CA1184947A - Process for preparing olefins from heavy petroleum oil - Google Patents
Process for preparing olefins from heavy petroleum oilInfo
- Publication number
- CA1184947A CA1184947A CA000416442A CA416442A CA1184947A CA 1184947 A CA1184947 A CA 1184947A CA 000416442 A CA000416442 A CA 000416442A CA 416442 A CA416442 A CA 416442A CA 1184947 A CA1184947 A CA 1184947A
- Authority
- CA
- Canada
- Prior art keywords
- oil
- heavy petroleum
- petroleum oil
- reactor
- steam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
SPECIFICATION
Title of the Invention:
Process for Preparing Olefins from Heavy Petroleum Oil Abstract of the Disclosure:
Disclosed is a process for preparing olefins from heavy petroleum oil which comprises mixing said heavy petroleum oil with superheated steam at a steam-oil ratio in the range of from 2 to 7, and indirectly heating the resulting mixture so that the temperature at the outlet of a reaction zone may be in the range of from 700 to 950°C
at a residence time of from 0.01 to 0.1 second in the reaction zone.
The aforesaid process is capable of preparing olefins from heavy petroleum oil at high yields without the deposition of carbonaceous substances or the development of coking on the inner wall of a reaction.
Title of the Invention:
Process for Preparing Olefins from Heavy Petroleum Oil Abstract of the Disclosure:
Disclosed is a process for preparing olefins from heavy petroleum oil which comprises mixing said heavy petroleum oil with superheated steam at a steam-oil ratio in the range of from 2 to 7, and indirectly heating the resulting mixture so that the temperature at the outlet of a reaction zone may be in the range of from 700 to 950°C
at a residence time of from 0.01 to 0.1 second in the reaction zone.
The aforesaid process is capable of preparing olefins from heavy petroleum oil at high yields without the deposition of carbonaceous substances or the development of coking on the inner wall of a reaction.
Description
9~'7
- 2 Background of the Invention:
lhis inveiltion relates to a procexs for pre~)lri~lg olefills SUC}l as e-tllylene, propylerle, alld the Like ftom heavy petroleulll oil l~y usc of an eYtcrnll.l tlea~ing tyr)e tubular reactor.
The term "heavy petroleum oil" used in the present invention is meant to include crude oil, atmospheric pressure residual oil, and reduced pressure residual oil.
Olefins such as ethylene, propylene and the like have long been produced on an industrial scale by use of an external heating type tubular reactor, wherein naphtha has been used as the raw material J while the crude oil, heavy oil and the like, which contain nonvolatile matter, have not been used as the raw material due to severe coking in the thermal cracking process and in the quenching process for a produced gas.
As a process for the preparation of olefins from heavy petroleum oil as the raw material, there are kno~n processes which use a fluidized bed and which use a high temperature medium stream. The process which uses the fluidized bed includes a process which uses a moving fluidized bed [Kagaku Kogaku (Chemical Engineering), Vol.
40, No. 7, pp. 358 - 362 ~1976)], and a process l~hich uses a spouted bed [Kagaku Kogaku (Chemical Engineering), ~Jol.
40S No. 7, pp. 340 - 346 ~1~76)]. Ho~rever, tllese pl`OCeSSeS
have such problems that quenching~ of the proclucecl gas, ~rllich is important in the preparation of oleflns, is difflcult to be effected, and that thermal cracking of heavy petroleum oil mus~ be carried out in a residence time of about one second at a relatively low temperature o about 750C, because it is difficult to make the resldence time le5s than one second.
On the other hand, according to the proce~s which uses a high temp~rature medium stream ~Kagaku Kogaku (Chemical Engineering), Yol. 40, No. 7, pp. 354 - 357 ~1976)J, a combustion flame which uses oxygen and fuel as a heating medium results in high cost, since the high temperature superheated steam is used as the dilution st~am for tempera~ure con~rol. Moxeover, a high yield of ace~ylene according ~o the aforesaid process makes it unsuitable as a process for the preparation of ethylene.
Brief Summar _ the Invention:
An object of an aspect of this invention is to provide a process for continuously preparing olefins from hea~y petroleum oil by use of an external heating type tubular reactor without coking~
An object of an aspect of this invention is to pxovide a process for preparing olefins from heavy petro-leum oil at high yield.
An aspect of the invention is as follows:
A process for preparing olefins from heavy pe~ro-leum oil, said heavy petroleum oil being mixed with steam and fed to a tubular reaction zone externally heated for the preparation of oleEins, which comprises mixlng said heavy petroleum oil with superh~ated steam at a steam-oil ratio in -the range of ~rom ~ to 7, and indirectly heating the resulting m:lx~ure so that th~
temperature at the outle-t of cl r~action zone may be in the range of from 700 to 950C at a xesidence time of from 0.01 to 0.1 second in the react:ion zone.
Brief Descri tion of the Dra ~ -Fig. 1 is a flow sheet showing one embodiment of the process of the present invention. Fig. 2 is a diagrammatic sectiona~ view showing an example of a raw material feeding mechanism used in the practice of the process of the present invention.
Detailed Descri tion of the Pre~erred Embodiments:
According to the present invention, an external heating type tubular reactor is used. The reactor con-sists of a hollow tube and is provided with a raw material feeding mechanism at the top thereof. The raw material ~eeding mechanism used may be of any type so long as the heavy petroleum oil is atomized by a superheated steam above 750C so that fine particles of the heavy petro-leum oil may be homogeneously mixed with the superheated steam, preferably of the type shown below. The tubular reactor preferably has an inner diameter of from 3 to 15 cm~ and a length of from 3 to 30 m. The reactor may be of a str~ight tube or o-f a hairpin-shaped tube, alld may be installed ver~isally or horizontally. '['lle tllbular reactot may aLso l)e in~;till1.ed plurally in a furnclce.
The heavy petroleum oil fed frolll the raw material feeding mechanism as an atomized mixture with the superheated steam above 750C is subjected to cracking, while being mixed with the high temperature superheated steam. Therefore, neither deposition of carbonaceous substances nor coking on the inner wall of the reactor takes place. The heavy petroleum oil to be introduced into the raw material feeding mechanism is fed thereinto at a temperature lower than 400C
in order to prevent coking in the nozzle.
The tempe-rature of the superheated steam is generally above 750C, preferably in the range of from 750C
to 1200C. Use of superheated steam above 750C provides the heat required for the cracking of the heavy petroleum oil, resulting in preventing coking onto the inner wall of the reactor, and in achieving a continuous operation. When the temperature of the superheated steam is lower than 750C, coking onto the inner wall of the reactor takes place. When higher than 1200~C, costs of the superheated steam hecome higher, while the effectiveness in preventing coking onto the inner wall of the reactor is not further increased.
9~7 A mixing ratio of the superheated steam and -the heavy petroleum oil is generally in the range of from 2 to 7, preferably 3 to 5 as a stcam-oil ra-tio ~moles of ~12O in the superheated steclm/carbon atOllls itl ~he ~leaVy p~rOl~UIII
oil). When the steam-oil rat:io i.s less than 2, allloun~s of both steam and heat given from other than thc reactor become insufficient, resulting in a reduction in both the degree of cracking and yields of ethylene, propylene, etc., and in coking within the tube. When greater than 7, the amount of unreacted steam is increased, and heat loss is also increased with no economic advantages.
