CN100368355C - Method for raising yield of ethene, propylene - Google Patents
Method for raising yield of ethene, propylene Download PDFInfo
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- CN100368355C CN100368355C CNB2005100288151A CN200510028815A CN100368355C CN 100368355 C CN100368355 C CN 100368355C CN B2005100288151 A CNB2005100288151 A CN B2005100288151A CN 200510028815 A CN200510028815 A CN 200510028815A CN 100368355 C CN100368355 C CN 100368355C
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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
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- 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 increasing the yields of ethylene and propylene products. The method comprises: (1) adding an olefin-rich mixture containing onr or more C4+ olefins into a reactor, and reacting at 400-600 deg.C, 0-0.5 MPa, and weight space velocity of 0.1-50 h-1 in the presence of a catalyst to obtain a mixture of ethylene and propylene; (2) continuously separating the mixture by the membrane on the inner wall of the reactor, discharging ethylene and propylene out of the reaction zone, and introducing the rest components to the following process. The method can be used in practical manufacture of ethylene and propylene.
Description
Technical field
The present invention relates to a kind of method that improves propylene, yield of ethene, particularly be used to improve the method for propylene, yield of ethene by membrane reactor about carbon four and above olefins by catalytic cracking process thereof.
Background technology
Propylene is the most important basic organic that is only second to ethene, and in the last few years, because the quick growth of acryloyl derivative demand, the whole world faced the propylene shortage problem, on the other hand, in the world wide, the appreciable C of quantity is arranged
4And C
4Above olefin feedstock.Be subjected to the influence of factors such as the variation in Chemicals market and transportation cost, it is a kind of approach that utilizes preferably that these raw materials are carried out deep processing on the spot.C wherein
4And above conversion of olefines is that propylene is a kind of promising technology.This technology can be utilized the lower C of superfluous relatively added value on the one hand
4And C
4Above olefin feedstock can obtain broad-spectrum propylene product again on the other hand, and the ethene of by-product makes this technology more attractive simultaneously.
Disclosing a kind of employing among the document CN1490287A is raw material with carbon containing four or carbon pentaene hydrocarbon mixture, in fixed-bed reactor, adopts 350 ℃～500 ℃ temperature, the pressure of 0.6～1.0MPa and 1～10 hour
-1Carry out the method for prepared in reaction ethene and propylene under the condition of weight space velocity.This method introduces the modification and the reaction result thereof of dissimilar catalyzer, and reaction raw materials is primarily aimed at carbon four and expect the carbon Wuyuan, and does not comprise the cracking situation of carbon five above alkene, and the overall selectivity and the yield of the ethylene, propylene of document report are lower simultaneously.
The patent WO:0026163 of Equistar company is to contain weight 60% C at least
4, C
5Alkene is raw material, adopts central hole zeolite catalyst, the kind of its zeolite has, and the zeolite of one-dimensional channels is as ZSM-23, AlPO4-11 etc., and its aperture is greater than 3.5 , and pore size index is 14～28; Also can be the zeolite in intersection duct: as ZSM-57, AlPO4-18 etc., its aperture, first duct be greater than 3.5 , and pore size index is that 14～28, the second duct pore size index is less than 20.This catalyzer can be Na type, H type etc., also can add oxidized metal such as the Pt and the Pd etc. of trace, removes carbon distribution when being beneficial to catalyst regeneration, generally adopts fixed-bed process.Its temperature of reaction is 200～750 ℃, and reaction pressure is 0.05～1MPa, and weight hourly space velocity is 0.5～1000 hour
-1The overall selectivity and the yield of ethylene, propylene are lower in same this patent.
LURGI has announced the Propylur technology of its carbon four and above alkene increased low carbon olefine output thereof, and this technology is under low pressure, high temperature, catalyzer existence and adiabatic reaction conditions, C
4To C
7Conversion of olefines be propylene, a technology of by-product ethene and pyrolysis gasoline simultaneously.Experiment is 1.6 hours at reaction velocity in the middle of it
-1Reactor inlet temperatures is 480 ℃; Reactor pressure is 0.2MPa; The reactor outlet temperature is 440 ℃, pressure 0.19MPa; Water and C
4Alkene mole thinning ratio is to react under 7.26: 1 the condition.Adopt traditional partitioning cycle pattern in this technology, energy consumption height not only, and also the yield and the selectivity of final propylene and ethylene are lower.
Summary of the invention
Problems such as technical problem to be solved by this invention is to exist the propylene and ethylene selectivity low in the technical literature in the past, and yield is low provide a kind of new raising propylene, the method for yield of ethene.This method has propylene, the higher technological merit of yield of ethene.
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 that improves propylene, yield of ethene, with carbon four, carbon more than four or the rich olefins mixture of carbon four and above alkene thereof be that raw material is 400～600 ℃ in temperature of reaction, reaction pressure is 0～0.5MPa, and weight space velocity is 0.1～50 hour
-1Under the condition, raw material contacts with catalyzer by the reaction zone in the reactor, and reaction generates the mixture that contains ethene, propylene; Wherein, propylene is constantly separated by the film on the reactor wall with ethylene product, discharges reaction zone, and all the other components in the mixture are introduced follow-up workshop section by the reaction zone outlet.
Rich olefins mixture material preferred version in the technique scheme is from carbon four and above cut or the coproduction of a-alkene, MTO (methanol-to-olefins) and the carbon four of MTP by-products such as (preparing propylene from methanol) and the above olefin fraction thereof of steam cracking device in plant catalytic cracker, the ethylene plant.Rich olefins mixture more preferably scope is C
4～C
12Normal olefine, best preferable range is C
4～C
8Normal olefine.The reactor preferred reaction conditions is as follows: temperature of reaction is 450～550 ℃, and reaction pressure is 0～0.1MPa, and weight space velocity is 1～20 hour
-1Film on the reactor wall is to be made of basement membrane and molecular screen membrane, and the basement membrane preferred version is α-Al
2O
3, the molecular screen membrane preferred version is the A type molecular sieve film.
A large amount of experimental studies show that carbon four and above alkene thereof carry out in the scission reaction process, C in the split product on solid acid catalyst
2～C
5The distribution of alkene is near thermodynamic equilibrium state, particularly importantly, and C
2～C
5After the mixture of any alkene or different alkene arbitrary proportion entered reactor, its products distribution was basic identical, and this proves absolutely C
2～C
5There is the height reversible reaction in alkene under the solid acid catalyst effect, and is subjected to thermodynamic control to a great extent.
Based on this, among the present invention, fully take into account the response characteristic of carbon four and above olefins by catalytic cracking increasing production of propylene and ethylene process thereof, the place is provided with molecular screen membrane at the reactor wall, propylene and ethylene selectivity infiltration that reaction produces are shifted out, thereby break the thermodynamic equilibrium state that carbon four and above olefins by catalytic cracking process thereof are set up, raw material olefin is moved to purpose product propylene, ethylene reaction direction to greatest extent, thereby reach the purpose that maximization improves propylene, yield of ethene, obtained better technical effect.
Description of drawings
Fig. 1 is for improving the schematic flow sheet of propylene, yield of ethene.
In the accompanying drawing 1: 1 be unstripped gas, 2 for the product passage, 3 for reaction zone, 4 for reactor heaters, 5 for the film on the reactor wall, 6 for the purpose product flow out component, 7 for the film outer tube, 8 for purpose product channel outlet, 9 be the reactor outlet effluent.
Workflow is as follows: the rich olefins mixture material gas 1 of one or more carbon four or above alkene enters reaction zone 3 and catalyst haptoreaction. The propylene that reaction produces, ethene enter film 5 on the reactor wall by the film 5 on the reactor wall and reaction zone 3 is left in the gap between the film outer tube 7, and enter follow-up workshop section by the purpose product channel outlet 8 of purpose product passage 2, because purpose product propylene and ethylene constantly shifts out in the reaction zone 3, the former balance of having set up is broken, and unreacted raw material just successively moves to ethene, propylene the Direction of Reaction.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
The preparation process of the film on the reactor wall:
(a) preparation of basement membrane.Basement membrane adopts α-Al
2O
3, diaphragm-operated is shaped as the disk shape, diameter is 60 millimeters, and thickness is 5 millimeters, and the aperture is 0.2 micron, and porosity is about 50%.Basement membrane polishes flat through fine sandpaper, and ultrasonic washing in distilled water is then 150 ℃ of dry for standby.
(b) process of synthetic A type molecular sieve film is, the gel of preparation molecular screen membrane is sodium silicate solution, sodium hydroxide solution, and aluminium hydroxide and deionized water mix, and the prescription of synthetic liquid is 2SiO
2: 3Na
2O: Al
2O
3: 200H
2O.The basement membrane diaphragm is fixed with support, vertically be positioned in the tetrafluoroethylene synthesis reactor.To synthesize liquid then and change synthesis reactor over to, place microwave oven.Be heated to 100 ℃ rapidly in 50 seconds, reduce the power of microwave oven then, the temperature of keeping synthetic liquid is 100 ℃, heating crystallization 3 hours.The synthetic diaphragm through deionized water wash to neutral, in 150 ℃ of heating, dryings 5 hours.
The reaction zone inner catalyst is the ZSM-5 molecular sieve catalyst, silica alumina ratio SiO
2/ Al
2O
3Be 500.Temperature of reaction is 480 ℃, and reaction pressure is 0.02MPa, and raw material is from FCC mixed c 4 (component distributes and sees Table 1), and its weight space velocity is 10 hours
-1Reaction result is, the yield of ethene is 18.7%, and the yield of propylene is 48.6%.
Table 1, the weight percent that derives from the hybrid C 4 of FCC are formed
| The component title | Weight percent is formed, % | The component title | Weight percent is formed, % |
| Trimethylmethane | 3.249 | 1-butylene | 51.857 |
| Normal butane | 13.368 | Iso-butylene | 0.048 |
| Propadiene | 0.068 | Suitable-2-butylene | 13.211 |
| Acetylene | 0.008 | Iso-pentane | 0.002 |
| Neopentane | 0.149 | Skellysolve A | 0.000 |
| Instead-2-butylene | 17.259 | 1,3-butadiene | 0.110 |
| Amylene and isohexane | 0.127 | Methylacetylene | 0.004 |
| Normal hexane | 0.007 | More than carbon six reaches | 0.531 |
[embodiment 2]
According to each step and the reaction conditions of embodiment 1, just change catalyzer ZSM-5 molecular sieve catalyst silica alumina ratio SiO
2/ Al
2O
3Be 100.Temperature of reaction is 450 ℃, and reaction pressure is 0.04MPa, and the pure 1-butylene of raw material, its weight space velocity are 0.2 hour
-1Reaction result is, the yield of ethene is 19.8%, and the yield of propylene is 49.8%.
[embodiment 3]
According to each step and the reaction conditions of embodiment 1, just change catalyzer ZSM-5 molecular sieve catalyst silica alumina ratio SiO
2/ Al
2O
3Be 30.Temperature of reaction is 550 ℃, and reaction pressure is 0MPa, pure mixing carbon eight normal olefines of raw material, and its weight space velocity is 20 hours
-1Reaction result is, the yield of ethene is 21.3%, and the yield of propylene is 53.7%.
[embodiment 4]
According to each step and the reaction conditions of embodiment 1, just change catalyzer ZSM-5 molecular sieve catalyst silica alumina ratio SiO
2/ Al
2O
3Be 1000.Temperature of reaction is 600 ℃, and reaction pressure is 0.4MPa, pure mixing carbon eight normal olefines of raw material, and its weight space velocity is 50 hours
-1Reaction result is, the yield of ethene is 19.3%, and the yield of propylene is 50.1%.
[embodiment 5]
According to each step and the reaction conditions of embodiment 1, just changing catalyzer is the ZSM-11 molecular sieve catalyst, silica alumina ratio SiO
2/ Al
2O
3Be 150.Temperature of reaction is 550 ℃, and reaction pressure is 0.02MPa, and raw material adopts C in the methanol decomposition producing light olefins by product
4To C
7Monoolefine, wherein C
4And C
5Olefin(e) centent is 85%, and all the other about 15% are C
6Above alkene, its weight space velocity are 5 hours
-1Reaction result is, the yield of ethene is 18.5%, and the yield of propylene is 48.8%.
[embodiment 6]
According to each step and the reaction conditions of embodiment 1, just changing catalyzer is the ZSM-42 molecular sieve catalyst, silica alumina ratio SiO
2/ Al
2O
3Be 100.Temperature of reaction is 480 ℃, and reaction pressure is 0MPa, and raw material is from FCC mixed c 4 (component distributes and sees Table 1), and its weight space velocity is 5 hours
-1Reaction result is, the yield of ethene is 17.9%, and the yield of propylene is 48.3%.
[Comparative Examples 1]
With reference to each step and the reaction conditions of embodiment 1, just adopt the conventional fixed-bed reactor that do not have permeable membrane, other condition is all identical with embodiment 1, and catalyzer is the ZSM-5 molecular sieve catalyst, silica alumina ratio SiO
2/ Al
2O
3Be 500.In temperature of reaction is 480 ℃, and reaction pressure is 0.02MPa, and raw material is from FCC mixed c 4 (component distributes and sees Table 1), and its weight space velocity is 10 hours
-1The time, reaction result is, and the yield of ethene is 10.3%, and the yield of propylene is 28.4%.
