CN109422609B - Process for the production of ethylene - Google Patents
Process for the production of ethylene Download PDFInfo
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- CN109422609B CN109422609B CN201710784643.3A CN201710784643A CN109422609B CN 109422609 B CN109422609 B CN 109422609B CN 201710784643 A CN201710784643 A CN 201710784643A CN 109422609 B CN109422609 B CN 109422609B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for producing ethylene, which comprises the step of feeding hydrocarbon material flow into an olefin cracking unit for reaction to obtain C 3 Ethane, etc., and the C 3 Feeding all or part of the components to an olefin disproportionation unit, feeding at least 0.2% of the ethane component to a steam cracking furnace, feeding a stream containing propylene to the olefin disproportionation unit, and feeding C produced in the olefin disproportionation unit 4 + Recycling all or part of the components to the olefin cracking unit, and removing unreacted C in the olefin disproportionation unit 3 The technical scheme that the components are sent into the steam cracking furnace after passing through the hydrogenation unit has the characteristics of high ethylene yield, good economy and the like, can be used for matching with an ethylene device, and is particularly suitable for an ethane cracking device.
Description
Technical Field
The invention relates to a method for producing ethylene, in particular to a method for producing ethylene by utilizing a catalytic and thermal cracking method.
Background
The triene Process (The toolfin Process) is: propylene is disproportionated to produce high-purity ethylene and butene-2; and the reverse of this reaction, ethylene and butene-2 react to produce propylene. The propylene disproportionation technology has not been reported to be industrially applicable since 1970. In recent years, with the global increase in the demand for propylene, the production of propylene by the conventional method has failed to meet the demand for propylene, and therefore, the technology for producing propylene by the reverse reaction of triene process has been commercialized. From the end of 1985, lyondell operated a propylene production plant with an annual capacity of 136,000 tons in Texas, usa, and it was a process for the production of propylene by the cross-disproportionation of ethylene and butene-2. In China, lummus transferred OCU technology based on reverse triene technology to Shanghai Seisaku in 2002, and then due to the great development of coal chemical industry, C4 as a byproduct of a plurality of MTO devices is increased by using the technology.
The olefin catalytic cracking technology is a method for catalytically cracking olefins contained in a raw material by using various mixed C4-C6 as the raw material, usually in the presence of a molecular sieve catalyst, to obtain light molecular olefins of propylene and ethylene. Currently, representative olefin catalytic cracking processes mainly include: a Propylur process, an OCP process, an Omega process, an OCC process and a Superflex process. The Propylur process is developed by Germany Lurgi company, adopts a fixed bed reaction process, uses steam as a diluting raw material, adopts a molecular sieve catalyst, and carries out adiabatic reaction at 500 ℃ and 0-0.1 MPaG, and the reactor is of a fixed bed type and is provided with one reactor for two reactors; the ratio of steam to raw material is 0.5-3.0, and the service life of catalyst can be up to 15 months. The olefin conversion rate of the Propylur process reaches 85%, the once-through propylene yield is 40mol%, and the ethylene yield is 10mol% (relative to the total amount of olefins in the feed); the process has a set of demonstration devices in German Worringer, and no industrial devices are built at present. The OCP process is developed by cooperation of UOP and Atofina, a fixed bed reaction process is adopted, and the reaction is carried out at 500-600 ℃ and 0.1-0.4 MPaG; a reaction system with high space velocity and no diluent gas is adopted. The Omega process was developed by Asahi Kasei corporation of Japan, the reaction was carried out in a single-stage, adiabatic fixed bed, and the catalyst was regenerated by switching between the two reactors; the molecular sieve catalyst is adopted, the reaction is carried out at 530-600 ℃ and 0-0.5 MPaG, the reaction space velocity WHSV is 3-10 h < -1 >, and the olefin conversion rate of the process is more than 75 percent. The Asahi formation in 2006 6 months creates a set of devices for producing propylene by an Omega method in the water island. The OCC process was developed by Shanghai institute of petrochemical engineering and the reaction was carried out adiabatically in a fixed bed. Adopts a process without diluent gas, the reaction airspeed WHSV is 15-30 h < -1 >, the reaction pressure is 0-0.15 MPaG, the reaction temperature is 500-560 ℃, and the single-pass conversion rate of olefin is more than 65 percent. The OCC process established a 100 ton/year scale pilot plant in ashore petrochemical co, ltd, 2004. In 2009, an OCC industrial plant of a scale of 6 million tons/year was built in central petrochemical company ltd.