The atomized mixture of the heavy petroleum oil and the superheated steam is heated indirectly externally to a temperature of from 700 to 950C, preferably 750 to 900C at the outlet of the reactor while flowing through the tubular reactor. The residence time in the reactor is in the range of from 0.01 to 0.1 second, preferably 0.03 to 0.06 second. As a result, the heavy petroleum oil is subjected to thermal cracking to be converted to gaseous components such as lower olefins, hydrogen, carbon mono~ide, arbon dioxide and lower saturated hydrocarbons, vapors or mists of various heavy hydrocarbons, and the like.
~;~ When the temperature of the fluid at the outlet o the reactor is lower than 700C, there is SUC}I a tendency that yields o olefins are reduced and coking onto the inner wall of the reactor takes place. I~hen higher than 900C, the amounts of carbon mono~iclc, carbon ~io~ide and hydrogen are increased, atld the yields of lower olefirls such as ethylene, and plopylenc are reduc~d. ~ ell ~h~
residence time in the reactor is l~ss th.lll 0.01 second, cracking of the heavy petrolcum oil bccornes insuf~icient.
When greater than 0.1 second, there is such a tendency that the yields of lower olefins such as ethylene and propylene are reduced, and coking onto the inner wall of the reactor takes place.
A mi~ed fluid produced by thermal cracking in the tubular reactor is quenched in an extremely short period of time, for example, less than 0.05 second to such a tempera-ture of from 500 to $00C that the thermal cracking reaction is substantially stopped. The aforesaid quenching process may be carried out according to the conventional processes, for example, those disclosed in Japanese Patent Publication No. 573/1966, Japanese Patent Laid-open Publication No.
110889fl980, etc.
One embodiment of the present invention will be illustrated with reference to the accompanying drawings.
In Fig. 1, steam at 5 to 10 kg/cm gauge is introduced from line 1 to a superheater 2, and heated to form superheated steam at a temperature above 750C, preferably of from 750 to 1200C. The superheated s-team is introduced through line
lhis inveiltion relates to a procexs for pre~)lri~lg olefills SUC}l as e-tllylene, propylerle, alld the Like ftom heavy petroleulll oil l~y usc of an eYtcrnll.l tlea~ing tyr)e tubular reactor.
The term "heavy petroleum oil" used in the present invention is meant to include crude oil, atmospheric pressure residual oil, and reduced pressure residual oil.
Olefins such as ethylene, propylene and the like have long been produced on an industrial scale by use of an external heating type tubular reactor, wherein naphtha has been used as the raw material J while the crude oil, heavy oil and the like, which contain nonvolatile matter, have not been used as the raw material due to severe coking in the thermal cracking process and in the quenching process for a produced gas.
As a process for the preparation of olefins from heavy petroleum oil as the raw material, there are kno~n processes which use a fluidized bed and which use a high temperature medium stream. The process which uses the fluidized bed includes a process which uses a moving fluidized bed [Kagaku Kogaku (Chemical Engineering), Vol.
40, No. 7, pp. 358 - 362 ~1976)], and a process l~hich uses a spouted bed [Kagaku Kogaku (Chemical Engineering), ~Jol.
40S No. 7, pp. 340 - 346 ~1~76)]. Ho~rever, tllese pl`OCeSSeS
have such problems that quenching~ of the proclucecl gas, ~rllich is important in the preparation of oleflns, is difflcult to be effected, and that thermal cracking of heavy petroleum oil mus~ be carried out in a residence time of about one second at a relatively low temperature o about 750C, because it is difficult to make the resldence time le5s than one second.
On the other hand, according to the proce~s which uses a high temp~rature medium stream ~Kagaku Kogaku (Chemical Engineering), Yol. 40, No. 7, pp. 354 - 357 ~1976)J, a combustion flame which uses oxygen and fuel as a heating medium results in high cost, since the high temperature superheated steam is used as the dilution st~am for tempera~ure con~rol. Moxeover, a high yield of ace~ylene according ~o the aforesaid process makes it unsuitable as a process for the preparation of ethylene.
Brief Summar _ the Invention:
An object of an aspect of this invention is to provide a process for continuously preparing olefins from hea~y petroleum oil by use of an external heating type tubular reactor without coking~
An object of an aspect of this invention is to pxovide a process for preparing olefins from heavy petro-leum oil at high yield.
An aspect of the invention is as follows:
A process for preparing olefins from heavy pe~ro-leum oil, said heavy petroleum oil being mixed with steam and fed to a tubular reaction zone externally heated for the preparation of oleEins, which comprises mixlng said heavy petroleum oil with superh~ated steam at a steam-oil ratio in -the range of ~rom ~ to 7, and indirectly heating the resulting m:lx~ure so that th~
temperature at the outle-t of cl r~action zone may be in the range of from 700 to 950C at a xesidence time of from 0.01 to 0.1 second in the react:ion zone.
Brief Descri tion of the Dra ~ -Fig. 1 is a flow sheet showing one embodiment of the process of the present invention. Fig. 2 is a diagrammatic sectiona~ view showing an example of a raw material feeding mechanism used in the practice of the process of the present invention.
Detailed Descri tion of the Pre~erred Embodiments:
According to the present invention, an external heating type tubular reactor is used. The reactor con-sists of a hollow tube and is provided with a raw material feeding mechanism at the top thereof. The raw material ~eeding mechanism used may be of any type so long as the heavy petroleum oil is atomized by a superheated steam above 750C so that fine particles of the heavy petro-leum oil may be homogeneously mixed with the superheated steam, preferably of the type shown below. The tubular reactor preferably has an inner diameter of from 3 to 15 cm~ and a length of from 3 to 30 m. The reactor may be of a str~ight tube or o-f a hairpin-shaped tube, alld may be installed ver~isally or horizontally. '['lle tllbular reactot may aLso l)e in~;till1.ed plurally in a furnclce.
The heavy petroleum oil fed frolll the raw material feeding mechanism as an atomized mixture with the superheated steam above 750C is subjected to cracking, while being mixed with the high temperature superheated steam. Therefore, neither deposition of carbonaceous substances nor coking on the inner wall of the reactor takes place. The heavy petroleum oil to be introduced into the raw material feeding mechanism is fed thereinto at a temperature lower than 400C
in order to prevent coking in the nozzle.
The tempe-rature of the superheated steam is generally above 750C, preferably in the range of from 750C
to 1200C. Use of superheated steam above 750C provides the heat required for the cracking of the heavy petroleum oil, resulting in preventing coking onto the inner wall of the reactor, and in achieving a continuous operation. When the temperature of the superheated steam is lower than 750C, coking onto the inner wall of the reactor takes place. When higher than 1200~C, costs of the superheated steam hecome higher, while the effectiveness in preventing coking onto the inner wall of the reactor is not further increased.
