CN100413827C - Method for producing propylene, ethene in hihg yield - Google Patents

Method for producing propylene, ethene in hihg yield Download PDF

Info

Publication number
CN100413827C
CN100413827C CNB2005100288170A CN200510028817A CN100413827C CN 100413827 C CN100413827 C CN 100413827C CN B2005100288170 A CNB2005100288170 A CN B2005100288170A CN 200510028817 A CN200510028817 A CN 200510028817A CN 100413827 C CN100413827 C CN 100413827C
Authority
CN
China
Prior art keywords
ethene
reaction
propylene
zsm
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
Application number
CNB2005100288170A
Other languages
Chinese (zh)
Other versions
CN1915937A (en
Inventor
谢在库
钟思青
刘俊涛
刘星
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CNB2005100288170A priority Critical patent/CN100413827C/en
Publication of CN1915937A publication Critical patent/CN1915937A/en
Application granted granted Critical
Publication of CN100413827C publication Critical patent/CN100413827C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This invention relates to a method for manufacturing propylene and ethylene with high yields. The method comprises: contacting a mixture of one or more of C4+ alkenes and oxygen-containing organic compounds with solid acid molecular sieve catalyst in a reactor, and reacting to obtain effluent containing propylene and ethylene.The weight ratio of alkenes to oxygen-containing organic compounds is (1-10): 1. The method solves the problems of low selectivity and low yields of propylene and ethylene, and can be used in propylene and ethylene industrial manufacture.

