CN100491305C - Production method for increasing production of propylene, ethene - Google Patents
Production method for increasing production of propylene, ethene Download PDFInfo
- Publication number
- CN100491305C CN100491305C CNB2005100288166A CN200510028816A CN100491305C CN 100491305 C CN100491305 C CN 100491305C CN B2005100288166 A CNB2005100288166 A CN B2005100288166A CN 200510028816 A CN200510028816 A CN 200510028816A CN 100491305 C CN100491305 C CN 100491305C
- Authority
- CN
- China
- Prior art keywords
- ethene
- carbon
- propylene
- reaction
- production method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
This invention relates to a method for manufacturing propylene and ethylene with high yields. The method comprises: contacting one or more of C4+ alkenes with 0.3-0.56 nm porous silicon aluminum phosphate molecular sieve catalyst in the presence of steam in a fluid bed reactor, and reacting to obtain effluent containing propylene and ethylene. The method solves the problems of low selectivity and low yields of propylene and ethylene, as well as frequent regeneration of the catalyst, and can be used in propylene and ethylene industrial manufacture.
Description
Technical field
The present invention relates to the method for a kind of propylene enhancing, ethene, particularly about the production method of carbon four and above olefins by catalytic cracking propylene enhancing thereof, ethene.
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 carbon Wuyuan material, and do not comprise the cracking situation of carbon five above alkene, there are problems such as life of catalyst yield short and the purpose product is lower in the fixed-bed reactor of document employing simultaneously.
The patent WO 00/26163 of Equistar company is to contain weight 60%C at least
4, C
5Alkene is raw material, adopts central hole zeolite catalyst, and the kind of its zeolite has, the zeolite of one-dimensional channels as: its apertures such as ZSM-23, AlPO4-11 are greater than 3.5
, pore size index is 14~28; Also can be to intersect the zeolite in duct: as its apertures, first duct such as ZSM-57, AlPO4-18 greater than 3.5
, 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.The general fixed-bed process that adopts.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 fixed-bed process that same this patent provides faces the catalyst carbon deposition inactivation equally, the less stable of catalyzer, and the ethylene, propylene yield is undesirable.
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
4Mol ratio be to react under the 7.26:1 condition.This technology faces the ethylene, propylene yield equally and advances the products distribution instability with the reaction times, needs the problem of frequent regeneration.
Summary of the invention
Technical problem to be solved by this invention is to exist catalyst activity stability requirement height in the technical literature in the past, purpose product ethylene, propylene selectivity is low and yield is low, and adopt the narrower problem of the raw material scope of application, a kind of new propylene enhancing, the method for ethene are provided.It is wide that this method has the raw material scope of application, purpose product ethylene, propylene yield height, and selectivity reaches the high technological merit of operation continous-stable well.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: with the rich olefins mixture that contains one or more carbon four or above alkene is raw material, in fluidized-bed reactor, is 400~650 ℃ in temperature of reaction, and weight space velocity is 0.8~50 hour
-1Reaction pressure is 0~0.5MPa, the weight ratio of water vapour and rich olefins is under 0.5~5: 1 the condition, and making the rich olefins raw material is that the aperture silicoaluminophosphamolecular molecular sieves catalyzer of 0.3~0.56 nanometer contacts with the aperture in the presence of water vapour, generates the effluent that contains propylene and ethylene.
The rich olefins mixture material of one or more carbon four or above alkene is from carbon four and above cut or alpha-olefin coproduction, MTO (methanol-to-olefins) and the carbon four of MTP (preparing propylene from methanol) by-product and the above olefin fraction thereof of steam cracking device in plant catalytic cracker, the ethylene plant in the technique scheme.Rich olefins mixture preferable range is C
4~C
12Normal olefine.The more preferably operational condition of fluidized-bed reactor: 450~550 ℃ of temperature of reaction, weight space velocity are 1~15 hour
-1, reaction pressure is 0.02~0.15MPa, the weight ratio of water vapour and rich olefins is 0.5~2: 1.Aperture silicoaluminophosphamolecular molecular sieves preferred version is the SAPO-34 molecular sieve catalyst.
Among the present invention because carbon four and above olefins by catalytic cracking propylene enhancing thereof, the process of ethene is a fast response, promptly mainly be subjected to thermodynamic control but not kinetic control, the characteristics of olefin cracking are numerous parallel consecutive reaction coexistences simultaneously, carbon distribution and cracked overall thermal effect are generally endothermic process easily, therefore, the present invention can control the duration of contact of reactant and catalyzer on the one hand flexibly by adopting fluidized-bed reactor, effectively suppress the generation of secondary side reaction, the catalyzer cyclic regeneration in time of simultaneously certain carbon distribution, the product yield that achieves the goal is higher, and products distribution purpose stably.Solid acid catalyst is selected from the SAPO-34 molecular sieve catalyst, mainly considers its ideal pore passage structure and good hydrothermal stability, finally reaches the purpose of maximization propene yield and operation steady in a long-term.
