CN101092323A - Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon - Google Patents
Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon Download PDFInfo
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- CN101092323A CN101092323A CNA2006100279087A CN200610027908A CN101092323A CN 101092323 A CN101092323 A CN 101092323A CN A2006100279087 A CNA2006100279087 A CN A2006100279087A CN 200610027908 A CN200610027908 A CN 200610027908A CN 101092323 A CN101092323 A CN 101092323A
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- olefin
- catalytic cracking
- lightweight
- containing carbon
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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
This invention relates to a method for preparing lightweight olefins from carbon-containing olefins by catalytic cracking. The method solves the problems of low added value of carbon-containing olefin mixture, low catalytic cracking conversion rate, and low associativity of catalytic cracking process faced by the previous technique. The method comprises: (1) gasifying and preheating liquid-phase carbon-containing olefin mixture by heat exchange with cracking products, and heating to the reaction temperature with a heating furnace; (2) partially condensing the cracking products, and separating C5 or higher fractions; (3) compressing the rest cracking products to 0.3-1.1 MPa, sending into a depropanizer, separating, sending C3 or lower fractions obtained at the overhead to an ethylene apparatus, and separating to obtain propylene and ethylene; (4) sending C4 or higher fractions into a debutanizer, sending 30-90 wt.% of C4 fraction obtained at the overhead to the reactor, and cracking again. The method can be used in industrial production of lightweight olefins such as propylene and ethylene.
Description
Technical field
The present invention relates to a kind of method of preparing olefin in lightweight by catalytic cracking olefin of containing carbon.
Background technology
Propylene, ethene are one of important basic Organic Chemicals.Propylene is mainly used in many products such as producing PP, isopropyl benzene, vinyl cyanide, vinylformic acid; Ethene is the main raw material of producing polyethylene (PE), polyvinyl chloride (PVC) and ethylene oxide/ethylene glycol important organic chemical industry's products such as (EO/EG).As important light olefin, propylene, ethene year demand in continuous growth.Hydrocarbon pyrolysis is still one of main method of producing ethene, but and the general overview of the technology of production propylene is byproduct technology and proprietary technology.Byproduct technology mainly is meant the propylene that obtains by steam cracking and catalytic cracking system ethylene unit.Proprietary technology refers to the technology of special Development and Production propylene, mainly contains Technologies such as dehydrogenating propane, low-carbon alkene disproportionation, low-carbon alkene cracking, preparing propylene from methanol at present.Low-carbon alkene cracking system propylene technology not only can be used for producing propylene, ethene, and can improve the added value of low-carbon alkene, has very big development prospect.The ultimate principle of low-carbon alkene preparing propylene by catalytic cracking technology is to utilize to have uniqueness and select type and tart ZSM-5 molecular sieve catalyst, selectively low-carbon alkene is cracked into propylene and ethene.
Document WO 2004096439 has been introduced a kind of technology of mixed olefins cracking system light olefin.This technology does not adopt shared material, and the raw material mixed olefins carries out scission reaction under the high-speed condition.This technology can obtain multiple light olefin, but very not high to propylene, selectivity of ethylene.
Document EP 109059 has been introduced a kind of C
4～C
12The technology of mixed olefins system propylene, ethene, this technology does not have shared material equally, and the raw material mixed olefins is directly greater than 50 hours
-1Weight space velocity under carry out scission reaction.This production technique is not very high to the selectivity of propylene, and to C
5The selectivity of above cut is on the contrary greater than 33%.
The described technology of above-mentioned document all is under the condition that does not need shared material mixed olefins to be carried out cracking, produces propylene and ethylene.Except scission reaction not high this shortcoming of selectivity to propylene, the both does not relate to the separation of split product, and is very high to the degree of dependence of other device.
Summary of the invention
Technical problem to be solved by this invention is that the carbonaceous olefin mixture added value is not high in the conventional art, the olefins by catalytic cracking transformation efficiency is not high and the not strong problem of olefins by catalytic cracking technology combinableness, and a kind of method of new preparing olefin in lightweight by catalytic cracking olefin of containing carbon is provided.This method has when carbonaceous olefin mixture carried out catalytic cracking reaction, can obtain the advantage of highly selective light olefin propylene, ethene; Simultaneously, this method increases depropanizing, debutylize separating step by split product is carried out condensation, compression, has reduced the isolating load of dependence ethylene unit, has reduced energy consumption, has improved combine with other device advantage of ability of this technology; In addition, this method also has employing C
4Cut circulates, and has improved the advantage of olefin conversion.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing olefin in lightweight by catalytic cracking olefin of containing carbon may further comprise the steps:
(1) gasification and preheating after liquid phase feed carbonaceous olefin and the split product heat exchange, and then be heated to 400～600 ℃, enter reactor and carry out catalytic cracking reaction;
(2) with the heat exchange of raw material carbonaceous olefin after split product, partial condensation enters knockout drum then again; Gas-liquid separation pot bottom cutting out partial liquid phase C
5Above cut after the vapor-phase thermal cracking product that obtains is compressed into 0.3～1.1MPa, enters depropanizing tower in the knockout drum top portion;
(3) C that obtains at the depropanizing tower cat head
3And following cut, send into the separation of ethene steam cracking device and obtain propylene, ethene;
(4) at the bottom of the depropanizing Tata, obtain C
4And above cut.