Disclosure of Invention
The invention aims to solve the technical problem of low ethylene yield in the prior art, and provides a novel ethylene production method, compared with the traditional method, the ethylene yield of the method can reach more than 65 percent, and the method is particularly suitable for a steam cracking device taking ethane as a raw material.
The industrial triene process, often its reverse reaction, is: the process for producing propylene by reacting ethylene and butylene has good economical efficiency when the price of ethylene and propylene is inversely hung, but once the price of ethylene and propylene is not inversely hung, the economical efficiency is severe. Meanwhile, the technology has poor adaptability to C5+ olefin as a raw material, and the yield is inferior to that of C4 olefin.
The industrialized olefin catalytic cracking technology has the advantages of good raw material adaptability, high ethylene and propylene yield, no consumption of ethylene and the like, but has the defects of low ethylene yield, uncontrollable E/P ratio and the like.
For a steam cracking device using ethane as a raw material, the yields of byproduct propylene, carbon tetraolefin and heavy olefin are low, the ethylene yield is often improved by a method of returning the hydrogenated product to a cracking furnace, and the cycle yield is often less than 45 percent
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for the production of ethylene comprising the steps of:
(1) The hydrocarbon material flow is sent into an olefin cracking unit to react to obtain C 3 Ethane, etc., and the C 3 Feeding all or part of the components to an olefin disproportionation unit, and feeding at least 0.2% of the ethane component to a steam cracking furnace;
(2) Feeding a stream comprising propylene to an olefin disproportionation unit;
(3) C produced by olefin disproportionation unit 4 + The components are wholly or partially recycled to the olefin cracking unit;
(4) Unreacted C in olefin disproportionation unit 3 The components are sent into a steam cracking furnace after passing through a hydrogenation unit.
Said hydrocarbon stream contains a component selected from C 4 ～C 8 At least one olefin of the olefins.
In the above technical solution, it is more preferable that at least 40% of ethane generated in the olefin cracking unit of the step (1) is fed to the steam cracking furnace.
In the above technical solution, it is more preferable that at least 95% of ethane generated in the olefin cracking unit of step (1) is fed to the steam cracking furnace.
In the above technical solution, preferably, unreacted C in the medium olefin disproportionation unit 3 ComponentsAll or part of the waste gas is sent into a steam cracking furnace.
In the above-mentioned embodiment, more preferably, at least 0.2% of C unreacted in the olefin disproportionation unit is 3 The components are sent into a steam cracking furnace.
In the above technical solution, more preferably, at least 45% of unreacted C in the olefin disproportionation unit 3 The components are sent into a steam cracking furnace.
In the above technical solution, more preferably, at least 95% of unreacted C in the olefin disproportionation unit 3 The components are sent into a steam cracking furnace.
In the above technical solution, it is preferable that at least the reaction of cracking the olefin into ethylene and propylene occurs in the olefin cracking unit.
In the above technical solution, it is preferable that at least propylene disproportionation reaction occurs in the olefin disproportionation unit to obtain ethylene and butene.
In the above technical solution, preferably, the catalyst used in the olefin cracking unit comprises a molecular sieve catalyst.
In the above technical scheme, preferably, the catalyst used in the olefin cracking unit contains a ZSM-5 catalyst.
In the above technical solution, preferably, the disproportionation catalyst used in the olefin disproportionation unit is a metal oxide catalyst.
In the above embodiment, it is preferred that the hydrocarbon stream contains C 4 ～C 6 At least one olefin of the olefins.
In the above technical solution, it is more preferable that the steam cracking furnace is a gas furnace.
In the above technical scheme, preferably, C produced in the olefin cracking unit in the step (1) 3 At least 55% of the components are fed to an olefin disproportionation unit.
In the above technical scheme, more preferably, C produced in the olefin cracking unit in the step (1) 3 At least 75% of the components are fed to an olefin disproportionation unit.
In the above technical scheme, more preferably, C produced in the olefin cracking unit in the step (1) 3 At least 95% of the components are sent to a disproportionation unit.