9~7 A mixing ratio of the superheated steam and -the heavy petroleum oil is generally in the range of from 2 to 7, preferably 3 to 5 as a stcam-oil ra-tio ~moles of ~12O in the superheated steclm/carbon atOllls itl ~he ~leaVy p~rOl~UIII
oil). When the steam-oil rat:io i.s less than 2, allloun~s of both steam and heat given from other than thc reactor become insufficient, resulting in a reduction in both the degree of cracking and yields of ethylene, propylene, etc., and in coking within the tube. When greater than 7, the amount of unreacted steam is increased, and heat loss is also increased with no economic advantages.
The atomized mixture of the heavy petroleum oil and the superheated steam is heated indirectly externally to a temperature of from 700 to 950C, preferably 750 to 900C at the outlet of the reactor while flowing through the tubular reactor. The residence time in the reactor is in the range of from 0.01 to 0.1 second, preferably 0.03 to 0.06 second. As a result, the heavy petroleum oil is subjected to thermal cracking to be converted to gaseous components such as lower olefins, hydrogen, carbon mono~ide, arbon dioxide and lower saturated hydrocarbons, vapors or mists of various heavy hydrocarbons, and the like.
~;~ When the temperature of the fluid at the outlet o the reactor is lower than 700C, there is SUC}I a tendency that yields o olefins are reduced and coking onto the inner wall of the reactor takes place. I~hen higher than 900C, the amounts of carbon mono~iclc, carbon ~io~ide and hydrogen are increased, atld the yields of lower olefirls such as ethylene, and plopylenc are reduc~d. ~ ell ~h~
residence time in the reactor is l~ss th.lll 0.01 second, cracking of the heavy petrolcum oil bccornes insuf~icient.
When greater than 0.1 second, there is such a tendency that the yields of lower olefins such as ethylene and propylene are reduced, and coking onto the inner wall of the reactor takes place.
A mi~ed fluid produced by thermal cracking in the tubular reactor is quenched in an extremely short period of time, for example, less than 0.05 second to such a tempera-ture of from 500 to $00C that the thermal cracking reaction is substantially stopped. The aforesaid quenching process may be carried out according to the conventional processes, for example, those disclosed in Japanese Patent Publication No. 573/1966, Japanese Patent Laid-open Publication No.
110889fl980, etc.
One embodiment of the present invention will be illustrated with reference to the accompanying drawings.
In Fig. 1, steam at 5 to 10 kg/cm gauge is introduced from line 1 to a superheater 2, and heated to form superheated steam at a temperature above 750C, preferably of from 750 to 1200C. The superheated s-team is introduced through line
3 to a raw material feeding ~lechanislll 5. On the other hand!
heavy petroleum oil as the ra~,r material is preheated to a temperature belo~ 400C and in-troduced through linc 4 to the raw material feeding mecharlisltl. A steam-oil ratio is set in the range o~ ~rom 2 to 7, pre~lably 3 to 5. Ihe raw material feeding mechanislll 5 may l)e o~ y type sv lon~
as the heavy petroleum oil as thc raw matctial CiLtl ~e atomized to form an atomized miYtu-~e with thc superheated steam, preferably of -the type show-ll in Fig. 2.
In Fig. 2, 11 represents an atomizer block, 12 a nozzle for use in heavy petroleum oil as -the raw material, and 13 a nozzle for use in the superheated steam ~hich surrounds the nozzle 12. The tip of the nozzle 12 extends a little forward of that of the nozzle 13, whereby atomization of the heavy petroleum oil as the raw material can preferably be effected to form an atomized mixed stream, in which the heavy petroleum oil and the superheated steam are homogeneously mixed.
The heavy petroleum oil as the raw material and the superheated steam, which are atomized and mixed by use of the raw material feeding mechanism 5, are fed into a -tubular reactor 6 in a furnace 7 preferably at a mass velocity of from 0.6 to 11.0 kg/hr/sectional area ~cm2) of the tubular reactor. The mixed stream of the heavy petroleum oil and tlle superheated steam is hea-ted with a combustion flame in the furnace 7 passing through the tubular reactor 6 at a residence time of from 0.01 to 0.] second, preferably 0.0~ to ().06 second, to reach a temperature of from 700 to 950C, prefer~bly 750 to 900C at the outlet of the reactor 6. The pressure at the outlct of the r~actol 6 is l)-r~ferably in the range of from 0 to 1 k~/cm2 ~ ILlge.
The mixed stre.llll resllltillg ~rom the r~actor 6 is passed to a quenchel 9 via lirle 8 to be quenched to a temperature of from 500 to 600C, so that thermal cracking may substantially be stopped. The mixed stream resulting from the reactor 6 should be reached to the quencher in less than 0.05 second. The quenching procedure may be performed, for example, in the manner below.
The mixed stream resulting from the reactor 6 is introduced into the quencher 9 at a mass velocity of from 50 to 120 kg/m2/sec, and quenched indirectly to a temperature of from 500 to 600C within 0.05 second to stop the thermal cracking reaction and to generate high pressure steam for recovery of heat energy. A direct quenching process, in which a hydrocarbon oil for quenching is injected into the mi~ed stream resulting from the reactor 6, is also widely known.
The quenched mixed stream is withdrawn from line 10. The resulting mixed stream has the following composition:
H2 0.6 - 1.6 ~ by weight CO 0.8 - 9.0 ~
C2 0.3 - 6.0 "
CH~ 8.0 - 22.0 "
C2H6 2.0 - 6.0 C2H4 1~.0 - 31.0 "
C2~12 o - 0.7 ~ by weight C3H8 0.1 - 0.7 "
C3~16 2.0 - 10.0 "
1,3-C4~16 1.0 - ~.() "
Other C4 o 7 - 3 "
Liquid 27 0 - 55 0 "
substances The mixed stream is separated into its respective ingredients by the conventional procedure.
The process of the present invention can be applied temporarily to the thermal cracking of naphtha 9 kerosine~
gas oil, and the like. Therefore, even in the case where the necessity to temporarily stop the feeding of heavy petroleum oil to the reactor occurs, the aforesaid operation can be continued with the use of light petroleum oil without changing operating conditions and then by replacing light petroleum oil with heavy petroleum oil for normal operation.
In accordance with the present invention, olefins are produced from heavy petroleum oil without coking onto the inner wall of the reactor by selecting specified thermal cracking conditions by use of the e~ternal heating type tubular reactor, resulting in high yields of olefins and a long period of continuous operation.
E~amples of the present invention will be sho~n below along with comparative e~amples.
9~
Examples 1-10, Comparative Examples 1-14:
A tubular reactor having an inner diameter of ~0 mm and a heating length of 1 m, on top of which a two-fluid nozzle of the type showrl in E:ig. 2 is mounte~, is installed vertically in the furnac0, and steam superheated by a superheater and heavy pe-~:roleum oll are Eed to the two-fluid nozzle to be atomized and mixed, forming a mixed stream. The mixed stream is subjected to thermal cracking to form olefins, hydrogen, other various hydrocarbons, and the like.
The heavy petroleum oils used are shown in Table 1.
The operating conditions, composition of produced gases, and conditions of operation for each example are shown in Table 2.
