CN101092325A - Method for preparing propylene by catalytic cracking olefin of containing carbon - Google Patents
Method for preparing propylene by catalytic cracking olefin of containing carbon Download PDFInfo
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- CN101092325A CN101092325A CN 200610027907 CN200610027907A CN101092325A CN 101092325 A CN101092325 A CN 101092325A CN 200610027907 CN200610027907 CN 200610027907 CN 200610027907 A CN200610027907 A CN 200610027907A CN 101092325 A CN101092325 A CN 101092325A
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- catalytic cracking
- olefin
- containing carbon
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Abstract
This invention relates to a method for preparing propylene by catalytic cracking of hydrocarbons. The method solves the problems of low added value, low conversion rate and low associativity of catalytic cracking process faced by traditional technique. The method comprises: gasifying liquid-phase hydrocarbon mixture by heat exchange with catalytic cracking product, mixing with overheated diluted steam to reach the reaction temperature, performing heat exchange between catalytic cracking product and condensed steam, passing through an air cooler and a cooler for cooling and separating out condensed steam, performing heat exchange between condensed steam and catalytic cracking product, utilizing as the heat source for the following debutanization and depropanization columns, compressing the catalytic cracking product to 0.3-1.1 MPa, sending into the depropanization column, separating to obtain C3 or below fractions at the overhead, separating with an ethylene apparatus to obtain propylene and ethylene, sending C4 or higher fractions at the bottom into the debutanization column, separating C4 fractions at the overhead, and recycling 30-90 wt.% into the reactor.
Description
Technical field
The present invention relates to a kind of method of preparing propylene 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 US 5059735 has been described a kind of C
3～C
7The technology of mixed olefins cracking system propylene, ethene, what be mixed into reactor with raw material in this technology is propane, the ratio of raw material and propane weight is 2～3: 1.Though this technology can improve C
2～C
4Selectivity, but also improved simultaneously C
6The selectivity of above aromatic hydrocarbons makes full use of C for the circulation cracking
3～C
7System propylene, ethene is very not favourable.
Document US 5981819 has been introduced a kind of C
4～C
7The technology of mixed olefins system propylene, ethene, the raw material mixed olefins needs to mix with superheated vapour in this technology, and the ratio of superheated vapour and raw material weight is 0.5～3.0: 1.0.Though contain the propylene and the butylene of 70% left and right sides raw material olefin total amount in the split product, butylene occupies ratio greatly.In addition, steam condensate does not reclaim heat with the cleavage reaction product heat exchange.
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 carbonaceous olefin mixture preparing propylene by catalytic cracking is provided.This method has when carbonaceous olefin mixture carried out catalytic cracking reaction, can obtain the advantage of the split product of highly selective propylene, ethene; Simultaneously, this method has by split product is carried out condensation, compression, increases depropanizing, debutylize separating step, has reduced the isolating load of dependence ethylene unit, 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 propylene by catalytic cracking olefin of containing carbon may further comprise the steps:
(1) with split product heat exchange gasification after the liquid phase feed carbonaceous olefin mixture, by mixing, reach 400～600 ℃ of feeding temperatures with superheated vapour, enter reactor and carry out catalytic cracking reaction;
(2) with the heat exchange of raw material carbonaceous olefin mixture after split product, again with the steam condensate heat exchange, enter gas-liquid separator by the cooling of air cooler, water cooler then;
(3) the isolated steam condensate in gas-liquid separator bottom, with after the split product heat exchange as the thermal source of follow-up tower reboiler; The isolated vapor-phase thermal cracking product in top is compressed into 0.3～1.1MPa, enters depropanizing tower;
(4) 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;
(5) at the bottom of the depropanizing Tata, obtain C
4And above cut.
In the technique scheme, the carbonaceous olefin mixture catalytic cracking catalyst is for selecting shape ZSM-5 molecular sieve catalyst; Liquid phase carbonaceous olefin raw material preferred version is C
4～C
8Carbonaceous olefin mixture; Reaction feed temperature preferred version enters reactor and carries out catalytic cracking reaction for reaching 450～550 ℃.Steam and raw material carbonaceous olefin weight ratio preferable range are 0.5～5.0: 1.0, and more preferably scope is 0.5～3.0: 1.0; Catalytic cracking reaction pressure preferable range is 0.02～0.3MPa, and more preferably scope is 0.02～0.15MPa; After the split product heat exchange, be 20～80 ℃ through air cooler, the cooled temperature preferable range of water cooler, more preferably scope is 30～60 ℃.The 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 inventive method adopts C
4Cut circulation has improved olefin conversion, and propylene that obtains and ethene are no less than 66% 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 US 5981819 process flow diagrams;
A is a steam among Fig. 1, Fig. 2, and B is the carbon containing mixed olefins, and C is a mixed C
4～C
7, 1 is process furnace, and 2 is mixing tank, and 3 is reactor, and 4 is feed exchanger, and 5 is the steam condensate interchanger, and 6 is water cooler, and 7 is gas-liquid separator, and 8 is compressor, and 9 is depropanizing tower, and 10 are rough segmentation tower reboiler, 11 is C
4And above cut, 12 is steam condensate, 13 is C
3And following cut, 14 is air cooler, 15 is C
5And above cut, 16 for effluxing C
4, 17 are circulation C
4, 18 is debutanizing tower, and 19 is fuel gas, and 20 is rectifying tower, and 21 is gasoline, 22 is C
4Following cut, 23 is the product condenser.
Among Fig. 1, raw material carbonaceous olefin mixture and reactor split product with superheated vapor mixing in process furnace 1, enter reactor 3 after interchanger 4 heat exchange.The reactor split product enters gas-liquid separator 7 again through interchanger 4,5 heat exchange after air cooler 14, water cooler 6 coolings.Gas-liquid separator 7 bottom liquid phases 12 are steam condensate, this part steam condensate after interchanger 5 heating as the thermal source of reboiler 10,19.Enter depropanizing tower 9 after compressed machine 8 compressions of gas-liquid separator 7 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 18, obtain C at the debutanizing tower top
4Cut 17 circulations enter reactor 3, C
4Cut 16 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 feed composition (weight %) is: butene-1: 45%, and butane: 35%, amylene-1:10%, pentane: 10%.Adopt document US 5981819 technical process, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 300 ZSM-5 molecular sieve, steam is 1.5 with the feed weight ratio, and temperature of reaction is 470 ℃, and reaction pressure is 0.13MPa, and the temperature behind the condenser 24 is 35 ℃, experimental results show that the product (weight %) that will obtain following ratio:
C
2～C
4：50.1％
Fuel gas: 4.6%
C
5Above cut: 45.3%
[comparative example 2]
By shown in Figure 2, carbonaceous olefin mixture feed composition (weight %) is: butene-1: 45%, and butane: 35%, amylene-1:10%, pentane: 10%.Adopt document US 5981819 technical process, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 300 ZSM-5 molecular sieve, steam is 2.5 with the feed weight ratio, and temperature of reaction is 500 ℃, and reaction pressure is 0.2MPa, and the temperature behind the condenser 24 is 40 ℃, evidence will obtain the product (weight %) of following ratio:
C
2～C
4：39.8％
Fuel gas: 9.6%
C
5Above cut: 50.6%
[embodiment 1]
By shown in Figure 1, carbonaceous olefin mixture feed composition (weight %) is: butene-1: 45%, and butane: 35%, amylene-1:10%, pentane: 10%.Adopt technical process of the present invention, catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 200 ZSM-5 molecular sieve, steam is 1.5 with the feed weight ratio, and temperature of reaction is 450 ℃, and reaction pressure is 0.06MPa, and the temperature behind the water cooler 6 is 35 ℃, split product is compressed into 0.8MPa, the C of 88 weight %
4The cut circulation, the pilot plant proof will obtain the product (weight %) of following ratio:
Ethene: 22.6%
Propylene: 42.1%
Other C
3Below: 3.0%
C
4Above cut: 32.3%
[embodiment 2]
By shown in Figure 1, the carbonaceous olefin mixture feed composition adopts technical process of the present invention with embodiment 1, and catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 200 ZSM-5 molecular sieve, steam is 2.0 with the feed weight ratio, and temperature of reaction is 500 ℃, and reaction pressure is 0.20MPa, and the temperature behind the water cooler 6 is 55 ℃, split product is compressed into 0.65MPa, the C of 68 weight %
4The cut circulation will obtain the product (weight %) of following ratio:
Ethene: 20.2%
Propylene: 45.0%
Other C
3Below: 2.8%
C
4Above cut: 32.0%
[embodiment 3]
By shown in Figure 1, the carbonaceous olefin mixture feed composition adopts technical process of the present invention with embodiment 1, and catalyzer is silica alumina ratio (SiO
2/ Al
2O
3) 200 ZSM-5 molecular sieve, steam is 3.5 with the feed weight ratio, and temperature of reaction is 550 ℃, and reaction pressure is 0.3MPa, and the temperature behind the water cooler 6 is 75 ℃, split product is compressed into 1.0MPa, the C of 48 weight %
4The cut circulation will obtain the product (weight %) of following ratio:
Ethene: 18.8%
Propylene: 43.3%
Other C
3Below: 3.6%
C
4Above cut: 34.3%.
Claims (9)
1, a kind of method of preparing propylene by catalytic cracking olefin of containing carbon may further comprise the steps:
(1) with split product heat exchange gasification after the liquid phase feed carbonaceous olefin mixture, by mixing, reach 400～600 ℃ of feeding temperatures with superheated vapour, enter reactor and carry out catalytic cracking reaction;
(2) with the heat exchange of raw material carbonaceous olefin mixture after split product, again with the steam condensate heat exchange, enter gas-liquid separator by the cooling of air cooler, water cooler then;
(3) the isolated steam condensate in gas-liquid separator bottom, with after the split product heat exchange as the thermal source of follow-up tower reboiler; The isolated vapor-phase thermal cracking product in top is compressed into 0.3～1.1MPa, enters depropanizing tower;
(4) 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;
(5) at the bottom of the depropanizing Tata, obtain C
4And above cut.