Claims (7)
1. method that improves propylene, yield of ethene, with carbon four, carbon more than four or the rich olefins mixture of carbon four and above alkene thereof be that raw material is 400～600 ℃ in temperature of reaction, reaction pressure is 0～0.5MPa, weight space velocity is 0.1～50 hour
-1Under the condition, raw material contacts with catalyzer by the reaction zone in the reactor, and reaction generates the mixture that contains ethene, propylene; Wherein, propylene is constantly separated by the film on the reactor wall with ethylene product, discharges reaction zone, and all the other components in the mixture are introduced follow-up workshop section by the reaction zone outlet.
2. according to the method for the described raising propylene of claim 1, yield of ethene, it is characterized in that carbon four and above cut or the carbon four of a-alkene coproduction, MTO and MTP by-product and the above olefin fraction thereof of rich olefins mixture material from steam cracking device in plant catalytic cracker, the ethylene plant.
3. according to the method for the described raising propylene of claim 1, yield of ethene, it is characterized in that the rich olefins mixture is C
4～C
12Normal olefine.
4. according to the method for the described raising propylene of claim 3, yield of ethene, it is characterized in that the rich olefins mixture is C
4～C
8Normal olefine.
5. according to the method for the described raising propylene of claim 1, yield of ethene, it is characterized in that the reactor reaction condition: temperature of reaction is 450～550 ℃, and reaction pressure is 0～0.1MPa, and weight space velocity is 1～20 hour
-1
6. according to the method for the described raising propylene of claim 1, yield of ethene, it is characterized in that the film on the reactor wall is to be made of basement membrane and molecular screen membrane.
7. according to the method for the described raising propylene of claim 6, yield of ethene, it is characterized in that basement membrane is α-Al
2O
3, molecular screen membrane is the A type molecular sieve film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100288151A CN100368355C (en) | 2005-08-15 | 2005-08-15 | Method for raising yield of ethene, propylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100288151A CN100368355C (en) | 2005-08-15 | 2005-08-15 | Method for raising yield of ethene, propylene |
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|---|---|
| CN1915922A CN1915922A (en) | 2007-02-21 |
| CN100368355C true CN100368355C (en) | 2008-02-13 |
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|---|---|---|---|
| CNB2005100288151A Active CN100368355C (en) | 2005-08-15 | 2005-08-15 | Method for raising yield of ethene, propylene |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8137631B2 (en) | 2008-12-11 | 2012-03-20 | Uop Llc | Unit, system and process for catalytic cracking |
| US8246914B2 (en) | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
| US8889076B2 (en) | 2008-12-29 | 2014-11-18 | Uop Llc | Fluid catalytic cracking system and process |
| CN102285851B (en) * | 2010-06-18 | 2015-04-15 | 中国石油化工股份有限公司 | Method for increasing yields of ethylene and propylene |
| CN102285854B (en) * | 2010-06-18 | 2013-11-06 | 中国石油化工股份有限公司 | Method for increasing yields of propylene, ethylene and butadiene |
| CN102285852B (en) * | 2010-06-18 | 2015-08-19 | 中国石油化工股份有限公司 | Utilize the method for refinery C four increasing output of ethylene and propylene |
| CN102285857B (en) * | 2010-06-18 | 2015-04-15 | 中国石油化工股份有限公司 | Method for increasing yields of propylene and ethylene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1027679C (en) * | 1989-08-10 | 1995-02-22 | 中国科学院兰州化学物理研究所 | Gas separation membrance with selective adsorbability |
| CN1279662A (en) * | 1997-10-16 | 2001-01-10 | 阿克西瓦有限公司 | Preparation of ethylene by gas permeation |
-
2005
- 2005-08-15 CN CNB2005100288151A patent/CN100368355C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1027679C (en) * | 1989-08-10 | 1995-02-22 | 中国科学院兰州化学物理研究所 | Gas separation membrance with selective adsorbability |
| CN1279662A (en) * | 1997-10-16 | 2001-01-10 | 阿克西瓦有限公司 | Preparation of ethylene by gas permeation |
Non-Patent Citations (4)
| Title |
|---|
| The first large-scale pervaporation plant using tubular-typemodule with zeolite NaA membrane. Morigami Y,Kondo M.Sep.Pur,Technol.,No.25. 2001 * |
| 分子筛膜的研制进展与应用前景. 成岳，李健生.中国陶瓷工业，第1期. 2004 * |
| 基本有机原料技术发展动向. 白尔铮，胡云光.当代石油石化，第5期. 2004 * |
| 气体分离分子筛膜. 程志林，晁自胜，万惠霖.化学进展，第1期. 2004 * |
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| Publication number | Publication date |
|---|---|
| CN1915922A (en) | 2007-02-21 |
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