Description

The production method of high yield propylene and ethene
Technical field
The present invention relates to the production method of a kind of high yield propylene, ethene, particularly about the method for carbon four and the high produced in yields propylene and ethylene of above olefins by catalytic cracking thereof.
Background technology
Propylene and ethene are most important basic organic, and in the last few years, because the quick growth of acryloyl derivative demand, the whole world faced the propylene shortage problem, and the demand of ethene also presents and increases progressively trend simultaneously.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, ethene are 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, simultaneously the document is not mentioned and is sneaked into oxygenatedchemicals in the raw material, has problems such as the yield of purpose product propylene, ethene is lower.
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, AlPO 4-11 wait its aperture greater than 3.5
Figure C20051002881700031
, pore size index is 14～28; Also can be the zeolite in intersection duct: as ZSM-57, AlPO 4-18 wait its aperture, first duct greater than 3.5
Figure C20051002881700032
, 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 less stable of same this patent 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 -1, reactor inlet temperatures is 480 ℃, and reactor pressure is 0.2MPa, and the reactor outlet temperature is 440 ℃, pressure 0.19MPa; Thinning ratio water and C 4Mol ratio is condition under to react at 7.26: 1.Obviously import and export the bigger temperature difference and must influence the distribution of product and the yield of purpose product.
Summary of the invention
Technical problem to be solved by this invention is to exist in the technical literature purpose product propylene and ethylene poor selectivity and yield low in the past, and the narrower problem of the raw material scope of application that adopts, and a kind of new high yield propylene and the production method of ethene are provided.This method has purpose product propylene and selectivity of ethylene is good, yield is high technological merit.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the production method of a kind of high yield propylene and ethene, with the rich olefins that contains one or more carbon four or above alkene and the mixture of organic oxygen-containing compound is raw material, raw material contacts in reactor with the solid acid molecular sieve catalyst, reaction generates the effluent that contains propylene and ethene, and wherein the weight ratio of rich olefins and organic oxygen-containing compound is 1～10: 1.
Rich olefins is C in the technique scheme 4～C 12Normal olefine, the organic oxygen-containing compound preferred version is selected from methyl alcohol, dme or its mixture, the weight ratio preferable range of rich olefins and organic oxygen-containing compound is 4～8: 1; Rich olefins more preferably scope is C 4～C 8Normal olefine.Solid acid molecular sieve preferred version is selected from ZSM-5, ZSM-11 or ZSM-42, its silica alumina ratio SiO 2/ Al 2O 3Preferable range is 10～3000; Another preferred version of solid acid molecular sieve is selected from aluminium silicophosphate molecular sieve, its silicon phosphorus al mole ratio Si xP yAl zBe x=0.01～0.98, y=0.01～0.52, z=0.01～0.60, and x+y+z=1; Solid acid molecular sieve more preferably scheme is selected from ZSM-5, its silica alumina ratio SiO 2/ Al 2O 3Be 80～500; The solid acid molecular sieve another more preferably scheme be selected from SAPO-34 and SAPO-11, its silicon phosphorus al mole ratio Si xP yAl zBe x=0.2～0.8, y=0.1～0.4, z=0.1～0.50, and x+y+z=1.Reactor is selected from fixed-bed reactor or fluidized-bed reactor, and its operational condition preferable range is: temperature of reaction is 400～650 ℃, and weight space velocity is 1～70 hour -1, reaction pressure is 0～0.5MPa, uses water as thinner in the reaction, the weight ratio of water vapour and rich olefins is 0.01～5: 1; Operational condition more preferably scope is: temperature of reaction is 450～560 ℃, and weight space velocity is 2～20 hours -1, reaction pressure is 0～0.3MPa, the weight ratio of water vapour and rich olefins is 0.8～3: 1.
Among the present invention because carbon four and above olefin catalytic cracking to produce propylene thereof, ethylene process are fast responses, promptly mainly be subjected to thermodynamic control but not kinetic control, the characteristics of olefin cracking are that numerous parallel consecutive reaction coexistences, easy carbon distribution and cracked overall thermal effect are generally endothermic process simultaneously, therefore, among the present invention a certain amount of organic oxygen-containing compound such as methyl alcohol, dme or its mixture are together entered reactor with hydrocarbon raw material.The yield that methyl alcohol or dme ethene that the one side dehydration forms under reaction conditions and propylene help improving purpose product propylene, ethene, the water of Sheng Chenging can be used as the diluent gas of carbon four and above olefin cracking thereof simultaneously, the carbon bond that the active intermediate that what is more important methyl alcohol or dimethyl ether catalysis cracking generate can activate hydro carbons reduces temperature of reaction, reduces at the supercentral carbon laydown of catalyst acid.By with two effective combinations of reaction, make that pilot process and energy have obtained effective utilization in the reaction process among the present invention, finally reached raising propylene and ethylene yield and purpose optionally, obtained better technical effect.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