In the technique scheme, the carbon-contained alkene by catalytic cracking preferred catalyst is for selecting shape ZSM-5 molecular sieve catalyst; Reacting used liquid phase feed preferred version is C
4～C
8Carbonaceous olefin mixture; The reaction feed preferred version is heated to 450～550 ℃, enters reactor and carries out catalytic cracking reaction; The reaction weight space velocity preferable range of scission reaction is 5～100 hours in the reactor
-1, more preferably scope is 5～50 hours
-1The reaction pressure preferable range is 0.02～0.3MPa in the reactor, and more preferably scope is 0.05～0.15MPa.Reaction split product preferred version enters the depropanizing tower stage casing for being compressed into 0.4～0.9MPa; The C that obtains at the bottom of the depropanizing Tata
4And above cut preferred version is for entering the debutanizing tower stage casing.The C that the debutanizing tower cat head obtains
4The cut preferred version is that 30～90 weight % circulation enters reactor cracking once more, and more preferably scheme is that 45～85 weight % circulation enters reactor; Preferred version is for obtaining C at the bottom of the debutylize Tata
5And above cut.Depropanizing tower, debutanizing tower preferred version are packing tower, tray column or valve tray column.The split product partial condensation, the temperature preferable range is 10～80 ℃ after the condensation, more preferably scope is 20～60 ℃.
The inventive method adopts C
4Cut circulation has improved olefin conversion, and propylene that obtains and ethene are no less than 62% of alkene total amount in the raw material.The C that the depropanizing tower cat head obtains
3Following cut enters the ethene steam cracking device, has reduced the isolating load of dependence ethylene unit, has saved repeated isolation C
4And the energy consumption of above cut; Because segregational load reduces, this production technique can be incorporated into preparing ethylene by steam cracking device, FCC apparatus and other propylene enhancing device such as the preparing propylene from methanol device of multiple scale according to practical situation.Therefore, the inventive method has good combinableness, has obtained better technical effect.
Description of drawings
Fig. 1 is the inventive method process flow diagram;
Fig. 2 is document EP 109059 process flow diagrams;
1 is the raw material carbonaceous olefin mixture among Fig. 1 or Fig. 2, and 2 is process furnace, and 3 is reactor, and 4 is feed exchanger, and 5 is fractional distillating tube, and 6 is gas-liquid separator, and 7 is compressor, and 8 is depropanizing tower, and 9 is C
5Above cut, 10 is C
3Following cut, 11 is debutanizing tower, 12 is C
5Above cut, 13 for effluxing C
4, 14 are circulation C
4, 15 is C
2Following cut, 16 is C
3Cut, 17 is other cut, 18 is mixed C
4～C
8
Among Fig. 1, carbonaceous olefin mixture 1 and reactor split product are heated to temperature of reaction through process furnace 2 in interchanger 4 heat exchange after gasification, the preheating again.The reactor split product enters knockout drum 6 again after fractional distillating tube 5 partial condensations after interchanger 4 heat exchange.Gas-liquid separator 6 bottom liquid phases 9 are C
5Above cut.Enter depropanizing tower 8 after compressed machine 7 compressions of gas-liquid separator 6 top gas phases, obtain C at the depropanizing tower top
3Following cut obtains C at the bottom of the tower
4Reach above cut and enter debutanizing tower 11, obtain C at the debutanizing tower top
4Cut 14 circulations enter reactor 3, C
4Cut 13 effluxes, and obtains C at the bottom of the tower
5And above cut.
The invention will be further elaborated below by embodiment.