9~7 - ~2 -r~Lb 1~ L
~ ~tllo ~ r .l. c l~ c ~l KuwaLtpressurepre.C.~Jurc crudere~idtlaLr~s klu~t 1 I oLl (MiddLe oiL (M:Lddlc East crudeEas~ crude oil) oil) Specific gravity (22/4C) 0.8532 0.9395 1.029 Moisture (vol. %) 0.05 0.1 Residual carbon (vol. %) 4.82 9.07 Elemental analysis (vol. %) C ~35.08 85.09 ~5.12 12.05 `11.75 11.17 S 2.93 2.9 4.9 ~ 0.1 0.2 0.45 Vanadium (ppm) 24 50 150 ¦ Nickel (ppm) 11 ' 25 45
heavy petroleum oil as the ra~,r material is preheated to a temperature belo~ 400C and in-troduced through linc 4 to the raw material feeding mecharlisltl. A steam-oil ratio is set in the range o~ ~rom 2 to 7, pre~lably 3 to 5. Ihe raw material feeding mechanislll 5 may l)e o~ y type sv lon~
as the heavy petroleum oil as thc raw matctial CiLtl ~e atomized to form an atomized miYtu-~e with thc superheated steam, preferably of -the type show-ll in Fig. 2.
In Fig. 2, 11 represents an atomizer block, 12 a nozzle for use in heavy petroleum oil as -the raw material, and 13 a nozzle for use in the superheated steam ~hich surrounds the nozzle 12. The tip of the nozzle 12 extends a little forward of that of the nozzle 13, whereby atomization of the heavy petroleum oil as the raw material can preferably be effected to form an atomized mixed stream, in which the heavy petroleum oil and the superheated steam are homogeneously mixed.
The heavy petroleum oil as the raw material and the superheated steam, which are atomized and mixed by use of the raw material feeding mechanism 5, are fed into a -tubular reactor 6 in a furnace 7 preferably at a mass velocity of from 0.6 to 11.0 kg/hr/sectional area ~cm2) of the tubular reactor. The mixed stream of the heavy petroleum oil and tlle superheated steam is hea-ted with a combustion flame in the furnace 7 passing through the tubular reactor 6 at a residence time of from 0.01 to 0.] second, preferably 0.0~ to ().06 second, to reach a temperature of from 700 to 950C, prefer~bly 750 to 900C at the outlet of the reactor 6. The pressure at the outlct of the r~actol 6 is l)-r~ferably in the range of from 0 to 1 k~/cm2 ~ ILlge.
The mixed stre.llll resllltillg ~rom the r~actor 6 is passed to a quenchel 9 via lirle 8 to be quenched to a temperature of from 500 to 600C, so that thermal cracking may substantially be stopped. The mixed stream resulting from the reactor 6 should be reached to the quencher in less than 0.05 second. The quenching procedure may be performed, for example, in the manner below.
The mixed stream resulting from the reactor 6 is introduced into the quencher 9 at a mass velocity of from 50 to 120 kg/m2/sec, and quenched indirectly to a temperature of from 500 to 600C within 0.05 second to stop the thermal cracking reaction and to generate high pressure steam for recovery of heat energy. A direct quenching process, in which a hydrocarbon oil for quenching is injected into the mi~ed stream resulting from the reactor 6, is also widely known.
The quenched mixed stream is withdrawn from line 10. The resulting mixed stream has the following composition:
H2 0.6 - 1.6 ~ by weight CO 0.8 - 9.0 ~
C2 0.3 - 6.0 "
CH~ 8.0 - 22.0 "
C2H6 2.0 - 6.0 C2H4 1~.0 - 31.0 "
C2~12 o - 0.7 ~ by weight C3H8 0.1 - 0.7 "
C3~16 2.0 - 10.0 "
1,3-C4~16 1.0 - ~.() "
Other C4 o 7 - 3 "
Liquid 27 0 - 55 0 "
substances The mixed stream is separated into its respective ingredients by the conventional procedure.
The process of the present invention can be applied temporarily to the thermal cracking of naphtha 9 kerosine~
gas oil, and the like. Therefore, even in the case where the necessity to temporarily stop the feeding of heavy petroleum oil to the reactor occurs, the aforesaid operation can be continued with the use of light petroleum oil without changing operating conditions and then by replacing light petroleum oil with heavy petroleum oil for normal operation.
In accordance with the present invention, olefins are produced from heavy petroleum oil without coking onto the inner wall of the reactor by selecting specified thermal cracking conditions by use of the e~ternal heating type tubular reactor, resulting in high yields of olefins and a long period of continuous operation.
E~amples of the present invention will be sho~n below along with comparative e~amples.
9~
Examples 1-10, Comparative Examples 1-14:
A tubular reactor having an inner diameter of ~0 mm and a heating length of 1 m, on top of which a two-fluid nozzle of the type showrl in E:ig. 2 is mounte~, is installed vertically in the furnac0, and steam superheated by a superheater and heavy pe-~:roleum oll are Eed to the two-fluid nozzle to be atomized and mixed, forming a mixed stream. The mixed stream is subjected to thermal cracking to form olefins, hydrogen, other various hydrocarbons, and the like.
The heavy petroleum oils used are shown in Table 1.
The operating conditions, composition of produced gases, and conditions of operation for each example are shown in Table 2.
9~7 - ~2 -r~Lb 1~ L
~ ~tllo ~ r .l. c l~ c ~l KuwaLtpressurepre.C.~Jurc crudere~idtlaLr~s klu~t 1 I oLl (MiddLe oiL (M:Lddlc East crudeEas~ crude oil) oil) Specific gravity (22/4C) 0.8532 0.9395 1.029 Moisture (vol. %) 0.05 0.1 Residual carbon (vol. %) 4.82 9.07 Elemental analysis (vol. %) C ~35.08 85.09 ~5.12 12.05 `11.75 11.17 S 2.93 2.9 4.9 ~ 0.1 0.2 0.45 Vanadium (ppm) 24 50 150 ¦ Nickel (ppm) 11 ' 25 45
4~
Table 2 I Example 1 ¦ Exa~ple 2I Example 3I E~ample 4 Heavy petroleum oil as I Kuwait ! Kuwalt I Kuw~lt I Kuwait raw material orude oil ¦ crude oil ~ oru~e olll cr~de oil Temperature of l .
superheated steam (C) I 1000 1000 ¦ 1200 ¦ Te~perature at the O , 750 j 800 ~ 900 1 800 outlet of the reactor ( C) Steam-oil ratio (moles of H20/carbon atoms) 1 2 1 ~ I 4 I 5 _ . ~ , Residence time ~sec) I 0.06 0.1 1 0.01 ¦ 0.03 Mass velocity (kg/hr/sectional area 1.8 0.9 8.1 2.8 ~cm2~ of the reactor) . ... .
¦ H2 (weight %~i 0.7 0.9 0.8 0.9 CO ( " ~I 1.1 2.3 1 1.8 2.3 2 ( " ~I 0 4 1.2 1 0.8 1.2 ~ CH4 ( 71 ~I15.8 19.3 1 18.8 17.2 I ~ C2H6 ( " )~ 3.8 4.2 1 4.4 5.1 .~ C2H4 ( " ) 18.0 26.0 ' 27.2 29.3 ~ ~ C2H2 ( " ), 0.2 ~0.3 ' 0.4 0.3 1~ O C3H8 ( " )¦ 0.4 10.3 1 0.2 0.4 I o C3H6 ( " ~¦10.0 ¦ 5.C 3.1 7.4 : g 1'3-C4H6 ~ " )I6.8 2.0 1 2.4 4.0 Other C4 ( ~ )'2.2 1.2 - 2.1 2.1 : hydrocarbons I i Liquid ( " )I40.6 37.3 1 32.Q 29.8 substances l ~
_ . .._ . __ ~
Conditions of operation Operation Operation Operation Operation (Coking, period of . for 8 hrs for 8 hrs for 8 hrs for 8 hrs continuous operation, Cokin~ at etc.) the outlet . of the tube _ .