The present invention is a catalyzer with the SAPO-34 molecular sieve, uses fluidized-bed reactor, and in operational condition: temperature of reaction is 400~650 ℃, and weight space velocity is 0.1~50 hour
-1, reaction pressure is 0~0.5MPa, water vapour and the weight ratio that is rich in alkene are under 0~5: 1 the condition, carbon four and above alkene thereof to be carried out catalytic cracking for producing propylene using, ethene, make the total recovery of propylene and ethene can reach 50%, have obtained better technical effect.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
With the mixed c 4 that derives from FCC is that raw material (component distributes and sees Table 1) is investigated SAPO-34 molecular sieve hydrocarbon catalytic cracking performance.
Preparation of Catalyst: with 12.4 gram γ-Al
2O
3Mix formation solution a with 31.0 gram deionized waters; 23.7 gram ortho-phosphoric acid (85% quality) and 37.5 gram deionized waters mix and form solution b; A and b mixing back are formed homogeneous jelly c 27 ℃ of stirrings after 4 hours.Keep whipped state, in c, add silicon sol 9.0 grams successively, 18.0 gram triethylamines and 24.4 gram deionized waters.Fully stir the back and form crystallization mixture d, 210 ℃ of following crystallization 50 hours, product obtained solid phase prod after centrifugation with d liquid.With solid phase prod in baking oven 110 ℃ the oven dry 18 hours, test shows, products obtained therefrom is the SAPO-34 molecular sieve, relative crystallinity is 72%, crystal particle diameter is 10.6 microns, specific surface area is 370.1 meters
2/ gram, the aperture is 0.34 nanometer.This sample obtains the catalyzer of requirement of experiment after moulding.
With 30 grams as stated above the catalyzer of preparation pack in the small-sized fluidized bed reactor.Be warming up to 350 ℃, and with steam activation 1 hour, be warming up to 530 ℃ of temperature of reaction then, the weight space velocity of material carbon four hydrocarbon is 2 hours
-1Reaching water and material carbon four hydrocarbon weight ratios is 1.5: 1, and reaction pressure is under the condition of 0.045MPa, sampling analysis after 2 minutes reaction times.Reaction result is 12.34% for the weight ethylene yield, and the propylene weight yield is 26.95%, and the total olefin transformation efficiency is 70.86%.
Table 1 derives from the mixed C of FCC
4Weight percent form
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 2~6]
According to each step and the operational condition of embodiment 1, just change: raw material is pure 1-butylene charging, and catalyzer still is the SAPO-34 molecular sieve catalyst, and the aperture is 0.34 nanometer.Differential responses condition and the results are shown in Table 2:
Table 2 different condition analytical results
Temperature of reaction [℃] | 400.0 | 450.0 | 500.0 | 560.0 | 610.0 |
Reaction pressure (MPa) | 0.015 | 0.082 | 0.1 | 0.3 | 0.05 |
Weight space velocity [hour -1] | 14.7 | 6.53 | 8.7 | 6.5 | 1.21 |
Water: raw material hydrocarbon (weight ratio) | 0.5 | 1.314 | 1.314 | 2.614 | 1.41 |
C4 =Transformation efficiency % | 69.818 | 61.689 | 58.193 | 72.338 | 67.515 |
Yield of ethene % | 4.218 | 7.784 | 11.393 | 13.064 | 14.755 |
Propene yield % | 21.939 | 22.171 | 25.543 | 27.784 | 28.198 |
(E+P) yield % | 26.157 | 29.955 | 36.936 | 40.848 | 42.953 |
[embodiment 7]
According to each step and the operational condition of embodiment 1, just change: with carbon eight monoolefine mixtures is raw material, and 30 gram SAPO-34 molecular sieve catalysts are packed in the small fixed flowing bed reactor.Be warming up to 350 ℃, and with steam activation 1 hour, be warming up to 550 ℃ of temperature of reaction then, the weight space velocity of material carbon eight hydrocarbon is 3.5 hours
-1, water and material carbon eight hydrocarbon weight ratios are 0.6: 1.After 2 minutes reaction times, sampling analysis the results are shown in Table 3:
Table 3
Project | Weight percent is formed, % | Project | Weight percent is formed, % |
Hydrogen | 0.299 | Iso-butylene | 0.850 |
Methane | 0.543 | Suitable-2-butylene | 10.568 |
Ethane | 0.384 | Pentane | 0.344 |
Ethene | 13.272 | Iso-pentane | 0.755 |
Propane | 6.190 | Skellysolve A | 0.398 |
Propylene | 27.163 | Methylacetylene | 0.173 |
Trimethylmethane | 0.181 | Amylene and isohexane | 6.955 |
Normal butane | 1.694 | Normal hexane | 5.462 |
Instead-2-butylene | 14.267 | Carbon is more than six | 1.890 |
Butene-1 | 8.612 |
Yield of ethene is 13.27%, and the yield of propylene is 27.16%, and the yield of ethene+propylene is 40.43%, and conversion of raw material is 75.63%.