1-butylene charging, fixed-bed reactor catalytic cracking reaction result investigate.
According to silica alumina ratio (SiO 2/ Al 2O 3) be that 200 proportional arrangement is siliceous, the slip of aluminium, template (n-Butyl Amine 99) and water, its feed molar proportioning is 200SiO 2: Al 2O 3: 60 n-Butyl Amine 99s: 17OH -: 200NaCl: 6300H 2O at room temperature stirred 15 hours.Crystallization 50 hours under 140 ℃ temperature is then washed crystallization liquid afterwards, is promptly obtained the ZSM-5 molecular sieve after the oven dry, roasting.After ZSM-5 molecular sieve adding 87 gram 40% (weight) silica gel mixing with 50 grams, extrusion moulding, and, make ZSM-5 type catalyzer after 430 ℃ of roastings 130 ℃ of oven dry.
5 these type ZSM 5 molecular sieve catalyzer of gram are packed in the fixed-bed reactor flat-temperature zone into the activation 3 hours under 480 ℃, nitrogen atmosphere of reaction procatalyst.Be 3: 1 at pure 1-butylene and methyl alcohol weight ratio then, water and 1-butylene weight ratio are 1.2: 1,600 ℃ of temperature of reaction, and reaction pressure 0.042MPa, 1-butylene weight space velocity are 62.53 hours -1React its reaction result under the condition: yield of ethene 7.32%, propene yield 26.57%, ethene+propene yield 33.89%, butene conversion is 54.71%.
[embodiment 2]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is the type ZSM 5 molecular sieve catalyzer, silica alumina ratio SiO 2/ Al 2O 3Be 950, pure 1-butylene and methyl alcohol weight ratio are 6: 1, and water and 1-butylene weight ratio are 0.5: 1,500 ℃ of temperature of reaction, and reaction pressure 0.48MPa, 1-butylene weight space velocity are 3.53 hours -1React its reaction result under the condition: yield of ethene 4.32%, propene yield 20.57%, ethene+propene yield 24.89%, butene conversion is 74.71%.
[embodiment 3]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is the type ZSM 5 molecular sieve catalyzer, silica alumina ratio SiO 2/ Al 2O 3Be 500, pure 1-butylene and methyl alcohol weight ratio are 6: 1, and water and 1-butylene weight ratio are 0.5: 1,500 ℃ of temperature of reaction, and reaction pressure 0.48MPa, 1-butylene weight space velocity are 3.53 hours -1React its reaction result under the condition: yield of ethene 4.39%, propene yield 20.63%, ethene+propene yield 25.02%, butene conversion is 75.38%.
[embodiment 4]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is the type ZSM 5 molecular sieve catalyzer, silica alumina ratio SiO 2/ Al 2O 3Be 58, C 8Normal olefine and methyl alcohol weight ratio are 10: 1, water and C 8The normal olefine weight ratio is 0.2: 1,410 ℃ of temperature of reaction, reaction pressure 0.28MPa, C 8The normal olefine weight space velocity is 3.53 hours -1React its reaction result under the condition: yield of ethene 2.31%, propene yield 19.76%, transformation efficiency are 73%.
Table 1 derives from the mixed C of FCC 4Weight percent form
The component title Weight percentage % The component title Weight percentage %
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 5]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is a ZSM-11 type molecular sieve catalyst, silica alumina ratio SiO 2/ Al 2O 3Be 600, pure 1-butylene and methyl alcohol weight ratio are 6: 1, and water and 1-butylene weight ratio are 0.5: 1,580 ℃ of temperature of reaction, and reaction pressure 0.01MPa, 1-butylene weight space velocity are 3.53 hours -1React its reaction result under the condition: yield of ethene 5.21%, propene yield 23.71%, ethene+propene yield 28.92%, butene conversion is 70.14%.
[embodiment 6]
According to each step and the operational condition of embodiment 1, just change: molecular sieve is a ZSM-42 type molecular sieve catalyst, silica alumina ratio SiO 2/ Al 2O 3Be 210, pure 1-butylene and methyl alcohol weight ratio are 6: 1, and water and 1-butylene weight ratio are 0.5: 1,620 ℃ of temperature of reaction, and reaction pressure 0.1MPa, 1-butylene weight space velocity are 4.03 hours -1React its reaction result under the condition: yield of ethene 6.83%, propene yield 25.23%, ethene+propene yield 32.06%, butene conversion is 76.55%.
[embodiment 7～11]
In fluidized-bed reactor, investigate the pyrolysis product distribution that hydrocarbon catalytic cracking is produced ethylene, propylene with various solid acid catalysts.
With the mixed c 4 that derives from FCC is raw material (component distributes and sees Table 1), in fluidized-bed reactor, uses catalyzer ZSM-5, ZSM-11, ZSM-42 respectively, SAPO-11, SAPO-34 (physico-chemical property sees Table 2).
30 gram catalyzer are packed in the small-sized fluidized bed reactor.Be warming up to 400 ℃, and with steam activation 2 hours, be warming up to temperature of reaction then, the weight space velocity of material carbon four hydrocarbon is 2.5 hours -1, reaction pressure is normal pressure, and during 3 minutes reaction times, sampling analysis the results are shown in Table 3:
Table 2 catalyzer ZSM-5, ZSM-11, ZSM-42, SAPO-11, the physical and chemical indexes of SAPO-34
Catalyst type ZSM-5 ZSM-11 ZSM-42 SAPO-11 SAPO-34
Si/Al mol ratio in the catalyzer, or Si/Al/P mol ratio 50 500 280 1∶1.5∶3 1∶3∶1
Particle diameter, micron 30～75 28～72 22～31 40～56 33～76
Density, grams per milliliter 0.59 0.64 0.51 0.67 0.73
Table 3 reaction result
Catalyst type ZSM-5 ZSM-11 ZSM-42 SAPO-11 SAPO-34
Temperature of reaction (℃) 480 500 550 580 620
Water: rich olefins (weight ratio) 0.5 5 2.8 0.75 0.02
Rich olefins: methyl alcohol (weight ratio) 1.2 3.8 9.3 5 0.8
C4 ＝Transformation efficiency % 62.23 69.89 72.93 74.98 76.28
Yield of ethene % 4.54 6.84 8.30 8.84 9.11
Propene yield % 24.65 25.02 24.63 28.91 26.74
(E+P) yield % 29.19 31.86 32.93 37.76 35.85
Annotate: E refers to that ethene, P refer to propylene, and E+P refers to ethene+propylene sum
[embodiment 12]
With carbon eight monoolefine mixtures is raw material, and ZSM-5 (the Si/Al mol ratio is 100) molecular sieve is a catalyzer, and 30 gram catalyzer are packed in the small-sized fluidized bed reactor.Be warming up to 400 ℃, and with steam activation 2 hours, be warming up to 550 ℃ of temperature of reaction then, the mass space velocity of material carbon eight hydrocarbon is 3.5 hours -1, water and raw material hydrocarbon weight ratio are 0.5: 1; Reaction pressure is 0.1MPa, methyl alcohol: dme: raw material ratio is 1: 0.5: 3.During 3 minutes reaction times, the sampling analysis result:
Table 4
Project Mass yield % Project Mass yield %
Hydrogen 0.09 Neopentane 0.20
Methane 0.30 Instead-2-butylene 6.83
Ethane 0.22 Butene-1 4.87
Ethene 8.15 Iso-butylene 10.62
Propane 1.62 Suitable-2-butylene 5.01
Cyclopropane 0.00 Pentane 0.77
Propylene 26.16 Iso-pentane 0.45
Trimethylmethane 5.63 Skellysolve A 0.50
Normal butane 14.99 Methylacetylene 0.10
Normal hexane 0.05 Amylene and isohexane 9.86
Carbon is more than six 3.61
Yield of ethene is 8.15%, propene yield is 26.16%, and ethene+propene yield is 34.31%, and material carbon four transformation efficiencys are 66.82%.
[embodiment 13～14]
With pure 1-butylene and methanol mixed charging, investigate the catalytic pyrolysis products distribution.
With ZSM-5 (the Si/Al mol ratio is 200) molecular sieve is catalyzer, the 30 gram catalyzer of packing on small-sized fluidized bed.Be warming up to 400 ℃, and with steam activation 2 hours, be warming up to temperature of reaction then, the weight space velocity of raw material hydrocarbon is 2.0 hours -1, reaction pressure is 0.03MPa, and water and raw material butylene weight ratio are 1.5: 1, and in 3 minutes following reaction times of condition, sampling analysis the results are shown in Table 5:
Table 5
Temperature of reaction 510℃ 560℃
Raw material hydrocarbon: methyl alcohol (weight ratio) 3∶1 8∶1
Ethylene selectivity % 11.351 13.950
Propylene selectivity % 37.194 40.625
(E+P) selectivity % 48.545 54.575
Yield of ethene % 8.230 10.439
Propene yield % 26.965 30.401
(E+P) yield % 35.195 40.841
[embodiment 15]
With carbon five hydrocarbon mixtures be raw material and add dme and and carbinol mixture, on the small-sized fluidized bed reactor, investigate the catalytic pyrolysis products distribution.
With ZSM-5 (the Si/Al mol ratio is 500) molecular sieve is catalyzer, and 30 gram catalyzer are packed in the small-sized fluidized bed reactor.Be warming up to 400 ℃, and with steam activation 2 hours, be warming up to 500 ℃ of temperature of reaction then, the weight space velocity of material carbon five hydrocarbon is 1.5 hours -1, water and material carbon five hydrocarbon weight ratios are 1.2: 1, and methyl alcohol: dme: raw material hydrocarbon (weight ratio) is 1: 1: 6, and the raw material composition sees Table 6.During 3 minutes reaction times, the sampling analysis result: yield of ethene is 6.03%, propene yield is 20.45%, and ethene+propene yield is 26.48%, and feed stock conversion is 70.25%.
Table 6 mixes carbon Wuyuan material weight percent and forms %
The component title Weight content, % The component title Weight content, wt%
Propane 0.019 Iso-butylene 0.314
Cyclopropane 0.001 Suitable-2-butylene 0.511
Propylene 0.012 Pentane 1.099
Trimethylmethane 0.207 Iso-pentane 40.621
Normal butane 0.859 Skellysolve A 15.356
Propadiene 0.005 1,3-butadiene 0.001
Instead-2-butylene 0.753 Methylacetylene 0.004
Butene-1 1.360 Amylene 38.654
Normal hexane 0.150 More than carbon six reaches 0.075
[comparative example 1～2]
Employing is with the identical experiment condition of embodiment 13～14, and different is not add methyl alcohol, and experimental result sees Table 7.
Table 7
Temperature of reaction 510℃ 560℃
Ethylene selectivity % 11.524 12.728
Yield of ethene % 5.767 9.473
Propene yield % 23.444 27.779
(E+P) yield % 29.210 37.252
As can be seen from the above table, under the same terms, the split product of obstructed methyl alcohol, the yield of its ethene and propylene are lower than the reaction result that feeds methyl alcohol under the same terms.

Claims (7)

1. the production method of one kind high yield propylene and ethene, with the rich olefins that contains one or more carbon four or above alkene and the mixture of organic oxygen-containing compound is raw material, raw material contacts in reactor with the solid acid molecular sieve catalyst, reaction generates the effluent that contains propylene and ethene, and wherein the weight ratio of rich olefins and organic oxygen-containing compound is 1～10: 1.
2. according to the production method of described high yield propylene of claim 1 and ethene, it is characterized in that rich olefins is C 4～C 12Normal olefine, organic oxygen-containing compound is selected from methyl alcohol, dme or its mixture, the weight ratio of rich olefins and organic oxygen-containing compound is 4～8: 1.
3. according to the production method of described high yield propylene of claim 2 and ethene, it is characterized in that rich olefins is C 4～C 8Normal olefine.
4. according to the production method of described high yield propylene of claim 1 and ethene, it is characterized in that the solid acid molecular screening from ZSM-5, ZSM-11 or ZSM-42, its silica alumina ratio SiO 2/ Al 2O 3Be 10～3000 or the solid acid molecular screening from aluminium silicophosphate molecular sieve, its silicon phosphorus al mole ratio SixPyAlz is x=0.01～0.98, y=0.01～0.52, z=0.01～0.60, and x+y+z=1.
5. according to the production method of described high yield propylene of claim 4 and ethene, it is characterized in that the solid acid molecular screening from ZSM-5, its silica alumina ratio SiO 2/ Al 2O 3Be 80～500 or the solid acid molecular screening from SAPO-34 and SAPO-11, its silicon phosphorus al mole ratio SixPyAlz is x=0.2～0.8, y=0.1～0.4, z=0.1～0.50, and x+y+z=1.
6. according to the production method of described high yield propylene of claim 1 and ethene, it is characterized in that reactor is selected from fixed-bed reactor or fluidized-bed reactor, its operational condition is: temperature of reaction is 400～650 ℃, and weight space velocity is 1～70 hour -1, reaction pressure is 0～0.5MPa, uses water as thinner in the reaction, the weight ratio of water vapour and rich olefins is 0.01～5: 1.
7. according to the production method of described high yield propylene of claim 6 and ethene, it is characterized in that reactor is selected from fixed-bed reactor or fluidized-bed reactor, its operational condition is: temperature of reaction is 450～560 ℃, and weight space velocity is 2～20 hours -1, reaction pressure is 0～0.3MPa, the weight ratio of water vapour and rich olefins is 0.8～3: 1.
CNB2005100288170A 2005-08-15 2005-08-15 Method for producing propylene, ethene in hihg yield Active CN100413827C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100288170A CN100413827C (en) 2005-08-15 2005-08-15 Method for producing propylene, ethene in hihg yield

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100288170A CN100413827C (en) 2005-08-15 2005-08-15 Method for producing propylene, ethene in hihg yield

Publications (2)

Publication Number Publication Date
CN1915937A CN1915937A (en) 2007-02-21
CN100413827C true CN100413827C (en) 2008-08-27

Family

ID=37737036

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100288170A Active CN100413827C (en) 2005-08-15 2005-08-15 Method for producing propylene, ethene in hihg yield

Country Status (1)

Country Link
CN (1) CN100413827C (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008029631A1 (en) * 2006-08-30 2008-03-13 Jgc Corporation Propylene production process and propylene production apparatus
JP5020587B2 (en) 2006-09-28 2012-09-05 日揮株式会社 Propylene production method and propylene production apparatus
CN101381272B (en) * 2007-09-06 2012-05-30 中国石油化工股份有限公司 Method for preparing ethylene and propylene by two-step method
CN101381271B (en) * 2007-09-06 2012-10-24 中国石油化工股份有限公司 Method for preparing ethylene and propylene by means of copyrolysis
CN103922882B (en) * 2014-04-02 2016-01-06 黄河三角洲京博化工研究院有限公司 A kind of method improving Propylene Selectivity in MTP reaction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6049017A (en) * 1998-04-13 2000-04-11 Uop Llc Enhanced light olefin production
CN1065853C (en) * 1996-05-24 2001-05-16 中国科学院大连化学物理研究所 Preparation of ethylene, propylene and other low-carton olefine from methyl alcohol or dimethyl ether
CN1592727A (en) * 2001-07-02 2005-03-09 埃克森美孚化学专利公司 Inhibiting catalyst coke formation in the manufacture of an olefin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065853C (en) * 1996-05-24 2001-05-16 中国科学院大连化学物理研究所 Preparation of ethylene, propylene and other low-carton olefine from methyl alcohol or dimethyl ether
US6049017A (en) * 1998-04-13 2000-04-11 Uop Llc Enhanced light olefin production
CN1592727A (en) * 2001-07-02 2005-03-09 埃克森美孚化学专利公司 Inhibiting catalyst coke formation in the manufacture of an olefin

Also Published As

Publication number Publication date
CN1915937A (en) 2007-02-21

Similar Documents

Publication Publication Date Title
CN102320912B (en) Method for maximizing total ethylene and propylene yield in process of preparing low-carbon olefin by oxygen compound conversion
CN101239878B (en) Method for increasing yield of ethylene and propylene from olefin with four carbon or above
JP2007051143A (en) Method for producing lower olefin by using multiple reaction zone
CN101367701B (en) Method for converting oxygen-containing compound into propylene with moving bed technique
KR20110026709A (en) Shaped zeolite catalysts for olefin cracking reaction and process for producing light olefins from synthesis gas
CN100413827C (en) Method for producing propylene, ethene in hihg yield
CN100567460C (en) Utilize catalyzing and cracking light-hydrocarbon material to prepare the method and the device of low-carbon alkene
CN100368355C (en) Method for raising yield of ethene, propylene
CN100413826C (en) Method for producing propylene
CN100398499C (en) Method for producing propylene by using cracking olefin of carbon four and higher
CN100491305C (en) Production method for increasing production of propylene, ethene
CN101381272B (en) Method for preparing ethylene and propylene by two-step method
CN100430349C (en) Method for producing propylene from methanol or dimethyl ether
CN101239872B (en) Method for increasing selectivity of low-carbon olefins
CN101585747B (en) Method for transforming oxygenates into propylene
CN100413823C (en) Method of preparing propylene by catalytic cracking
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
CN100460368C (en) Production system of propylene
CN102190549B (en) Method for producing propylene
CN101165024B (en) Method for increasing selectivity and yield of propylene
CN101239879B (en) Method for producing propylene
CN102190539B (en) Method for increasing propylene yield
CN100586908C (en) Production method for propylene

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