TCIb1e 2 ~COnt. ~
Comyarat-ive Comparat:i,ve ('o~rlpar~ ive C'otllE~ar.l~ive ~.Y.1111l~ L~ 1 E-~LI(;IP 1.~! 2. ~ IIIP 1~ 3 ~ rlr~P Le ~j ___............ __ ~ .,_ ._ __ . . ~. _ _ . _. _ ... , . . .. _ , ~ _ . . _ . _.. _ , .. .. ._~ . ____ . _ .
Heavy petroleum oil as Kuwait K~lwai~ KllwaL~ Kuwait raw material cru~le o~ rude o~ rucle oL:I. crl~cl~! oi:l Temperature of 800 800 700 lOOO
superheated steam ( C) Temperature at the outlet of the reactor (C) 680 950 SOO 900 8team-oil ratio (moles 2 , 2 4 4 of H20/carbon atoms) .
Residence time (sec) 0.06 0~03 0.1 0.008 Mass velocîty (kg/hr/section~l area I 1.9 ~I 3.0 0.9 10.1 ~cm2~ of the reactor) ~ ' i f (weight ~) 0-3 1 1.4 ' 0.7 0.8 CO ( " ) 0.7 ` 7.8 2.1 ~1.7 2 ( " ) 0.2 4.5 1.1 0.8 12.1 21.2 17.3 18.5 ( ) 2.4 : 3.7 3.S 4.2 , ~1 '.
C2~4 ( ~- )15.7 22.2 24.3 ~ 27.0 , h I C2H2 ( 1l ) - ,0-5 0.2 0.4 C3H8 ( )0.4 ~ 0.1 ~0.4 0.2 1 3 6 )9.8 2.3 5.7 3.6 3~C4H6 ( )7.2 1.9 2.3 2.7 ¦ hydrocarbons ( " ) 2.7 1.0 ~ 1.3 ~.3 bstances ( ) 4S.5 33.4 40.S 37-~
__ ___ . _ ¦ Conditions of operation IOperat~oll Operation Operatioll Operation I (Coking, period of i for 8 hrs Eor S hrs i for S hrs for S hrs continuous operation, ICoking all 1 ¦ Pod~
etc.) lover the I the inn~r ¦inner wall I w~l L o f th~
I~ the tube I
Table 2 (cont . ~
Icompara~ive!co~parative Comparatlvel Exam 1 5 ¦ Example 5 I Example 6 Exa~lple 7 ¦ P
_ __ _ _ ; _ ~_ . ......... A ~_ I _~_ Heavy petroleum oil ~s ¦ Kuwait Kuwalt KU~it j~tmo5pheric raw material ¦ crude oil crucl~! oll ~ru~e Oillpre~sure ~ t~ ~ re~idual oll !
I Temperature of I superheated steam (C~ I 1000 1000 ¦ :L000 800 ~ . _ , . .
Temperature at the l ou~let of the reactor (C) 800 900 1900 750 _ .............. ! ---- __ Steam-oil ratio ~moles l l of H2O/carbon atoms) 1 4 0.8 1 8 2 1.
. ~
Residence time (sec) ¦0.15 ¦ 0.01 ¦0.01 0.06 Mass velocity (kg/hr/sectional area 0.6 13.3 7.4 1.8 (cm2) of the r~actor) . _ .___ ! ~2 ~weight %) 1.0 ¦ 1.2 1 0.6 CO ( " ~ 3.1 12.1 11.1 l ~ C2 ( " ) 1.8 1 11.1 10.5 ¦ x CH4 ( " ~I20.0 ¦ ,18.2 ¦14.7 ¦ ~ C2H6 ( " )I4 3 , ¦4.3 3.7 C2H4 , ¦ ,27 8 15.1 h C2H2 ( ~ 0.1 10.5 0.2 o C3H8 ( " ~!0 3 0.3 0.4 1 ~ ~ C3H6 ( " ) 4.0 j4.6 8.9 ~: O 1'3-C4H6 ( " ) 2.0 !3.1 6.3 ~: ~ Other C4 t " ) 0.8 ¦ 2.4 2.3 : ~ substances ( ) 40.1 34.4 46.8 _ . ,. . _._ .
: Conditions of operation Operation Coking Operation Operation (Coking, period of for 8 hrs Incapable for 8 hrs for 8 hrs oontinuous operation, Coking at of . the outl.et operation _ . of the l.. ube _ Table 2 (cont .
.. .._ ~_ Exa~ple 6 Comparative I Comparati~e Example 8 , Example 9 Heavy petroleum oil as I Atomospheric Atomospher$c~ Atomosyheric raw materialpressure prcssurc I pre.~ re _ ____ residual oll re~idual oil Temperature of superheated steanl (C) 1000 700 ¦ 1000 _. _ __ . _ _ __ _ _ Temperature at the ou~let oE the reactor (C) 850 850 700 .~ .. _ _ - .. _ _ . .
Steam-oil ratio (moles l of H20/carbon atoms) 1 4 4 ~ 4 _ - _ __ !
Residence time (sec) ¦ 0.03 0 03 ! 0.15 _ . ~ _ .__ . _ _ . I
Mass velocity (kg/hr/sectional area 2.8 2.8 0.6 (cm2) of the reactor) , _ _ H2 (weight %) ¦ 0.9 0.8 ¦ 0.7 C0 ( " ) 2.4 2.3 1 2.3 2 ~ " ) 1.3 1.1 1.0 CH4 ( " ) 17.5 ¦15.8 ! 14.9 . C2~6 ( " ) I 4-2 1 3.8 1l 2.8 C2H4 ( " ) 24.3 21.2 20.8 o C2H2 ( " ) 0.2 0.1 1 ~
~ C3H8 ( " ) ¦ 0.3 0.3 1 0.5 .~ C3H6 ( " ) 6.8 7.0 8.0 : I ~ 1'3-C4H6 ( ) 3.5 3.4 3.7 hydrocarbons ( ) 1.9 1.7 2.1 : substances ( " ) 36.7 49.5 43,2 ~ __ _ .. . ._ Conditions of operation (Coking, period of continuous operation, : etc.) _ _ . . ____ _ . . ~__ ____ _ g47 Table 2 (cont~) j I Example 7 r Example 8 ¦ Y,xample 9 Hea~y petroleum oil as I Reduced I Reduced I l~educed . pressure pressure pressure raw materlal residual oil residu/ll oll residuaL oi~.!