Embodiment
[comparative example 1]
By shown in Figure 2, carbonaceous olefin mixture is formed (weight %) and is: iso-butylene: 45%, and Trimethylmethane: 55%.Adopt document EP 109059 technical process, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 300 ZSM-5 molecular sieve, weight hourly space velocity is 80 hours
-1, temperature of reaction is 575 ℃, reaction pressure is 0.05MPa, experimental results show that the product (weight %) that will obtain following ratio:
C
2Alkene: 0.11%
C
3Alkene: 23.3%
C
4：28.5％
C
5More than: 48.09%
[comparative example 2]
By shown in Figure 2, carbonaceous olefin mixture is formed (weight %) and is: iso-butylene: 45%, and Trimethylmethane: 55%.Adopt document EP 109059 technical process, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 300 ZSM-5 molecular sieve, weight hourly space velocity 60 hours
-1, temperature of reaction is 550 ℃, and reaction pressure is 0.15MPa, and evidence will obtain the product (weight %) of following ratio:
C
2Alkene: 0.07%
C
3Alkene: 34.11%
C
4：18.25％
C
5More than: 47.64%
[embodiment 1]
By shown in Figure 1, carbonaceous olefin mixture is formed (weight %) and is: iso-butylene: 45%, and Trimethylmethane: 55%.Adopt technical process of the present invention, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 200 ZSM-5 molecular sieve, the reaction weight hourly space velocity is 15 hours
-1, temperature of reaction is 450 ℃, and reaction pressure is 0.08MPa, and the temperature behind the fractional distillating tube 5 is 25 ℃, and split product is compressed into 0.5MPa, the C of 48 weight %
4The cut circulation, the pilot plant proof will obtain the product (weight %) of following ratio:
Ethene: 20.2%
Propylene: 43.3%
Other C
3Below: 3.2%
C
4Above cut: 33.3%
[embodiment 2]
By shown in Figure 1, carbonaceous olefin mixture is formed with embodiment 1.Adopt technical process of the present invention, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 200 ZSM-5 molecular sieve, the reaction weight hourly space velocity is 60 hours
-1, temperature of reaction is 500 ℃, and reaction pressure is 0.15MPa, and the temperature behind the fractional distillating tube 5 is 45 ℃, and split product is compressed into 0.85MPa, the C of 68 weight %
4The cut circulation will obtain the product (weight %) of following ratio:
Ethene: 21.6%
Propylene: 44.3%
Other C
3Below: 3.0%
C
4Above cut: 31.1%
[embodiment 3]
By shown in Figure 1, carbonaceous olefin mixture is formed with embodiment 1.Adopt technical process of the present invention, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 200 ZSM-5 molecular sieve, the reaction weight hourly space velocity is 100 hours
-1, temperature of reaction is 550 ℃, and reaction pressure is 0.30MPa, and the temperature behind the fractional distillating tube 5 is 55 ℃, and split product is compressed into 0.65MPa, the C of 88 weight %
4The cut circulation will obtain the product (weight %) of following ratio:
Ethene: 23.5%
Propylene: 45.3%
Other C
3Below: 3.5%
C
4Above cut: 27.7%.
Claims (10)
1, a kind of method of preparing olefin in lightweight by catalytic cracking olefin of containing carbon may further comprise the steps:
(1) gasification and preheating after liquid phase feed carbonaceous olefin and the split product heat exchange, and then be heated to 400～600 ℃, enter reactor and carry out catalytic cracking reaction;
(2) with the heat exchange of raw material carbonaceous olefin after split product, partial condensation enters knockout drum then again; Gas-liquid separation pot bottom cutting out partial liquid phase C
5Above cut after the vapor-phase thermal cracking product that obtains is compressed into 0.3～1.1MPa, enters depropanizing tower in the knockout drum top portion;
(3) C that obtains at the depropanizing tower cat head
3And following cut, send into the separation of ethene steam cracking device and obtain propylene, ethene;
(4) at the bottom of the depropanizing Tata, obtain C
4And above cut.
2, according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 1, it is characterized in that reacting used liquid phase feed is C
4～C
8Carbonaceous olefin mixture; Reaction feed is heated to 450～550 ℃, enters reactor and carries out catalytic cracking reaction.
3, according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 1, the reaction weight space velocity that it is characterized in that scission reaction in the reactor is 5～100 hours
-1, reaction pressure is 0.02～0.3MPa.
4, according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 3, the reaction weight space velocity that it is characterized in that scission reaction in the reactor is 5～50 hours
-1, reaction pressure is 0.05～0.15MPa.
5, according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 1, it is characterized in that split product is compressed into 0.4～0.9MPa, enter the depropanizing tower stage casing; Wherein depropanizing tower, debutanizing tower are packing tower, tray column or valve tray column.
6,, it is characterized in that the C that obtains at the bottom of the depropanizing Tata according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 1
4And above cut enters the debutanizing tower stage casing.
7,, it is characterized in that the C that the debutanizing tower cat head obtains according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 6
4Cut 30～90 weight % circulation enters reactor cracking once more, all the other dischargings; Obtain C at the bottom of the tower
5And above cut.