In the above technical solution, more preferably, at least 45% of C produced in the olefin disproportionation unit of the step (3) is 4 + The components are sent to a disproportionation unit.
In the above technical solution, more preferably, at least 75% of C produced in the olefin disproportionation unit of the step (3) is 4 + The components are sent to a disproportionation unit.
In the above technical solution, more preferably, at least 95% of C produced in the olefin disproportionation unit of the step (3) is 4 + The components are sent to a disproportionation unit.
In the above embodiment, the weight yield of ethylene is more preferably at least 45%.
In the above embodiment, the weight yield of ethylene is more preferably at least 55%.
In the above embodiment, the weight yield of ethylene is more preferably at least 65%.
By adopting the technical scheme of the invention, a good technical effect is achieved by a combined process of the olefin disproportionation unit, the olefin cracking unit, the hydrogenation unit and the cracking furnace, wherein the olefin disproportionation unit is used for obtaining ethylene and butylene through propylene disproportionation, and simultaneously, the materials of each unit are preferably recycled.
The invention is further illustrated by the following examples.
Drawings
FIG. 1 is a schematic process flow diagram of a preferred embodiment of the present invention.
I is an olefin cracking unit;
II is an olefin disproportionation unit;
III is a hydrogenation unit;
IV is a steam cracking furnace
1 is hydrocarbon material flow raw material;
2 is an ethylene-containing stream produced by an olefin cracking unit;
3 is other products produced by the olefin cracking unit;
4 is a propylene containing stream produced by an olefin cracking unit;
5 is a propylene containing stream;
6 isC produced by an olefin cracking unit 3 Logistics;
7 is an ethylene stream produced by an olefin disproportionation unit;
8 is unreacted C of olefin disproportionation unit 3 Logistics;
9 is C produced by an olefin disproportionation unit 4 A + stream;
10 is ethane produced by an olefin cracking unit;
11 is hydrogenated C 3 Stream (recycle fraction);
12 is the ethylene containing stream obtained after steam cracking.
Sending the hydrocarbon material flow 1 and the circulating material flow 9 into a unit I to carry out olefin cracking reaction to generate light hydrocarbon, ethylene, ethane, propylene and heavy hydrocarbon, separating the light hydrocarbon, the ethylene, the ethane, the propylene and the heavy hydrocarbon into a material flow 2 containing ethylene, a material flow 3 containing heavy hydrocarbon, a material flow 4 rich in propylene and ethane 10, sending the material flow 4 into a unit II, and sending the material flow 5 to be propylene. Sending the material flow 6 rich in propylene into a unit II to perform reaction of propylene disproportionation into ethylene and butylene, and separating to obtain an ethylene product material flow 7, and unreacted propylene material flows 8 and C 4 And (6) recycling the material flow 9 to the I, passing the material flow 8 through a hydrogenation unit III to obtain a material flow 11, and sending the material flow 11 and the material flow 10 to a steam cracking furnace IV, wherein the steam cracking furnace is used for obtaining a material flow 12 containing ethylene.
FIG. 2 is a schematic process flow diagram of a conventional process.
III is a hydrogenation unit;
IV is a steam cracking furnace
1 is hydrocarbon material flow raw material;
5 is a propylene containing stream;
the hydrocarbon material flow 1 and the material flow 5 containing propylene are sent into a steam cracking furnace IV after passing through a hydrogenation unit III, and the steam cracking furnace obtains a material flow 12 containing ethylene.
Detailed Description
[ example 1 ]
The flow shown in fig. 1 is adopted:
The obtained product contains target product flows of 2, 7 and 12, wherein 2 contains 389 kg/h of ethylene, 7 contains 519kg/h of ethylene and 12 contains 202kg/h of ethylene. The overall ethylene yield was 74.0%.
[ example 2 ] A method for producing a polycarbonate
The flow shown in fig. 1 is adopted:
95% of stream 4 from I (flow 1201kg/h, propylene content 93.5%) was fed to II, while stream 5 was also fed to II, and 100% of stream 9 from II (flow 1005kg/h, C4 olefin content 96.4%) was returned to I.
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 370 kg/h ethylene, 7 contained 483kg/h ethylene and 12 contained 193kg/h ethylene. The overall ethylene yield was 69.7%.