[embodiment 8]
Adopt C in the methanol decomposition producing light olefins by product
4To C
7Monoolefine is a raw material, investigates the cracking performance of catalyzer.
Each step and operational condition according to embodiment 1 just change the catalytic pyrolysis raw material, and cracking stock 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.
30 grams are prepared catalyzer as stated above packs in the small fixed flowing bed reactor.Be warming up to 350 ℃, and with steam activation 2 hours, be warming up to 530 ℃ of temperature of reaction then, the weight space velocity of raw material hydrocarbon is 5.70 hours
-1, water and raw material hydrocarbon weight ratio are 3: 1, reaction pressure is 0.05MPa, sampling analysis after 2 minutes reaction times.Reaction result is 11.98% for the weight ethylene yield, and the propylene weight yield is 31.57%, and the total olefin transformation efficiency is 70.85%.
[embodiment 9]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is the SAPO-14 molecular sieve, and the aperture is 0.40 nanometer.With the mixed c 4 that derives from FCC is raw material (component distributes and sees Table 1), and temperature of reaction is 530 ℃, and weight space velocity is 2.7 hours
-1, water and material carbon four hydrocarbon weight ratios are 1.8: 1, reaction pressure is 0.22MPa, sampling analysis during 2 minutes reaction times.Its reaction result: yield of ethene is 10.37%, and propene yield is 25.81%, and the C 4 olefin transformation efficiency is 73.7%.
[embodiment 10]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is the SAPO-26 molecular sieve, and the aperture is 0.43 nanometer.With the mixed c 4 that derives from FCC is raw material (component distributes and sees Table 1), and temperature of reaction is 500 ℃, and weight space velocity is 0.8 hour
-1, water and material carbon four hydrocarbon weight ratios are 2.7: 1, reaction pressure is 0.45MPa, sampling analysis during 2 minutes reaction times.Its reaction result: yield of ethene is 8.93%, and propene yield is 20.15%, and the C 4 olefin transformation efficiency is 75.34%.
[embodiment 11]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is the SAPO-34 molecular sieve, and the aperture is 0.34 nanometer.To mix carbon five is raw material, and temperature of reaction is 580 ℃, and weight space velocity is 2.1 hours
-1, water and material carbon five hydrocarbon weight ratios are 1.8: 1, reaction pressure is 0.02MPa, sampling analysis during 2 minutes reaction times.Its reaction result: yield of ethene is 15.15%, and propene yield is 36.24%, and the C 4 olefin transformation efficiency is 69.73%.
[comparative example 1]
Employing is formed and appreciation condition with the identical catalyzer of embodiment 11, identical raw material, and different is to adopt fixed-bed reactor.Its reaction result: yield of ethene is 10.23%, and propene yield is 30.86%, and the C 4 olefin transformation efficiency is 75.53%.
Claims (5)
1, the production method of a kind of propylene enhancing, ethene is a raw material with the rich olefins mixture that contains one or more carbon four or above alkene, in fluidized-bed reactor, is 400~650 ℃ in temperature of reaction, and weight space velocity is 0.8~50 hour
-1Reaction pressure is 0~0.5MPa, the weight ratio of water vapour and rich olefins is under 0.5~5: 1 the condition, and making the rich olefins raw material is that the aperture silicoaluminophosphamolecular molecular sieves catalyzer of 0.3~0.56 nanometer contacts with the aperture in the presence of water vapour, generates the effluent that contains propylene and ethylene.
2,, it is characterized in that carbon four and above cut or the carbon four of alpha-olefin coproduction, MTO and MTP by-product and the above olefin fraction thereof of the rich olefins mixture material of one or more carbon four or above alkene from steam cracking device in plant catalytic cracker, the ethylene plant according to the production method of the described propylene enhancing of claim 1, ethene.
