regeneration zone.
0.4 117 3. Process according to claim 2, wherein the absorbent
100.0 29,030 35
regenerated in said desorption has a water content of
from 1 to 10%.
4. Process according to claim 3, wherein the absorbet
regenerated in said desorption has a water content of
from 3 to 6%.
The composition (vol. percent) and the output (Nm.8/ 5. Process according to claim 1, wherein said absorb
hr.) from the regeneration tower 3 of the gas impurities 40 ent is N-methyl pyrrollidone.
stripped out of the loaded absorbent are as follows: 6. Process according to claim 1, wherein said absorb
ent is N-methyl 2-methyl pyrrollidone.
7. Process according to claim 1, wherein said absorb
ent is N-methyl piperidone.
Wol percent Nrm.8hr. 45 8. Process according to claim 1, wherein said scrub
bing is effected at a temperature of from 0 to 15 C.
49.0
40.0
270
220 9. Process according to claim 1, wherein said absorb
5.5 30 ent prior to admission into said desorption zone is pre
4.9 27 heated.
0.6 3
50 10. Process according to claim 1 in which said scrub
bing is effected at a temperature of from about 0 to
15° C. and which includes after said scrubbing remov
ing the remaining carbon dioxide from the gas by scrub
The design of the installation can be modified or sim bing the gas in a second stage with a polar organic sol
plified for obtaining other gas qualities. Thus, a water vent at a tenniperature below -20° C. and under in
washing under pressure can be employed for washing out creased pressure.
the carbon dioxide. The adjustment of temperature for 11. Process for the separation of hydrogen suffide from
the first stage is then effected by cooling water in the industrial gases which comprises scrubbing the indus
coolers 13 and 8 because no cold surplus is available from trial gases with a liquid organic water-soluble absorbent
the second stage. A scrubbing with heptane or a light 60 selected from the group consisting of N-alkylated pyrroli
washing oil can be introduced before or instead of the dones and piperidones in an absorption zone to thereby
carbon dioxide scrubbing treatment for removal of the absorb hydrogen sulfide, conducting said absorbent con
hydrocarbons from natural gases which contain consider taining the absorbed hydrogen sulfide from said absorp
able quantities of gaseous hydrocarbons (C3, CA). tion to a de-absorption zone, liberating the absorbed hy
For coke-oven gas, the first washing stage according to 65 drogen sulfide from the absorbent to thereby regenerate
the invention can be installed as general gas purification the same and recycling the regenerated absorbent to the
after the conventional ammonia separation. absorption Zone.
As can be seen from the foregoing description, the
ananlyses of the crude gases and of the gas mixtures ab References Cited in the file of this patent
sorbed by the N-methyl pyrrollidone show that less than 70 UNITED STATES PATENTS
10% of the C and C3 hydrocarbons contained in the 2,781,862 Fussman -------------- Feb. 19, 1957
crude gas are absorbed, with complete absorption of the
hydrogen sulfide. The pyrrolidones and piperidones to be FOREIGN PATENTS
used as absorbents have in addition to selectivity for hy
drogen sulfide in preference to carbon dioxide also a selec 75 702,876 Great Britain ---------- Jan. 27, 1954