[ example 3 ] A method for producing a polycarbonate
The flow shown in fig. 1 is adopted:
The streams containing the desired product in the product obtained were 2, 7 and 12, 2 containing 333 kg/h ethylene, 7 containing 374kg/h ethylene and 12 containing 172kg/h ethylene. The overall ethylene yield was 58.6%.
[ example 4 ]
The flow shown in fig. 1 is adopted:
55% of the stream 4 resulting from I (with a flow rate of 970kg/h and a propylene content of 93%) was fed to II, while stream 5 was also fed to II, and 100% of the stream 9 resulting from II (with a flow rate of 623kg/h and a C4 olefin content of 96%) was returned to I.
The streams containing the desired product in the product obtained were 2, 7 and 12, 2 containing 302 kg/h ethylene, 7 containing 291kg/h ethylene and 12 containing 153kg/h ethylene. The overall ethylene yield was 49.7%.
[ example 5 ] A method for producing a polycarbonate
The flow shown in fig. 1 is adopted:
The streams containing the desired product in the product obtained were 2, 7 and 12, 2 containing 398 kg/h ethylene, 7 containing 521kg/h ethylene and 12 containing 208kg/h ethylene. The overall ethylene yield was 75.1%.
[ example 6 ]
The flow shown in fig. 1 is adopted:
The streams containing the desired product in the product obtained were 2, 7 and 12, 2 containing 362 kg/h ethylene, 7 containing 493kg/h ethylene and 12 containing 195kg/h ethylene. The overall ethylene yield was 70.0%.
[ example 7 ]
The flow shown in fig. 1 is adopted:
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 307 kg/h ethylene, 7 contained 442kg/h ethylene and 12 contained 174kg/h ethylene. The overall ethylene yield was 61.5%.
[ example 8 ]
The flow shown in fig. 1 is adopted:
The streams containing the desired product in the product obtained were 2, 7 and 12, 2 containing 248 kg/h ethylene, 7 containing 380kg/h ethylene and 12 containing 154kg/h ethylene. The overall ethylene yield was 52.1%.
[ example 9 ]
The flow shown in fig. 1 is adopted:
100% of the stream 10 resulting from I and 95% of the stream 8 resulting from II are fed via III to IV to give a stream 12 comprising ethylene.
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 395 kg/h ethylene, 7 contained 520kg/h ethylene and 12 contained 193kg/h ethylene. The overall ethylene yield was 73.9%.
[ example 10 ]
The flow shown in fig. 1 is adopted:
100% of the stream 10 resulting from I and 45% of the stream 8 resulting from II are fed via III to IV to produce the stream 12 comprising ethylene.
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 395 kg/h ethylene, 7 contained 520kg/h ethylene and 12 contained 146kg/h ethylene. The overall ethylene yield was 70.9%.
[ example 11 ]
The flow shown in fig. 1 is adopted:
100% of stream 10 from I and 0.2% of stream 8 from II are fed via III to IV to produce stream 12 containing ethylene.
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 395 kg/h ethylene, 7 contained 520kg/h ethylene and 12 contained 102kg/h ethylene. The overall ethylene yield was 67.8%.
[ example 12 ]
The flow shown in fig. 1 is adopted:
the material flow 1 contains 55% of C4 olefin, 20% of C5 olefin, 5% of C6 olefin, 15% of C4 alkane and 5% of C5 alkane, and the total flow rate is 1000kg/h; stream 5 contains 80% propylene and 20% propane, the total flow being 500kg/h.
95% of the stream 10 resulting from I and 100% of the stream 8 resulting from II are fed via III to IV to give a stream 12 comprising ethylene.
The product obtained contains the desired product streams 2, 7 and 12, of which 2 contains 395 kg/h of ethylene, 7 contains 520kg/h of ethylene and 12 contains 198kg/h of ethylene. The overall ethylene yield was 74.2%.
[ example 13 ]
The flow shown in fig. 1 is adopted:
40% of stream 10 from I and 100% of stream 8 from II are fed via III to IV to produce stream 12 containing ethylene.
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 395 kg/h ethylene, 7 contained 520kg/h ethylene and 12 contained 136kg/h ethylene. The overall ethylene yield was 70.1%.
[ example 14 ]
The flow shown in fig. 1 is adopted:
the material flow 1 contains 55% of C4 olefin, 20% of C5 olefin, 5% of C6 olefin, 15% of C4 alkane and 5% of C5 alkane, and the total flow rate is 1000kg/h; stream 5 contains 80% propylene and 20% propane, the total flow being 500kg/h.
0.2% of stream 10 from I and 100% of stream 8 from II are fed via III to IV to produce stream 12 containing ethylene.
The streams containing the desired product in the product obtained were 2, 7 and 12, of which 2 contained 395 kg/h ethylene, 7 contained 520kg/h ethylene and 12 contained 125kg/h ethylene. The overall ethylene yield was 69.3%.
Comparative example 1
The flow shown in fig. 2 is adopted:
The stream containing the desired product in the product obtained was 12, containing 675kg/h ethylene. The overall ethylene yield was 45.0%.
TABLE 1
Claims (13)
1. A process for the production of ethylene comprising the steps of:
(1) The hydrocarbon material flow is sent to an olefin cracking unit to react to obtain the product containing C 3 A mixture of component (C) and ethane component (C) 3 Feeding at least 95% of the ethane component to a steam cracking furnace;
(2) Feeding a stream comprising propylene to an olefin disproportionation unit;
(3) C produced by olefin disproportionation unit 4 + The components are wholly or partially recycled to the olefin cracking unit;
(4) At least 95% of the unreacted C in the olefin disproportionation unit 3 The components are sent into a steam cracking furnace after passing through a hydrogenation unit; said hydrocarbon stream contains a component selected from C 4 ～C 6 At least one olefin of the olefins.
2. The process for the production of ethylene according to claim 1, characterized in that at least the cracking of olefins into ethylene and propylene takes place in the olefin cracking unit.
3. The method for producing ethylene according to claim 1, wherein at least propylene disproportionation reaction to obtain ethylene and butene occurs in the olefin disproportionation unit.
4. The process for producing ethylene according to claim 1, wherein the catalyst used in the olefin cracking unit comprises a molecular sieve-type catalyst.
5. The process for the production of ethylene according to claim 1, wherein the olefin cracking unit uses a catalyst comprising a ZSM-5 type catalyst.
6. The method for producing ethylene according to claim 1, wherein the disproportionation catalyst used in the olefin disproportionation unit is a metal oxide catalyst.
7. The process for the production of ethylene according to claim 1, characterized in that the steam cracking furnace is a gas furnace.
8. Process for the production of ethylene according to claim 1, characterized in that the C of at least 45% of the olefins produced by the olefin disproportionation unit 4 + The components are recycled to the olefin cracking unit.
9. Process for the production of ethylene according to claim 8, characterized in that at least 75% of the C produced by the olefin disproportionation unit 4 + The components are recycled to the olefin cracking unit.
10. Process for the production of ethylene according to claim 9, characterised in that the olefin disproportionation unit produces at least 95% C 4 + The components are recycled to the olefin cracking unit.
11. The process for the production of ethylene according to claim 1, characterized in that the yield by weight of ethylene is at least 45%.
12. Process for the production of ethylene according to claim 11, characterized in that the yield by weight of ethylene is at least 55%.
13. Process for the production of ethylene according to claim 12, characterized in that the yield by weight of ethylene is at least 65%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2580002A (en) * | 1949-12-24 | 1951-12-25 | Standard Oil Dev Co | Process for the production of ethylene |
| US3485890A (en) * | 1967-04-03 | 1969-12-23 | Phillips Petroleum Co | Conversion of propylene into ethylene |
| CN101684059A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Method for producing propylene and ethylene through catalytic cracking of olefins |
| CN104250187A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Low carbon olefin preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026935A (en) * | 1989-10-02 | 1991-06-25 | Arco Chemical Technology, Inc. | Enhanced production of ethylene from higher hydrocarbons |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2580002A (en) * | 1949-12-24 | 1951-12-25 | Standard Oil Dev Co | Process for the production of ethylene |
| US3485890A (en) * | 1967-04-03 | 1969-12-23 | Phillips Petroleum Co | Conversion of propylene into ethylene |
| CN101684059A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Method for producing propylene and ethylene through catalytic cracking of olefins |
| CN104250187A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Low carbon olefin preparation method |
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