8,, it is characterized in that the C that the debutanizing tower cat head obtains according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 7
4Cut 45～85 weight % circulation enters reactor cracking once more.
9, according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 1, it is characterized in that the split product partial condensation, temperature is 10～80 ℃ after the condensation.
10, according to the method for the described preparing olefin in lightweight by catalytic cracking olefin of containing carbon of claim 1, it is characterized in that the split product partial condensation, temperature is 20～60 ℃ after the condensation.
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|---|---|---|---|
| CN2006100279087A CN101092323B (en) | 2006-06-21 | 2006-06-21 | Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon |
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|---|---|---|---|
| CN2006100279087A CN101092323B (en) | 2006-06-21 | 2006-06-21 | Method for preparing olefin in lightweight by catalytic cracking olefin of containing carbon |
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| CN101092323B CN101092323B (en) | 2010-07-21 |
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| CN101857520A (en) * | 2009-04-10 | 2010-10-13 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and ethylene |
| CN103936542A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工集团公司 | Alkene catalysis cracking system and method for improving alkene total conversion rate |
| CN110526797A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | A kind of method and apparatus that steam cracking device depressurizes gasified raw material carbon four and recycles cooling capacity |
| CN112592250A (en) * | 2020-12-17 | 2021-04-02 | 国家能源集团宁夏煤业有限责任公司 | Method and system for preparing propylene by catalytic cracking of coal-based byproduct |
| CN113769662A (en) * | 2020-06-10 | 2021-12-10 | 中国石油化工股份有限公司 | Method for catalytic cracking of olefin |
| CN113845937A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Method for reducing olefin by catalyzing light gasoline |
| CN113845400A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from light gasoline |
| CN114456025A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
| CN114507113A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for preparing ethylene and propylene from waste plastics |
| WO2022147972A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Fluidized catalytic conversion method for producing low-carbon olefins from hydrocarbons |
| WO2022147970A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Fluidized catalytic conversion method for preparing low-carbon olefins |
| WO2022147971A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Fluidized catalytic conversion method for maximizing production of propylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10233069C1 (en) * | 2002-07-19 | 2003-09-18 | Lurgi Ag | Propylene production from liquid feed stream containing higher olefins by catalytic steam cracking includes compression of gaseous product, separating gas and separating liquid into 2 fractions before partial recycling |
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| CN101857520B (en) * | 2009-04-10 | 2013-02-27 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and ethylene |
| CN101857520A (en) * | 2009-04-10 | 2010-10-13 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and ethylene |
| CN103936542A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工集团公司 | Alkene catalysis cracking system and method for improving alkene total conversion rate |
| CN103936542B (en) * | 2013-01-23 | 2016-02-10 | 中国石油化工集团公司 | A kind of olefins by catalytic cracking system and method improving alkene total conversion rate |
| CN110526797B (en) * | 2018-05-24 | 2021-12-14 | 中国石油化工股份有限公司 | Method and device for gasifying carbon four as raw material through decompression of steam cracking device and recovering cold energy |
| CN110526797A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | A kind of method and apparatus that steam cracking device depressurizes gasified raw material carbon four and recycles cooling capacity |
| CN113769662A (en) * | 2020-06-10 | 2021-12-10 | 中国石油化工股份有限公司 | Method for catalytic cracking of olefin |
| CN113845937A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Method for reducing olefin by catalyzing light gasoline |
| CN113845400A (en) * | 2020-06-28 | 2021-12-28 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from light gasoline |
| CN113845937B (en) * | 2020-06-28 | 2023-06-06 | 中国石油化工股份有限公司 | Method for reducing olefin by catalyzing light gasoline |
| CN114456025A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
| CN114456025B (en) * | 2020-10-21 | 2024-05-28 | 中国石油化工股份有限公司 | Method and system for producing ethylene and propylene by catalyzing light gasoline |
| CN114507113A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for preparing ethylene and propylene from waste plastics |
| CN114507113B (en) * | 2020-10-28 | 2024-03-12 | 中国石油化工股份有限公司 | Method and system for preparing ethylene and propylene from waste plastics |
| CN112592250A (en) * | 2020-12-17 | 2021-04-02 | 国家能源集团宁夏煤业有限责任公司 | Method and system for preparing propylene by catalytic cracking of coal-based byproduct |
| WO2022147972A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Fluidized catalytic conversion method for producing low-carbon olefins from hydrocarbons |
| WO2022147970A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Fluidized catalytic conversion method for preparing low-carbon olefins |
| WO2022147971A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Fluidized catalytic conversion method for maximizing production of propylene |
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