United States Patent (19) 11 4,376,694

Lohr et al. 45) Mar. 15, 1983

(54) METHOD OF DECOKING A CRACKING 56) References Cited
PLANT U.S. PATENT DOCUMENTS
2,405,364 8/1946 Markley ... ... 585/950
(75 Inventors: Bernhard Lohr, Saarbricken; Peter 3,365,387 1/1968 Cahn et al. ... ... 208/48 R
Hesse; Robert Schuster, both of 3,532,542 10/1970 Shimizu et al. ......................... 134/2
Munich, all of Fed. Rep. of Germany
OTHER PUBLICATIONS
73) Assignee: Linde Aktiengesellschaft, Wiesbaden, Sato et al., Bulletin of the Japan Petroleum Institute, vol.
Fed. Rep. of Germany 13, No. 2, 11/1971, pp. 279-284.
Primary Examiner-Thomas A. Waltz
21 Appl. No.: 281,344 Attorney, Agent, or Firm-Karl F. Ross; Herbert Dubno
57 ABSTRACT
22 Filed: Jul. 8, 1981 A method of decoking (decarbonizing) surfaces of a
cracking plant in which the cracking furnace is con
Related U.S. Application Data nected to a heat exchanger for cooling the cracked gas
mixture, in which steam and air are admitted as a gas
63 Continuation-in-part of Ser. No. 156,608, Jun. 5, 1980, mixture to the cracking furnace and then the gas mix
abandoned. ture is conducted through the cooler. The cooling me
dium is thus passed through the cracking gas cooler
30 Foreign Application Priority Data during the decoking operation while in a first stage the
mixture is fed through the device at such a mass flow
Jun. 8, 1979 IDE Fed. Rep. of Germany ....... 2923326 rate that the temperature of the deposits on the heat
Aug. 27, 1979 (DE) Fed. Rep. of Germany ....... 2934570 exchange surface is approximately at the temperature
corresponding to cracking operations while, in a second
51 Int. Cl. .......................... C10G 9/12; C10G 9/16 stage, the gas flow rate is increased to raise the tempera
52) U.S. C. ..................................... 208/48 R; 134/2; ture of the deposits on the heat exchange surfaces of the
134/20, 134/39; 208/132; 585/648; 585/950 cooler.
58) Field of Search ................. 208/48 R, 132; 134/2,
134/20, 39; 585/950, 648 6 Claims, 2 Drawing Figures
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Consequently, it is customary to interrupt the crack
METHOD OF DECOKING A CRACKING PLANT ing operation from time to time and mechanically
decoke or decarbonize the apparatus, i.e. remove the
CROSS REFERENCE TO RELATED carbonaceous deposits.
APPLICATION It is also possible to use a chemical cleaning ap
This application is a continuation-in-part of Ser. No. proach, i.e. to introduce a mixture of air and steam to
156,608 filed June 5, 1980, now abandoned. the externally heated cracking tubes and to the gas
cooler. In the cracking tubes a temperature of 750 to
FIELD OF THE INVENTION 850 C. can be maintained to burn off the carbonaceous
Our present invention relates to a method of decok 10 deposits. However, such temperatures are not provided
ing and, more particularly, to a method of decarboniz within the gas cooler and hence little burnoff of the
ing or removing deposits from surfaces of a cracking deposits in the cooler can occur. At best, inlet zones of
plant in which a cracking furnace is followed by a the gas cooler show a reduction in the amount of carbon
cracking-gas cooler or heat exchanger. The invention which is deposited.
also relates to a method of operating a cracking plant or 15 The balance of the gas cooler remains contaminated
installation more efficiently because deposits are re with the carbonaceous deposits and hence these zones
of the cooler or the cooler itself must be disconnected
moved and to a cracking plant which can be subjected from the cracking reactor and subjected to mechanical
to the improved decoking process. cleaning.
BACKGROUND OF THE INVENTION 20 The mechanical cleaning approach generally uses a
In the production of ethylene and lower olefins, it is high-pressure water jet, e.g. at a pressure of 700 to 1,000
known to subject a hydrocarbon, generally a petroleum bar, which breaks loose the deposit and scours it from
the tubes.
fraction, to thermal degradation, referred to hereinafter A cleaning process of this type has been known to
as cracking, in a cracking furnace and thereafter to cool 25 require about three days, during which the ethylene
the cracking-gas mixture in a cooler or heat exchanger production is terminated, but has the additional disad
by indirect heat exchange with a coolant, e.g. steam or vantage of generating mechanical problems for the
water with the recovered heat being thereby trans apparatus because of the periodic reheating and cooling
formed into steam, usually high-pressure steam or su which is required and the expansion and contraction
perheated steam. 30 phenomena associated therewith which, because of the
The cracking furnace generally comprises a heated stresses they produce, reduce the useful life of the appa
chamber e.g. provided with burners, through which the ratus.
cracking-gas mixture can pass via tubes (so-called
cracking tubes) which can be of an undulating configu OBJECTS OF THE INVENTION
ration in a large number of turns or loops at least in the 35 It is the principal object of the present invention to
cracking Zone. provide an improved method of decoking (decarboniz
In the thermal cracking of hydrocarbon mixtures, ing) a cracking installation, especially for the produc
especially for the production of ethylene and other tion of ethylene and other lower olefins.
lower olefins, there are significant secondary and by Another object of this invention is to provide an
product-producing reactions which are generally tech 40 improved method of operating a cracking installation to
nologically uninteresting because of the low value of eliminate the disadvantages described above and espe
the products produced and which must be tolerated. cially the need to drastically cool the heat exchanger or
These reactions can result in heavy products giving cooler periodically in conjunction with deposit removal
rise to carbon deposits on the walls of the cracking operations.
tubes and upon the heat-exchange surfaces of the crack 45 Still another object of the invention is to provide an
ing-gas cooler. These deposits of carbon, referred to as improved plant for the cracking of hydrocarbons which
coking of the surfaces, can pose significant problems for facilitates the decoking or deposit-removal operations.
long-term use of the apparatus. For example, they re
duce the heat exchange efficiency at the externally SUMMARY OF THE INVENTION
heated coking tubes and externally cooled heat ex 50 These objects and others which will become apparent
changer passages so that fluctuation can occur in the hereinafter are attained, in accordance with our inven
process parameters and a decrease in the overall energy tion, which is based upon our discovery that special
efficiency and productivity of the apparatus. In addi mechanical decoking procedures can be eliminated for
tion, in extreme cases, the carbonization can completely the heat exchanger or cooler if, during the first stage of
block flow passages and bring operations to a standstill 55 the deposit-removal operation a mixture of air and
until these flow passages are mechanically cleaned. steam is allowed to contact the heat exchange surface at
Even before flow blockage, however, it is found that approximately the same temperature as is used for
significant additional heat must be supplied to maintain cracking but thereafter the mass flow rate of this gas
the cracking operation, thereby increasing the energy mixture is sharply increased to raise the temperature by
consumption in the cracking furnace and is paralleld by a watergas-type of carbon elimination reaction and heat
a decrease in the high-pressure steam production in the transfer from the cracking furnace, so that deposits
cooler which is used to recover the energy invested in throughout the cooler are removed.
the cracking operation to the greatest extent possible. According to the invention, therefore, the coolant
Eventually the process must be brought to a standstill continues to flow through the cooler during the decok
for cleaning in the conventional approach because the 65 ing or decarbonization reaction and the decoking or
loss in heat exchange efficiency in the cooler is incapa decarbonization is carried out in two stages. In the first
ble of rapidly terminating the cracking reaction which stage the gas stream, i.e. the mixture of air and steam
is essential to a high yield. from the cracking furnace, is conducted through the
 4,376,694
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heat exchanger so that the temperature of the deposits conductivity layer, as determined by a sudden improve
therein is approximately the same as the temperature ment in heat transfer, can be used as the measure of
prevalent at these surfaces during cracking operations. removal of the deposit.
In the second stage the mass flow rate of the gas is Nevertheless it should be noted that the renoval of
increased such that the temperature of the deposits on the carbon deposits cannot be equated fully with the
the heat exchange surfaces of the cooler is increased. burnoff which occurs in the cracking tubes since the
It is thus an advantage of the present invention that mere increase in gas velocity and mass flow rate does
the decoking or decarbonization can be carried out not bring the temperature of the deposit in the cooler to
without separation of the cooler from the cracking zone the same level as in the cracking furnace. indeet, tem
without cooling the apparatus, and without the need for 10 peratures of 600 C. may not be reached.
any mechanical deposit-removal operations. Nonetheless a significant watergas reaction decom
Mention should be made of the fact that it is known to poses the carbon which in part is broken away by the
provide a cracking gas cooler which can be decarbo increased mass flow of the gases.
nized by thermal techniques (see Bulletin of the Japan Carrying out the decarbonization process of the in
Petroleum Institute, Vol. 13, No. 2, November 1971, pp. 5 vention in two stages is necessary in order to maintain a
279-284). However in this system, the coolant is re long useful life of the cooler tubes. If the mass flow rate
moved from the heat exchanger during the deposit of the gases would be chosen high enough to initiate the
removal phase to allow the passages of the cooler to watergas reaction in the cooler tubes already in the first
function simply as extensions of the cracking zone and stage of the process, then a danger of erosion by me
to be heated to the temperature of the latter. This, how 20 chanical action between dislodged carbonaceous mate
ever, has even greater disadvantages than the systems rial and the tubes would arise.
previously described because the temperature changes We have found further that although the watergas
to which parts of the cooler are subjected are here so reaction does not require oxygen, it is advantageous to
extreme that the stress mechanically developed because utilize a mixture of steam and oxygen for the decoking
of temperature changes poses problems of danger to the 25 gas and indeed the carbon is more readily decomposed
installation. when oxygen is present.
Since the system operates under pressure, the pres Apparently the watergas reaction is catalyzed by
sure retentivity is diminished and the apparatus cannot traces of chromium and nickel which may diffuse from
be thought of as either safe or reliable. the tube materials into the coke layer. However, the
Furthermore, this process has been found to increase 30 catalytic effect is at its greatest only when the sulfur
the danger of corrosion of those surfaces which nor component in the carbonaceous layer is minimized. The
mally would be exposed to the coolant because of the presence of oxygen in the gas stream ensures transfor
high temperature to which these surfaces are brought in mation of any sulfur therein to sulfur dioxide so that the
the absence of the coolant during the decoking process. sulfur cannot remain as a catalyst poison.
With the two-stage process of the present invention, 35 The process of the present invention is preferably
the steam productions is continuous, the temperature carried out under conditions such that the gas flow rate
change in the tubes of the gas cooler themselves is mini during the second stage ensures a discharge tempera
mized and practically all of the sharp increase in tem ture of the gases from the cooler of at least 400° C.
perature is applied to the deposits. The process of the Experience has shown that coke removal velocities at
invention can be carried out with gas coolers using lower temperatures are too low to ensure effective de
conventional straight-tube bundles, eliminating the need carbonization.
for spiral or helical tube constructions as has been found When the decarbonization gas mass flow rate is held
to be essential for the earlier thermal process described. constant during the second process stage, one can select
In the first stage of the process according to the in a discharge temperature at the beginning of this stage
vention, the decarbonization gas mixture should include 45 which lies above about 400 C., the discharge tempera
steam and oxygen and preferably is a mixture of steam ture falling with increased decarbonization and reach
and air fed through the cracking furnace and effecting ing a minimum temperature which is also above 400 C.
therein a burnoff of the deposits in the manner de in the best mode embodiment of this invention.
scribed. During the first decoking phase the greater part During decoking, the deposit layer in the tubes be
of the carbon deposits are removed from the cracking 50 comes progressivly thinner so that heat exchange in
tubes and the cracking-gas cooler is cleaned only to a proves with the progress of decarbonization. The de
negligible extent because the temperature is not suffi carbonization can be considered complete when the
cient for a burnoff of the carbon deposits therein. outlet temperature becomes constant, all other condi
At the end of the first process stage, which can be tions (e.g. the gas flow rate) being likewise constant.
carried out over several hours, usually four to eight 55 We have found that the invention is especially effec
hours, the volume rate of flow of the gas mixture is tive for installations or apparatus for the cracking of
significantly increased. During the second stage, any heavy hydrocarbons such as gas oil or vacuum gas oil.
traces of deposit which remained in the cracking tubes However, it is not as effective for the decarbonization
after the first stage are removed and the coke deposit in of cracking installations utilizing lighter hydrocarbons
the cooler is removed. We have found here that the gas 60 such as naphtha and ethane where the cracking gas
mixture should be fed during the second stage in such temperatures lie below the temperatures at which sig
quantity that the temperature of the coke deposit will be nificant watergas reaction can occur. Because of the
raised significantly, at least to ensure that the watergas continuous cooling of the cooler, in such systems the
reaction will predominate at this surface. temperature in the cooler does not always reach ten
Surprisingly, this temperature increase is possible in 65 peratures to sustain the watergas reaction. In practice
spite of the continued cooling of the tubes by the cool temperatures of about 350° to 370° C. prevail in the
ant because the thermal conductivity of the coke layer cooler. In this case, and especially when the installation
is extremely low. In fact, the elimination of this low is designed for the cracking of hydrocarbons having a
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boiling point below 200 C., it has been found to be by the arrows to close the upper or lower halves of the
advantageous to carry out the decarbonization of the flow cross section as required.
cooler in stages, i.e. to decarbonize one set of cooling In the cooler embodiment of FIG. 2, on the other
surfaces after another, thereby reducing the overall hand, the tubes 4 communicate with resprective domes
cooling effect during decarbonization and allowing the 12 and 113 at their discharge sides, these domes having
watergas reaction to prevail. In this case the gas cooler respective pipes 114, 115 with selectively operable
is divided into zones as described in connection with the valves 117, 118 and communicating within outlet pipe
drawing and the entire gas mixture is passed through 16.
one zone at a time while the other zones are cut off. For
10
To select a flow cross section corresponding to only
example, it has been found to be sufficient to divide the part of a total, the respective valve 117 or 118 is opened
gas cooler into two zones or halves as described with while the other valve is closed.
each zone undergoing the two-step decoking operation When the total flow cross section is to be available,
separately. Naturally, the splitting of the gas cooler into both valves 117 and 118 are opened.
zones with the decarbonization being effected in each 15
In the drawing we have also shown a cracking fur
zone separately and the zones are decarbonized in suc nace 10 which can be supplied with hydrocarbons at all
cession, it suffices that the second stage decarbonization and which can include a multiplicity of flow cross sec
only be effected in the separate zones. In other words, tions represented by the cracking tube 13 which has an
during the first stage or phase when the cracking tubes undulating shape and can represent a large number of
are primarily decarbonized, the gas can pass through similarly shaped tubes in a multiplicity of loops disposed
the entire flow cross section of the cooler and then one 20 in the cracking zone of the furnace 10.
or more portions are cut off as the mass flow rate of the The cracking tubes 13 are externally heated, e.g. by
gas is increased for selective decarbonization of partial burners 14 opening into the furnace and supplied with
cross section of the cooler. fuel by a distrubtion network 15.
It has been found to be desirable to carry out a step 25 The exhaust gas is discharged at 17.
wise decoking of the cracking gas cooler only during During the usual cracking operation, the cracking gas
the second process stage, i.e. when an increased mass mixture is fed via line 16 and a valve 18 to the gas
flow of the decoking gases is provided. In some cases, cooler, shown to be a tube-bundle heat exchanger
however, it may also be advantageous to pass the gas whose straight tubes 4 are subdivided into two flow
stream only through a section of the gas cooler during 30 cross sections 4'', 4', respectively communicating with
the decoking in the first stage. the sections of dome 7 controlled by the plates 9,9".
BRIEF DESCRIPTION OF THE DRAWING Water or low temperature steam serving as the cool
ant is fed via duct 5 to the space around the tubes 4 and
The above and other objects, features and advantages high-pressure superheated steam is recovered at 6.
of the present invention will become more readily ap 35 The valve 40 can cut off the influx of the hydrocar
parent from the following description, reference being bon and feed to the cracking tubes 13, a mixture of
made to the accompanying drawing in which: steam and air via line 12, the burners 14 being main
FIG. 1 is a cross-sectional view through a cooler in tained fired so that carbonaceous deposits are burned up
accordance with the present invention, shown to be in the tubes 13. The gas mixture, generally consisting of
provided at its inlet side whith a diagrammatically illus residual steam and oxygen but also containing hydro
trated cracking furnace and operated in accordance gen, carbon dioxide, carbon monoxide and sulfur diox
with the method of the present invention; and ide, is then passed through the cooler in which the
FIG. 2 is a similar view diagrammatically illustrating coolant flow is continued.
another embodiment of the cooling device of the inven The cooler is thus subdivided into a plurality of flow
tion. 45 sections and the gas mixture traverses one section at a
time while the other sections are cut off,
SPECIFIC OESCRIPTION AND EXAMPLE During the second stage, the temperature of the gas is
As is apparent from the foregoing, a key to the appli measured and the volume rate of flow is increased,
cability of the present invention in a plant for the crack being certain to maintain the discharge temperature
ing of low boiling hydrocarbons is the fact that a crack 50 above 400° C. The decoking operation is being repeated
ing gas cooler during the decarbonization or decoking for the second section of the cooler.
operation is subdivided into a plurality of flow cross A conventional cracking gas cooler utilized for the
sections. During the actual cracking operation, the cooling of the cracking products can be employed with
cooling apparatus is utilized in such manner that the only limited modification at its outlet side, as shown
product gas flows through the entire or total cross sec 55 above.
tion.