3,, it is characterized in that the rich olefins mixture is C according to the production method of the described propylene enhancing of claim 1, ethene
4~C
12Normal olefine.
4, according to the production method of the described propylene enhancing of claim 1, ethene, it is characterized in that the operational condition of fluidized-bed reactor: 450~550 ℃ of temperature of reaction, weight space velocity are 1~15 hour
-1, reaction pressure is 0.02~0.15MPa, the weight ratio of water vapour and rich olefins is 0.5~2: 1.
5,, it is characterized in that the aperture silicoaluminophosphamolecular molecular sieves is the SAPO-34 molecular sieve catalyst according to the production method of the described propylene enhancing of claim 1, ethene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100288166A CN100491305C (en) | 2005-08-15 | 2005-08-15 | Production method for increasing production of propylene, ethene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100288166A CN100491305C (en) | 2005-08-15 | 2005-08-15 | Production method for increasing production of propylene, ethene |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1915936A CN1915936A (en) | 2007-02-21 |
CN100491305C true CN100491305C (en) | 2009-05-27 |
Family
ID=37737035
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100288166A Active CN100491305C (en) | 2005-08-15 | 2005-08-15 | Production method for increasing production of propylene, ethene |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100491305C (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101705110B (en) * | 2009-10-28 | 2013-11-13 | 中国石油大学(华东) | Method for enhancing propylene production by catalyzing and splitting coking waxy oil and modifying coker naphtha |
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 |
CN112679309B (en) * | 2019-10-18 | 2022-11-04 | 中国石油化工股份有限公司 | Method for producing propylene by olefin disproportionation |
CN114054081B (en) * | 2021-11-08 | 2022-10-21 | 吉林大学 | SAPO-34/SAPO-14 composite molecular sieve, and preparation method and application thereof |
CN114570420B (en) * | 2022-03-30 | 2023-09-08 | 江南大学 | Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof |
-
2005
- 2005-08-15 CN CNB2005100288166A patent/CN100491305C/en active Active
Non-Patent Citations (4)
Title |
---|
C_4烯烃催化转化增产丙烯研究进展. 张昕,王建伟.石油化工,第8卷. 2004 |
C_4烯烃催化转化增产丙烯研究进展. 张昕,王建伟.石油化工,第8卷. 2004 * |
增产丙烯,提高炼化企业盈利能力. 曹湘洪.化工进展,第22卷第9期. 2003 |
增产丙烯,提高炼化企业盈利能力. 曹湘洪.化工进展,第22卷第9期. 2003 * |
Also Published As
Publication number | Publication date |
---|---|
CN1915936A (en) | 2007-02-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101239878B (en) | Method for increasing yield of ethylene and propylene from olefin with four carbon or above | |
CN102320912B (en) | Method for maximizing total ethylene and propylene yield in process of preparing low-carbon olefin by oxygen compound conversion | |
AU608411B2 (en) | Process for preparing normally liquid hydrocarbonaceous products from a hydrocarbon feed containing linear-and branched olefins | |
JP5881856B2 (en) | Catalyst for producing ethylene and propylene from methanol and / or dimethyl ether, its production method and use | |
WO2010061179A1 (en) | Catalytic cracking process of a stream of hydrocarbons for maximization of light olefins | |
CN100491305C (en) | Production method for increasing production of propylene, ethene | |
CN103121892A (en) | Method for producing low-carbon olefin by alkane | |
CN100413827C (en) | Method for producing propylene, ethene in hihg yield | |
CN1915928A (en) | Method for producing propylene continuously in switch mode | |
CN100368355C (en) | Method for raising yield of ethene, propylene | |
CN100413823C (en) | Method of preparing propylene by catalytic cracking | |
CN100398499C (en) | Method for producing propylene by using cracking olefin of carbon four and higher | |
CN101585747B (en) | Method for transforming oxygenates into propylene | |
CN100413826C (en) | Method for producing propylene | |
CN108276238A (en) | The method that F- T synthesis light oil is total to preparing low-carbon olefin by catalytically cracking with methanol | |
CN100430349C (en) | Method for producing propylene from methanol or dimethyl ether | |
CN101165020B (en) | Method for increasing yield of propylene | |
CN100368359C (en) | Production system for increasing production of propylene | |
CN100443454C (en) | Method for raising selectivity of propylene | |
CN103121891B (en) | Method for producing low-carbon olefin | |
CN113620767A (en) | Method and reaction system for producing low-carbon olefin and aromatic hydrocarbon | |
CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
CN100460368C (en) | Production system of propylene | |
CN101165024B (en) | Method for increasing selectivity and yield of propylene | |
CN1259293C (en) | Method for producing propene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |