CN100413822C - Method for increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture - Google Patents
Method for increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture Download PDFInfo
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- CN100413822C CN100413822C CNB2005100294665A CN200510029466A CN100413822C CN 100413822 C CN100413822 C CN 100413822C CN B2005100294665 A CNB2005100294665 A CN B2005100294665A CN 200510029466 A CN200510029466 A CN 200510029466A CN 100413822 C CN100413822 C CN 100413822C
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- olefin mixture
- ethene
- propylene
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Abstract
The present invention relates to the process of catalytically cracking carbon-containing olefin mixture to produce propylene and ethylene, and the process is superior to available technology and has greatly increased value of carbon-containing olefin mixture and optimized catalytically cracking process. The technological scheme of the present invention includes the heat exchange between the carbon-containing olefin mixture liquid material and cracked product to gasify and the further mixing of the gasified material with diluted overheat steam to reach the reaction temperature; treating the cracked product through heat exchange with the material, heat exchange with steam condensate and cooling in the cooler to separate out steam condensate; using the steam condensate as the heat source of subsequent separating tower; and further separation of the cracked product to obtain propylene, ethylene and other fractions in different concentrations. The process may be used in industrial production.
Description
Technical field
The present invention relates to a kind of method of increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture.
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.Simultaneously, this technology can only with just can use after other device combines, can't set up as isolated system.
The described technology of above-mentioned document all needs raw material and other inert reaction gas to be mixed together the generation catalytic cracking reaction, as technology independently, and all can't apparatus for establishing.
Summary of the invention
Technical problem to be solved by this invention is the independence and the not strong problem of combinableness of the not high and carbonaceous olefin cracking technology of carbonaceous olefin mixture added value in the conventional art, and a kind of method of new increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture 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 increases separating step by split product is carried out condensation, compression, can obtain propylene, ethene that different purity requires, can not only improve self independence, and can combine with multiple device, improves economy.
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 increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture may further comprise the steps:
(1) with split product heat exchange gasification after liquid phase feed C
4～C
8Carbonaceous 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 water cooler cooling then;
(3) the isolated steam condensate in gas-liquid separator bottom, with after the split product heat exchange as the thermal source of the first and second knockout tower reboilers; The isolated vapor-phase thermal cracking product in top is compressed into 1.0～4.0MPa, enters first knockout tower;
(4) obtaining weight concentration at the first knockout tower cat head is 90～99% ethene, obtains C at the bottom of the tower
3Above cut is sent into second knockout tower;
(5) C that obtains at the second knockout tower cat head
3Cut enters the 3rd knockout tower; Obtain C at the bottom of the tower
4Above cut;
(6) at the 3rd knockout tower cat head for not coagulating gas, side line is extracted out and is obtained the propylene that weight concentration is 90-99%, obtains weight concentration at the bottom of the tower and be 80～95% propane.
In the technique scheme, the carbonaceous olefin mixture catalytic cracking catalyst is the shape-selective molecular sieve catalyzer; The reaction feed preferred version enters reactor and carries out catalytic cracking reaction for reaching 450～550 ℃; The reactor preferred version is one or more snippets fixed-bed reactor.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; The reaction pressure preferable range is 0.02～0.3MPa, and more preferably scope is 0.02～0.15MPa; Temperature preferable range after steam condensate and the split product heat exchange is 80～160 ℃, and more preferably scope is 100～150 ℃; After the split product heat exchange, be 20～80 ℃ through water cooler refrigerative temperature preferable range, more preferably scope is 30～60 ℃.The split product preferred version enters the first knockout tower stage casing for being compressed into 2.0～3.0MPa; The C that the first knockout tower preferred version obtains at the bottom of for tower
3Above cut is sent into the second knockout tower stage casing; The second knockout tower preferred version is the C that cat head obtains
3Cut enters the 3rd knockout tower 1/4th places at the bottom of tower, the C that obtains at the bottom of the tower
422～76 weight % of above cut, preferable range is 30～66 weight %, circulation is as cracking stock; The 3rd knockout tower preferred version is extracted out for the top of tower side line and is obtained propylene; First to the 3rd knockout tower preferred version is packing tower, tray column or valve tray column.
Propylene that the inventive method obtains and ethene are no less than 56% of alkene total amount in the raw material.The first, the 3rd knockout tower obtains propylene, ethene respectively, and both purity can be optimized by the parameter of regulating knockout tower.If as self-contained system, the purity that then can regulate propylene, ethene is polymerization-grade; If be incorporated into preparing ethylene by steam cracking device, FCC apparatus and other propylene enhancing device such as preparing propylene from methanol device, then the propylene in this production technique, ethene purity can reduce, and carry out high precision by these main devices again and purify.Therefore, the inventive method has very high independence, 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, 4 is feed exchanger, and 5 is the steam condensate interchanger, and 6 is water cooler, and 7 is gas-liquid separator, 8 is compressor, and 9 is first knockout tower, and 10 is the first knockout tower reboiler, and 11 is second knockout tower, 12 is the second knockout tower reboiler, and 13 is the 3rd knockout tower reboiler, and 14 is the 3rd knockout tower, 15 is the gaseous ethene product, and 16 is the liquid propylene product, and 17 is noncondensable gas, 18 is propane, and 19 is steam condensate, and 20 are the outer C of out-of-bounds
4Above cut, 21 are circulation C
4Above cut, 22 is the product condenser, and 23 is rectifying tower, and 24 is fuel gas, and 25 is C
4Following cut, 26 is gasoline.
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 water cooler 6 coolings.Gas-liquid separator 7 bottom liquid phases 19 are steam condensate, this part steam condensate after interchanger 5 heating as the thermal source of reboiler 10 and reboiler 12.Enter first knockout tower 9 after compressed machine 8 compressions of gas-liquid separator 7 top gas phases, obtain the gaseous ethene 15 of different purity at the first knockout tower top, the bottom is C
3Above cut is sent into second knockout tower 11.At the second knockout tower top is C
3Cut is sent into the 3rd knockout tower 14; The bottom is C
4Above cut, portion C
4Above cut 21 is circulated to reactor 3 as cracking stock, and rest part 20 is sent out-of-bounds.The top of the 3rd knockout tower 14 is a noncondensable gas 17, and side line is extracted the liquid propylene 16 of different purity out, and the bottom is the propane 18 of different purity.
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, 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 22 is 35 ℃, experimental results show that the product (weight %) that will obtain following ratio:
C
2～C
4：51.6％
Fuel gas: 4.6%
C
5Above cut: 43.8%
[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, steam is 2.5 with the feed weight ratio, and temperature of reaction is 500 ℃, and reaction pressure is 0.2MPa, and evidence will obtain the product (weight %) of following ratio:
C
2～C
4：39.8％
Fuel gas: 11.6%
C
5Above cut: 48.6%
[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 the ZSM-5 molecular sieve of silica alumina ratio 200, reactor is one section fixed bed pattern, steam is 1.5 with the feed weight ratio, and temperature of reaction is 450 ℃, and reaction pressure is 0.06MPa, temperature after the steam condensate heat exchange is 160 ℃, temperature behind the water cooler 6 is 35 ℃, and split product is compressed into 1.5MPa, the C of 26 weight %
4Above cut circulation is as cracking stock, and the pilot plant proof will obtain the product (weight %) of following ratio:
Weight concentration is 92% ethene: 16.3%
Weight concentration is 93% propylene: 39.5%
Non-condensable gas: 0.06%
Weight concentration is 95% propane: 2.5%
C
4Above cut: 41.6%
[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 the ZSM-5 molecular sieve of silica alumina ratio 200, reactor is two sections fixed bed patterns, steam is 2.0 with the feed weight ratio, and temperature of reaction is 500 ℃, and reaction pressure is 0.20MPa, temperature after the steam condensate heat exchange is 120 ℃, temperature behind the water cooler 6 is 55 ℃, and split product is compressed into 2.5MPa, the C of 46 weight %
4Above cut circulation will obtain the product (weight %) of following ratio as cracking stock:
Weight concentration is 97% ethene: 9.1%
Weight concentration is 96% propylene: 48.6%
Non-condensable gas: 0.08%
Weight concentration is 92% propane: 3.5%
C
4Above cut: 38.8%
[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 the ZSM-5 molecular sieve of silica alumina ratio 200, reactor is two sections fixed bed patterns, steam is 3.5 with the feed weight ratio, and temperature of reaction is 550 ℃, and reaction pressure is 0.3MPa, temperature after the steam condensate heat exchange is 80 ℃, temperature behind the water cooler 6 is 75 ℃, and split product is compressed into 3.5MPa, the C of 76 weight %
4Above cut circulation will obtain the product (weight %) of following ratio as cracking stock:
Weight concentration is 98% ethene: 12.3%
Weight concentration is 99% propylene: 45.5%
Non-condensable gas: 0.05%
Weight concentration is 80% propane: 5.5%
C
4Above cut: 36.7%
Claims (10)
1. the method for a carbonaceous olefin mixture catalytic pyrolysis propylene enhancing, ethene may further comprise the steps:
(1) with split product heat exchange gasification after liquid phase feed C
4～C
8Carbonaceous 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 water cooler cooling then;
(3) the isolated steam condensate in gas-liquid separator bottom, with after the split product heat exchange as the thermal source of the first and second knockout tower reboilers; The isolated vapor-phase thermal cracking product in top is compressed into 1.0～4.0MPa, enters first knockout tower;
(4) obtaining weight concentration at the first knockout tower cat head is 90～99% ethene, obtains C at the bottom of the tower
3Above cut is sent into second knockout tower;
(5) C that obtains at the second knockout tower cat head
3Cut enters the 3rd knockout tower; Obtain C at the bottom of the tower
4Above cut;
(6) at the 3rd knockout tower cat head for not coagulating gas, side line is extracted out and is obtained the propylene that weight concentration is 90-99%, obtains weight concentration at the bottom of the tower and be 80～95% propane.
2. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that reaction feed reaches 450～550 ℃, enter reactor and carry out catalytic cracking reaction; Reactor is one or more snippets fixed-bed reactor.
3. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that steam and raw material carbonaceous olefin weight ratio are 0.5～5.0: 1.0, reaction pressure is 0.02～0.3MPa; Temperature after steam condensate and the split product heat exchange is 80～160 ℃; After the split product heat exchange, it is 20～80 ℃ through water cooler refrigerative temperature.
4. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 3 propylene enhancing, ethene, it is characterized in that steam and raw material carbonaceous olefin weight ratio are 0.5～3.0: 1.0, reaction pressure is 0.02～0.15MPa; Temperature after steam condensate and the split product heat exchange is 100～150 ℃; After the split product heat exchange, it is 30～60 ℃ through water cooler refrigerative temperature.
5. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that split product is compressed into 2.0～3.0MPa, enter the first knockout tower stage casing.
6. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that first separates the C that obtains at the bottom of the Tata
3Above cut is sent into the second knockout tower stage casing.
7. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that the C that the second knockout tower cat head obtains
3Cut enters the 3rd knockout tower 1/4th places at the bottom of tower, the C that obtains at the bottom of the tower
422～76 weight % circulation of above cut is as cracking stock.
8. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 7 propylene enhancing, ethene, its spy just is being that second separates the C that obtains at the bottom of the Tata
430～66 weight % circulation of above cut is as the catalytic pyrolysis raw material.
9. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that the 3rd knockout tower top side line extraction obtains propylene.
10. according to the method for the described carbonaceous olefin mixture catalytic pyrolysis of claim 1 propylene enhancing, ethene, it is characterized in that first to the 3rd knockout tower is packing tower, tray column or valve tray column.
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|---|---|---|---|
| CNB2005100294665A CN100413822C (en) | 2005-09-07 | 2005-09-07 | Method for increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture |
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|---|---|---|---|
| CNB2005100294665A CN100413822C (en) | 2005-09-07 | 2005-09-07 | Method for increasing production of propylene and ethylene by catalytic cracking carbonaceous olefin mixture |
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| CN100413822C true CN100413822C (en) | 2008-08-27 |
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| CN109369318B (en) * | 2018-12-07 | 2021-05-21 | 宁波旭合瑞石化工程有限公司 | Method for maximizing production of propylene by using C5 olefin as main raw material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5059735A (en) * | 1989-05-04 | 1991-10-22 | Mobil Oil Corp. | Process for the production of light olefins from C5 + hydrocarbons |
| US5981819A (en) * | 1996-11-26 | 1999-11-09 | Metallgesellschaft Aktiengesellschaft | Process of generating C3 - and C4 -olefins from a feed mixture containing C4 to C7 olefins |
| US6410813B1 (en) * | 1999-06-17 | 2002-06-25 | Fina Research, S.A. | Production of olefins |
| CN1653020A (en) * | 2002-07-19 | 2005-08-10 | 乐吉股份公司 | Method for producing propylene from a flow containing C4 to C8 olefins |
-
2005
- 2005-09-07 CN CNB2005100294665A patent/CN100413822C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5059735A (en) * | 1989-05-04 | 1991-10-22 | Mobil Oil Corp. | Process for the production of light olefins from C5 + hydrocarbons |
| US5981819A (en) * | 1996-11-26 | 1999-11-09 | Metallgesellschaft Aktiengesellschaft | Process of generating C3 - and C4 -olefins from a feed mixture containing C4 to C7 olefins |
| US6410813B1 (en) * | 1999-06-17 | 2002-06-25 | Fina Research, S.A. | Production of olefins |
| CN1653020A (en) * | 2002-07-19 | 2005-08-10 | 乐吉股份公司 | Method for producing propylene from a flow containing C4 to C8 olefins |
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