In FIG. 1, therefore, the output of the cracking fur SPECIFIC EXAMPLE
nace is fed to the cooler via a line and enters the dome The following specific example is related to the
2 from which the gas passes through the tubes 4 which cracking of heavy hydrocarbons. Therefore, a conven
are surrounded by the shell 3, the product emerging tional cracking gas cooler without any modification, i.e.
into dome 7 and being discharged at 8. without means for subdividing the cooler into several
The coolant, e.g. steam, is fed into the shell 3 as repre partitions during decarbonization, is used.
sented at 5 and emerges as a heated product, e.g. high A high-severity cracker for heavy atomspheric gas
pressure steam at 6. oil, operating after 60 days with a discharge tempera
To enable the gas to flow through only a portion of 65 ture of the cracking gas mixture from the furnace of
the flow cross section during decarbonization, the dome 800° C. and a discharge temperature from the cooler of
7 is provided with a partition 9 and a pair of valve plates 634 C. is subjected to decoking after significant carbo
9, 9', which can be selectively inserted as represented naceous deposits are found to be present.
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In a first phase, the decoking is carried out by passing faces of said cracking tubes and said cooler devel
for eight hours a steam/air mixture at a mass flow rate oping carbonaceous deposits;
of 25 kg/sec./m2 through the combination of the fur (c) while further heating said furnace and cooling said
nace and the cooler with the furnace output tempera surfaces of said cooler with said coolant, interrupt
ture being about 750° C. and the colling of the heat ing the passage of said feedstock through said
exchanger continued. cracking installation, feeding a gas mixture of oxy
The mass flow rate of the mixture in the gas cooler is gen and steam through said cracking tubes and at
increased to 45 kg/sec./m2 and the furnace outlet tem least a portion of the flow cross section of said
perature was 800 C. cooler, thereby effecting substantial reduction of
After a two-hour induction period in which the coke O said carbonaceous deposits in said cracking tubes;
decomposition was found to be slight, a noticeable in (d) thereafter, while continuing to heat said furnace
crease in the coke decomposition speed occurred. The and cool said surfaces of said cooler, increasing the
coke decomposition speed was measured in terms of the mass rate of flow of said gas mixture until the tem
drop on the cooler outlet temperature during decoking perature in said cooler increases so far that carbo
15 naceous deposits in said cooler are subjected to a
with all other conditions being constant. watergas reaction; and
The coke decomposition velocity during the induc (e) continuing step (d) until said carbonaceous depos
tion phase was 2 K./hr and thereafter reached a maxi its are removed from said cracking installation.
mum of 15 K./hr. The second decoking phase was 2. The method defined in claim 1 wherein the temper
terminated after 16 hours. 20 ature of the carbonaceous deposits on said surfaces of
After a total decoking time of 24 hours, the outlet said cooler is controlled by maintaining the gas dis
temperature of the decoking gas at the cooler was about charge temperature of said cooler at at least 400° C.
400 C. during step (d).
After further cracking operations with heavy gas oil 3. The method defined in claim 2, further comprising
the cracking gas cooler outlet temperature was found to 25 measuring the temperature of the gas discharged from
be 470° C. indicating that the cooler had been practi said cooler and terminating step (d) when the tempera
cally completely cleaned. The system was operated for ture becomes constant reflecting elimination of deposits
another 60 days and then decoking was repeated. At the from said surfaces of said cooler.
end of 60 days it was found that the coking velocity, i.e. 4. The method defined in claim 1, claim 2 or claim 3
the rate of buildup of the deposit, was not greater than 30 wherein said gas mixture is passed only through a por
with mechanically cleaned coolers. tion of the flow cross section of said gas cooler during
We claim: step (d) while at least one other portion of the flow
cross section of said cooler is cut off and the flow of said
1. A method of operating a hydrocarbon cracking gas mixture is thereafter switched to said other portion
installation in which a cracking furnace is followed by a 35 while the first-mentioned portion is cut off.
cracking gas cooler, said method comprising the steps 5. The method defined in claim 4 wherein the gas
of: flow to said portions is switched so that both steps (c)
(a) subjecting a hydrocarbon feedstock to a cracking and (d) are carried out in succession in each portion
temperature in said furnace by heating cracking while the other portion is cut off.
tubes in said furnace and passing said feedstock 6. The method defined in claim 5 wherein the gas
therethrough, thereby producing cracking gases; cooler has a cool end, wherein the selective cut-off of
(b) passing said cracking gases through said cooler said portions of said cross section is effected at said cool
while supplying said cooler with a coolant to re end.
duce the temperature of said cracking gases, sur : sk : sk k

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