2,, it is characterized in that liquid phase carbonaceous olefin raw material is C according to the method for the described preparing propylene by catalytic cracking olefin of containing carbon of claim 1
4～C
8Carbonaceous olefin mixture; The reaction feed temperature reaches 450～550 ℃, enters reactor and carries out catalytic cracking reaction.
3, according to the method for the described preparing propylene by catalytic cracking olefin of containing carbon of claim 1, it is characterized in that steam and raw material carbonaceous olefin weight ratio are 0.5～5.0: 1.0, catalytic cracking reaction pressure is 0.02～0.3MPa; After the split product heat exchange, it is 20～80 ℃ through air cooler, the cooled temperature of water cooler.
4, according to the method for the described preparing propylene by catalytic cracking olefin of containing carbon of claim 3, it is characterized in that steam and raw material carbonaceous olefin weight ratio are 0.5～3.0: 1.0, catalytic cracking reaction pressure is 0.02～0.15MPa; After the split product heat exchange, it is 30～60 ℃ through air cooler, the cooled temperature of water cooler.
5, according to the method for the described preparing propylene 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.
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 propylene 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 propylene 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 propylene by catalytic cracking olefin of containing carbon of claim 7
4Cut 45～85 weight % circulation enters reactor cracking once more.
9,, it is characterized in that depropanizing tower, debutanizing tower are packing tower, tray column or valve tray column according to the method for the described preparing propylene by catalytic cracking olefin of containing carbon of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610027907A CN101092325B (en) | 2006-06-21 | 2006-06-21 | Method for preparing propylene by catalytic cracking olefin of containing carbon |
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|---|---|---|---|
| CN200610027907A CN101092325B (en) | 2006-06-21 | 2006-06-21 | Method for preparing propylene by catalytic cracking olefin of containing carbon |
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| CN101092325B CN101092325B (en) | 2010-05-12 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286296A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene |
| CN102286292A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate |
| CN104603241A (en) * | 2012-08-09 | 2015-05-06 | 林德股份公司 | Method for producing olefins by means of thermal steam cracking in cracking furnaces |
| CN107281771A (en) * | 2016-04-11 | 2017-10-24 | 中国石化工程建设有限公司 | The combination process that a kind of gas fractionation unit depropanizing tower is expanded production and saved |
| CN107739291A (en) * | 2017-10-20 | 2018-02-27 | 山西沸石科技有限公司 | A kind of method that FCC gasoline modification produces chemical products simultaneously |
| CN110087748A (en) * | 2016-12-20 | 2019-08-02 | 沙特基础工业全球技术有限公司 | The method for separating straightαolefin |
| 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 |
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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2006
- 2006-06-21 CN CN200610027907A patent/CN101092325B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286296A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene |
| CN102286292A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate |
| CN102286296B (en) * | 2010-06-18 | 2013-08-14 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene |
| CN102286292B (en) * | 2010-06-18 | 2013-11-06 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene by pyrolyzing C4 raffinate |
| US9505679B2 (en) | 2012-08-09 | 2016-11-29 | Linde Aktiengesellschaft | Process for preparing olefins by thermal steamcracking in cracking furnaces |
| CN104603241B (en) * | 2012-08-09 | 2016-10-12 | 林德股份公司 | The method preparing alkene by the vapours cracking in cracking funace |
| CN104603241A (en) * | 2012-08-09 | 2015-05-06 | 林德股份公司 | Method for producing olefins by means of thermal steam cracking in cracking furnaces |
| CN107281771A (en) * | 2016-04-11 | 2017-10-24 | 中国石化工程建设有限公司 | The combination process that a kind of gas fractionation unit depropanizing tower is expanded production and saved |
| CN107281771B (en) * | 2016-04-11 | 2020-03-06 | 中国石化工程建设有限公司 | Composite process for expanding production and saving energy of depropanizer of gas fractionation device |
| CN110087748A (en) * | 2016-12-20 | 2019-08-02 | 沙特基础工业全球技术有限公司 | The method for separating straightαolefin |
| CN107739291A (en) * | 2017-10-20 | 2018-02-27 | 山西沸石科技有限公司 | A kind of method that FCC gasoline modification produces chemical products simultaneously |
| CN107739291B (en) * | 2017-10-20 | 2021-12-07 | 山西沸石科技有限公司 | Method for modifying FCC gasoline and producing chemical products simultaneously |
| 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 |
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|---|---|
| CN101092325B (en) | 2010-05-12 |
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