Temperature of ¦ 1000 1200 900 . superheated steam ( C) ! ~
¦ outlet of the reactor (C) 900 800 ,50 ¦ Steam-oil ratio (moles l ! of H2/carbon atoms) 1 4 5 4 - -- _ _ _ ¦ Residence time (sec) I 0,03 0.01 ¦ 0.1 . Mass velocity (kg/hr/sectional area 2.7 8.5 0.9 . (cm~ ) of the reactor) ~ _ H~ (weight %) ¦0.~ 0.8 1 0.7 CO ( " ~1 2.3 2.3 1 2.0 2 ( " )I 1.3 1.2 1.0 ~ CU4 ( " ~I 16.2 16.8 8.2 oC2H6 ( " ) 3.2 3.2 3.0 2H4 ( " ) 22,3 22.4 1 15.1 . oC2~2 ( " )I 0.2 0.2 1 0.1 : o 3 8 ( ) 0.2 0.3 0.3 : .~C3~6 ( " ) 6.3 4.~ 5.0 :~ ~1~3 C4H6 ( ) 3.1 2.2 2.4 Other C4 ( " ) 1.2 1.0 I.0 hydrocarbons Li~uid ( " ~1 42.8 44.8 61.2 substances I _ .
Conditions of operation Operation Operation CCokingg period of for 8 hrs for 4 hrs continuous operation, etc.) Coking 9~7 Table ~ (cont . ) -r-~
F,~campl~ 10 ~ Comparative Compara~i~re Ex~ ple 10 EY.ample 11 ----~ ~
Heavy petroletlm oil asI Reduced I ~educed Reduced raw material I pressure pres~u:rf3 pre~sure _ _ I residu 1 oLl _ ~idual oLl re31dual oil_ Temperature of . .
superheated steam (C) :LOOO 1000 1~00 . .~ . .. .
Temperature at the outlet of the reactor (C) ¦ 950 800 ~ ._ . _ Steam-oil ratio (moles of H20/carbon atoms) 4 4 5 , __ .
Residence time (sec) ¦ 0.030.03 0.008 . . . . __ .__ Mass velocity (kg/hr/sectional area 2.9 2.6 10.6 (cm2) of the reactor) - H2 (weight %~ 0.8 1.0 0.7 CO ( ") I 2.1 2.6 2.2 C2 ( "~ I 1.0 1.3 1.1 x CH4 ( ..) 1 9.8 12.8 15.8 g C2H6 ( "~ I 3.2 3.2 3.o ~ C2H4 ( ) ¦ 19.2 20.2 22.3 o C2H2 ( ") I 0.2 0.2 0.2 C3H8 ( "~ ! 0 3 0.1 0.2 o C H ~ ~ 5 1 3.2 4.5 1,3-C4H6 () ¦ 2.6 1.5 2.1 Other C4 ( " ) ¦ O 9 0.8 l.Q
substances ( ) ¦ 54.8 53.1 49.2 _ Conditions of operation . Operation (Coking, period of for S hrs continuous operation, etc.) _ . __. _ . , , _______ . . ____~__ _ Table 2 (cont . ) ¦Comparatlve ~ Comparative Colnpatatlve ~E~ampLe 12 I Exanlple 13 ~xalllple 14 Heavy petroleum oll as ~Reduced ~ ~ecluc~d Redu~f~l raw material pressure pressure pressllra ~_ __ _ l eSlllU9 _ _il _esldual ~ reci:Ldual. o:L;L
Temperature of superheated steam (~C) 1200 1000 1~00 _ . _ .. _ ... ._ ___ Temperature at the outlet of the reactor (C) ¦ 800 800 800 . ._ .... .. . . .. .
Steam-oil ratio (moles l I
of H2O/carbon atoms) ' 5 1 8 0.8 . ._ l _ Residence time (sec) 0.15 ¦ 0.03 ¦ 0.03 ~- .._ Mass velocity (kg/hr/sectional area 0.6 2.7 4.9 (cm2~ of the reactor) - . ~ . ._, H~ (weight %) 0.9 ~0.9 CO ( " -) 2.4 ~ 2.3 C2 ( " ) 1.3 ~ 1.2 CH4 ( " ) 16.3 ¦ 10.1 6 ( " ) 2.8 1 3.2 2H4 ( " ) 21.1 j 21.2 C2H2 ~ " ) 0.2 ~ 0.2 4~
.~C3~1~. ( " ) 0.2 0.3 uC8H6 ( " ~ 3.9 5.7 , C4H6 ( ) 1.9 2.7 Other C4 ( " ) 1.0 1 0.9 hydrocarbons Liguid ( " ) 50.6 53.8 _ . . . . I
Conditions of operationOperation Operation Incapable o~
(Coking, period of for ~ hrs for 3 hrs operation continuous operation9 due to etc.) coking _ .. , . _ ~
As is apparent: from the results shown i.n the Examples and the Comparative E'xamples, the process o~ the present invention is capable o~ preparirl~ olefitls ~rolll heavy petroleum oil with high yielcls o:~ ol.cfins w-ithout coking onto the i.nller wall of the reactor.
Table 2 I Example 1 ¦ Exa~ple 2I Example 3I E~ample 4 Heavy petroleum oil as I Kuwait ! Kuwalt I Kuw~lt I Kuwait raw material orude oil ¦ crude oil ~ oru~e olll cr~de oil Temperature of l .
superheated steam (C) I 1000 1000 ¦ 1200 ¦ Te~perature at the O , 750 j 800 ~ 900 1 800 outlet of the reactor ( C) Steam-oil ratio (moles of H20/carbon atoms) 1 2 1 ~ I 4 I 5 _ . ~ , Residence time ~sec) I 0.06 0.1 1 0.01 ¦ 0.03 Mass velocity (kg/hr/sectional area 1.8 0.9 8.1 2.8 ~cm2~ of the reactor) . ... .
¦ H2 (weight %~i 0.7 0.9 0.8 0.9 CO ( " ~I 1.1 2.3 1 1.8 2.3 2 ( " ~I 0 4 1.2 1 0.8 1.2 ~ CH4 ( 71 ~I15.8 19.3 1 18.8 17.2 I ~ C2H6 ( " )~ 3.8 4.2 1 4.4 5.1 .~ C2H4 ( " ) 18.0 26.0 ' 27.2 29.3 ~ ~ C2H2 ( " ), 0.2 ~0.3 ' 0.4 0.3 1~ O C3H8 ( " )¦ 0.4 10.3 1 0.2 0.4 I o C3H6 ( " ~¦10.0 ¦ 5.C 3.1 7.4 : g 1'3-C4H6 ~ " )I6.8 2.0 1 2.4 4.0 Other C4 ( ~ )'2.2 1.2 - 2.1 2.1 : hydrocarbons I i Liquid ( " )I40.6 37.3 1 32.Q 29.8 substances l ~
_ . .._ . __ ~
Conditions of operation Operation Operation Operation Operation (Coking, period of . for 8 hrs for 8 hrs for 8 hrs for 8 hrs continuous operation, Cokin~ at etc.) the outlet . of the tube _ .
TCIb1e 2 ~COnt. ~
Comyarat-ive Comparat:i,ve ('o~rlpar~ ive C'otllE~ar.l~ive ~.Y.1111l~ L~ 1 E-~LI(;IP 1.~! 2. ~ IIIP 1~ 3 ~ rlr~P Le ~j ___............ __ ~ .,_ ._ __ . . ~. _ _ . _. _ ... , . . .. _ , ~ _ . . _ . _.. _ , .. .. ._~ . ____ . _ .
Heavy petroleum oil as Kuwait K~lwai~ KllwaL~ Kuwait raw material cru~le o~ rude o~ rucle oL:I. crl~cl~! oi:l Temperature of 800 800 700 lOOO
superheated steam ( C) Temperature at the outlet of the reactor (C) 680 950 SOO 900 8team-oil ratio (moles 2 , 2 4 4 of H20/carbon atoms) .
Residence time (sec) 0.06 0~03 0.1 0.008 Mass velocîty (kg/hr/section~l area I 1.9 ~I 3.0 0.9 10.1 ~cm2~ of the reactor) ~ ' i f (weight ~) 0-3 1 1.4 ' 0.7 0.8 CO ( " ) 0.7 ` 7.8 2.1 ~1.7 2 ( " ) 0.2 4.5 1.1 0.8 12.1 21.2 17.3 18.5 ( ) 2.4 : 3.7 3.S 4.2 , ~1 '.
C2~4 ( ~- )15.7 22.2 24.3 ~ 27.0 , h I C2H2 ( 1l ) - ,0-5 0.2 0.4 C3H8 ( )0.4 ~ 0.1 ~0.4 0.2 1 3 6 )9.8 2.3 5.7 3.6 3~C4H6 ( )7.2 1.9 2.3 2.7 ¦ hydrocarbons ( " ) 2.7 1.0 ~ 1.3 ~.3 bstances ( ) 4S.5 33.4 40.S 37-~
__ ___ . _ ¦ Conditions of operation IOperat~oll Operation Operatioll Operation I (Coking, period of i for 8 hrs Eor S hrs i for S hrs for S hrs continuous operation, ICoking all 1 ¦ Pod~
etc.) lover the I the inn~r ¦inner wall I w~l L o f th~
I~ the tube I
Table 2 (cont . ~
Icompara~ive!co~parative Comparatlvel Exam 1 5 ¦ Example 5 I Example 6 Exa~lple 7 ¦ P
_ __ _ _ ; _ ~_ . ......... A ~_ I _~_ Heavy petroleum oil ~s ¦ Kuwait Kuwalt KU~it j~tmo5pheric raw material ¦ crude oil crucl~! oll ~ru~e Oillpre~sure ~ t~ ~ re~idual oll !
I Temperature of I superheated steam (C~ I 1000 1000 ¦ :L000 800 ~ . _ , . .
Temperature at the l ou~let of the reactor (C) 800 900 1900 750 _ .............. ! ---- __ Steam-oil ratio ~moles l l of H2O/carbon atoms) 1 4 0.8 1 8 2 1.
. ~
Residence time (sec) ¦0.15 ¦ 0.01 ¦0.01 0.06 Mass velocity (kg/hr/sectional area 0.6 13.3 7.4 1.8 (cm2) of the r~actor) . _ .___ ! ~2 ~weight %) 1.0 ¦ 1.2 1 0.6 CO ( " ~ 3.1 12.1 11.1 l ~ C2 ( " ) 1.8 1 11.1 10.5 ¦ x CH4 ( " ~I20.0 ¦ ,18.2 ¦14.7 ¦ ~ C2H6 ( " )I4 3 , ¦4.3 3.7 C2H4 , ¦ ,27 8 15.1 h C2H2 ( ~ 0.1 10.5 0.2 o C3H8 ( " ~!0 3 0.3 0.4 1 ~ ~ C3H6 ( " ) 4.0 j4.6 8.9 ~: O 1'3-C4H6 ( " ) 2.0 !3.1 6.3 ~: ~ Other C4 t " ) 0.8 ¦ 2.4 2.3 : ~ substances ( ) 40.1 34.4 46.8 _ . ,. . _._ .
: Conditions of operation Operation Coking Operation Operation (Coking, period of for 8 hrs Incapable for 8 hrs for 8 hrs oontinuous operation, Coking at of . the outl.et operation _ . of the l.. ube _ Table 2 (cont .
.. .._ ~_ Exa~ple 6 Comparative I Comparati~e Example 8 , Example 9 Heavy petroleum oil as I Atomospheric Atomospher$c~ Atomosyheric raw materialpressure prcssurc I pre.~ re _ ____ residual oll re~idual oil Temperature of superheated steanl (C) 1000 700 ¦ 1000 _. _ __ . _ _ __ _ _ Temperature at the ou~let oE the reactor (C) 850 850 700 .~ .. _ _ - .. _ _ . .
Steam-oil ratio (moles l of H20/carbon atoms) 1 4 4 ~ 4 _ - _ __ !
Residence time (sec) ¦ 0.03 0 03 ! 0.15 _ . ~ _ .__ . _ _ . I
Mass velocity (kg/hr/sectional area 2.8 2.8 0.6 (cm2) of the reactor) , _ _ H2 (weight %) ¦ 0.9 0.8 ¦ 0.7 C0 ( " ) 2.4 2.3 1 2.3 2 ~ " ) 1.3 1.1 1.0 CH4 ( " ) 17.5 ¦15.8 ! 14.9 . C2~6 ( " ) I 4-2 1 3.8 1l 2.8 C2H4 ( " ) 24.3 21.2 20.8 o C2H2 ( " ) 0.2 0.1 1 ~
~ C3H8 ( " ) ¦ 0.3 0.3 1 0.5 .~ C3H6 ( " ) 6.8 7.0 8.0 : I ~ 1'3-C4H6 ( ) 3.5 3.4 3.7 hydrocarbons ( ) 1.9 1.7 2.1 : substances ( " ) 36.7 49.5 43,2 ~ __ _ .. . ._ Conditions of operation (Coking, period of continuous operation, : etc.) _ _ . . ____ _ . . ~__ ____ _ g47 Table 2 (cont~) j I Example 7 r Example 8 ¦ Y,xample 9 Hea~y petroleum oil as I Reduced I Reduced I l~educed . pressure pressure pressure raw materlal residual oil residu/ll oll residuaL oi~.!
Temperature of ¦ 1000 1200 900 . superheated steam ( C) ! ~
¦ outlet of the reactor (C) 900 800 ,50 ¦ Steam-oil ratio (moles l ! of H2/carbon atoms) 1 4 5 4 - -- _ _ _ ¦ Residence time (sec) I 0,03 0.01 ¦ 0.1 . Mass velocity (kg/hr/sectional area 2.7 8.5 0.9 . (cm~ ) of the reactor) ~ _ H~ (weight %) ¦0.~ 0.8 1 0.7 CO ( " ~1 2.3 2.3 1 2.0 2 ( " )I 1.3 1.2 1.0 ~ CU4 ( " ~I 16.2 16.8 8.2 oC2H6 ( " ) 3.2 3.2 3.0 2H4 ( " ) 22,3 22.4 1 15.1 . oC2~2 ( " )I 0.2 0.2 1 0.1 : o 3 8 ( ) 0.2 0.3 0.3 : .~C3~6 ( " ) 6.3 4.~ 5.0 :~ ~1~3 C4H6 ( ) 3.1 2.2 2.4 Other C4 ( " ) 1.2 1.0 I.0 hydrocarbons Li~uid ( " ~1 42.8 44.8 61.2 substances I _ .
Conditions of operation Operation Operation CCokingg period of for 8 hrs for 4 hrs continuous operation, etc.) Coking 9~7 Table ~ (cont . ) -r-~
F,~campl~ 10 ~ Comparative Compara~i~re Ex~ ple 10 EY.ample 11 ----~ ~
Heavy petroletlm oil asI Reduced I ~educed Reduced raw material I pressure pres~u:rf3 pre~sure _ _ I residu 1 oLl _ ~idual oLl re31dual oil_ Temperature of . .
superheated steam (C) :LOOO 1000 1~00 . .~ . .. .
Temperature at the outlet of the reactor (C) ¦ 950 800 ~ ._ . _ Steam-oil ratio (moles of H20/carbon atoms) 4 4 5 , __ .
Residence time (sec) ¦ 0.030.03 0.008 . . . . __ .__ Mass velocity (kg/hr/sectional area 2.9 2.6 10.6 (cm2) of the reactor) - H2 (weight %~ 0.8 1.0 0.7 CO ( ") I 2.1 2.6 2.2 C2 ( "~ I 1.0 1.3 1.1 x CH4 ( ..) 1 9.8 12.8 15.8 g C2H6 ( "~ I 3.2 3.2 3.o ~ C2H4 ( ) ¦ 19.2 20.2 22.3 o C2H2 ( ") I 0.2 0.2 0.2 C3H8 ( "~ ! 0 3 0.1 0.2 o C H ~ ~ 5 1 3.2 4.5 1,3-C4H6 () ¦ 2.6 1.5 2.1 Other C4 ( " ) ¦ O 9 0.8 l.Q
substances ( ) ¦ 54.8 53.1 49.2 _ Conditions of operation . Operation (Coking, period of for S hrs continuous operation, etc.) _ . __. _ . , , _______ . . ____~__ _ Table 2 (cont . ) ¦Comparatlve ~ Comparative Colnpatatlve ~E~ampLe 12 I Exanlple 13 ~xalllple 14 Heavy petroleum oll as ~Reduced ~ ~ecluc~d Redu~f~l raw material pressure pressure pressllra ~_ __ _ l eSlllU9 _ _il _esldual ~ reci:Ldual. o:L;L
Temperature of superheated steam (~C) 1200 1000 1~00 _ . _ .. _ ... ._ ___ Temperature at the outlet of the reactor (C) ¦ 800 800 800 . ._ .... .. . . .. .
Steam-oil ratio (moles l I
of H2O/carbon atoms) ' 5 1 8 0.8 . ._ l _ Residence time (sec) 0.15 ¦ 0.03 ¦ 0.03 ~- .._ Mass velocity (kg/hr/sectional area 0.6 2.7 4.9 (cm2~ of the reactor) - . ~ . ._, H~ (weight %) 0.9 ~0.9 CO ( " -) 2.4 ~ 2.3 C2 ( " ) 1.3 ~ 1.2 CH4 ( " ) 16.3 ¦ 10.1 6 ( " ) 2.8 1 3.2 2H4 ( " ) 21.1 j 21.2 C2H2 ~ " ) 0.2 ~ 0.2 4~
.~C3~1~. ( " ) 0.2 0.3 uC8H6 ( " ~ 3.9 5.7 , C4H6 ( ) 1.9 2.7 Other C4 ( " ) 1.0 1 0.9 hydrocarbons Liguid ( " ) 50.6 53.8 _ . . . . I
Conditions of operationOperation Operation Incapable o~
(Coking, period of for ~ hrs for 3 hrs operation continuous operation9 due to etc.) coking _ .. , . _ ~
As is apparent: from the results shown i.n the Examples and the Comparative E'xamples, the process o~ the present invention is capable o~ preparirl~ olefitls ~rolll heavy petroleum oil with high yielcls o:~ ol.cfins w-ithout coking onto the i.nller wall of the reactor.
Claims (2)
1. A process for preparing olefins from heavy petroleum oil, said heavy petroleum oil being mixed with steam and fed to a tubular reaction zone externally heated for the preparation of olefins, which comprises mixing said heavy petroleum oil with superheated steam at a steam-oil ratio in the range of from 2 to 7, and indirectly heating the resulting mixture so that the temperature at the outlet of a reaction zone may be in the range of from 700 to 950°C
at a residence time of from 0.01 to 0.1 second in the reaction zone.
at a residence time of from 0.01 to 0.1 second in the reaction zone.
2. A process for preparing olefins from heavy petroleum oil as claimed in claim 1, wherein said tubular reaction zone externally heated is composed of a plurality of tubular reactors provided in a furnace.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP189216/1981 | 1981-11-27 | ||
| JP18921681A JPS5891791A (en) | 1981-11-27 | 1981-11-27 | Preparation of olefin from heavy oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1184947A true CA1184947A (en) | 1985-04-02 |
Family
ID=16237496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416442A Expired CA1184947A (en) | 1981-11-27 | 1982-11-26 | Process for preparing olefins from heavy petroleum oil |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5891791A (en) |
| CA (1) | CA1184947A (en) |
| DD (1) | DD204939A5 (en) |
| DE (1) | DE3243310A1 (en) |
| FR (1) | FR2517321A1 (en) |
| GB (1) | GB2110233A (en) |
| IN (1) | IN156279B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3406910A1 (en) | 1984-02-25 | 1985-09-05 | Hoechst Ag, 6230 Frankfurt | MONOFILES AND BRUSHES MADE OF HOMO- OR COPOLYMERISATEN OF ACRYLNITRILE AND METHOD FOR THE PRODUCTION THEREOF |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2890256A (en) * | 1955-05-03 | 1959-06-09 | Kellogg M W Co | Pyrolitic hydrocarbon conversion process for making ethylene |
| DE1518607A1 (en) * | 1965-11-12 | 1969-08-07 | Basf Ag | Process for the production of olefins, in particular ethylene, by thermal cracking of hydrocarbons |
| FR1545436A (en) * | 1967-02-23 | 1968-11-08 | Sir Soc Italiana Resine Spa | Ethylene production process |
-
1981
- 1981-11-27 JP JP18921681A patent/JPS5891791A/en active Pending
-
1982
- 1982-11-18 IN IN1346/CAL/82A patent/IN156279B/en unknown
- 1982-11-23 DE DE19823243310 patent/DE3243310A1/en not_active Withdrawn
- 1982-11-23 GB GB08233301A patent/GB2110233A/en not_active Withdrawn
- 1982-11-26 CA CA000416442A patent/CA1184947A/en not_active Expired
- 1982-11-26 FR FR8219875A patent/FR2517321A1/en active Pending
- 1982-11-26 DD DD24525982A patent/DD204939A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DD204939A5 (en) | 1983-12-14 |
| JPS5891791A (en) | 1983-05-31 |
| IN156279B (en) | 1985-06-15 |
| GB2110233A (en) | 1983-06-15 |
| DE3243310A1 (en) | 1983-06-09 |
| FR2517321A1 (en) | 1983-06-03 |
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