CN101367699B - Preparation of propylene - Google Patents
Preparation of propylene Download PDFInfo
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- CN101367699B CN101367699B CN2007101766041A CN200710176604A CN101367699B CN 101367699 B CN101367699 B CN 101367699B CN 2007101766041 A CN2007101766041 A CN 2007101766041A CN 200710176604 A CN200710176604 A CN 200710176604A CN 101367699 B CN101367699 B CN 101367699B
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 171
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 55
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 21
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 39
- 239000002808 molecular sieve Substances 0.000 claims description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002796 Si–Al Inorganic materials 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- -1 olefin hydrocarbon Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 235000012976 tarts Nutrition 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 description 36
- 150000001336 alkenes Chemical class 0.000 description 31
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000002152 alkylating effect Effects 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000007233 catalytic pyrolysis Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing propylene is characterized in that at least two reaction areas are mounted. The method comprises: (a) in the first reaction area, the hydrocarbon with a carbon number not less than 4 gives a catalytic cracking reaction on solid acid catalyst and transforms to hydrocarbon production which includes ethylene and the propylene; (b) in the second reaction area, methanol (and or dimethyl ether) and gas including the ethylene reacts on the solid acid catalyst and transforms to the product with the propylene and the hydrocarbon with higher carbon number; (c) in the product of the first reaction area, at least one part of the ethylene serves as the raw material of the second reaction area; in the product of the second reaction area, at least one part of the hydrocarbon with the carbon number not less than 4 serves as the raw material of the first reaction area.
Description
Technical field
The present invention relates to a kind of method of producing propylene.
Background technology
Propylene is a kind of important petrochemical complex basic raw material.For a long time, the propylene source depends on ethylene cracker and FCC apparatus.Because the propylene rate of increase continues to be higher than the ethene rate of increase, people update traditional production of propylene technology, further improve productivity of propylene.Propylene enhancing receives the restriction of raw material composition, apparatus processes ability, plant modification and process cost on existing apparatus, and the technological process of therefore developing new propylene enhancing is to satisfy the important directions of growing propylene demand.In recent years; People have developed the employing different material and have produced the propylene novel process, like preparing propylene by dehydrogenating propane, ethene and butene inverse disproportionation system propylene, number of carbons hydro carbons cracking producing light olefins, methanol-to-olefins (MTO), preparing propylene from methanol (MTP), ethene and the co-fed system propylene of alkylating reagent etc.
With number of carbons alkene, particularly to contain number of carbons olefin feed (like FCC gasoline and hybrid C 4 etc.) than polyene hydrocarbon be raw material, to be converted into the propylene through catalytic pyrolysis be master's low-carbon alkene, is the new process that receives extensive attention in recent years, has some commercial potential.The advantage of this conversion process is, available materials kind source is abundant, is worth low, propylene/ethylene ratio height in product, whole process has better economic property.Existing multinomial patent has been announced and has been adopted the number of carbons olefin catalytic to transform the method for producing propylene.
U.S.Patent 6,222, and 087 B1 has announced that a kind of feedstock conversion that will contain C4-C7 alkene and alkane is the method for low-carbon alkene, catalyzer be the ZSM-5 of P modification or/and the ZSM-11 molecular sieve, the silica alumina ratio of molecular sieve is greater than 300.Adopt the dense, fluidized bed process, reaction conditions be temperature at 510-704 ℃, between the 8bar, WHSV is at 1-20hr in negative pressure for reaction pressure
-1Between.Yield of light olefins is higher than 20%, reaches as high as more than 30%, and the propylene/ethylene ratio can reach more than 3.0
EP 0109059 has announced that one is the method for propylene with the C4-C12 conversion of olefines.The catalyzer that adopts be silica alumina ratio be less than or equal to 300 ZSM-5 or and the ZSM-11 molecular sieve, WHSV is greater than 50hr
-1, temperature of reaction is 400-600 ℃.The total recovery of ethene and propylene is 36-44%, and wherein the yield of propylene is 30-40%.
U.S.Patent 5,171, and 921 have announced with EP0511013 A3 and a kind of number of carbons hydrocarbon mixture (containing alkene and alkane) to be converted into the technology of low-carbon alkene, and temperature of reaction is 500-700 ℃, and WHSV is at 10-1000hr
-1Between, contain the ZSM-5 that silica alumina ratio is 20-60 in the catalyzer, and through P modification and water vapour burin-in process.
U.S.Patent 5,981, and 819 have announced that a kind of material that will contain C4-C7 alkene is converted into the technology of propylene.Reaction mass and water vapor are mixed into fixed-bed reactor and sieve catalyst contact reacts, and feed water/oil ratio is 0.5: 1-3: 1, and temperature of reaction is 380-500 ℃.The Si/Al atomic ratio of molecular sieve is 10-200.Alkene is converted into propylene and butylene in the raw material more than 60%.WO 01/05909A1 discloses technology similar to the above process, and the material that will contain C4-C8 alkene is converted into low-carbon alkene.
US Patent 2003/0139636 A1 discloses and a kind ofly will contain the method that olefin feed is converted into propylene.The catalyzer that adopts is rare earth or metal-modified SAPO, MeAPO, MeASPO, ELAPO and ELASPO.
CN 1600757 discloses and has a kind ofly produced the particularly method of propylene of light olefin by the hydrocarbon feed that contains C4-C6 alkene; This method contacts the silica alumina ratio of olefin feedstock and modification greater than 30 ZSM-5/ZSM-11 zeolite catalyst; Flow out thing to produce light olefin, the selectivity of light olefin is more than 60%, and yield is 40-55%; Reaction conditions is temperature 500-650 ℃, weight space velocity 1-50, pressure 0.1-8atm.
CN 1490288 discloses the method for a kind of C4 and above olefin catalytic cracking to produce propylene, and the selectivity that mainly solves propylene in the purpose product that exists in the technology in the past is low, yield is low, the problem of poor catalyst stability.The catalyzer that adopts is that silica alumina ratio is the ZSM-5 of 50-1000, and in the crystallization process of molecular sieve, adds a certain amount of halogen sodium salt.Reaction conditions is temperature 400-600 ℃, liquid air speed 10-50hr-1, pressure 0-0.15MPa.
Another kind has the novel process of the production of propylene of applications well prospect to be, ethene and alkylating reagent (like methyl alcohol or/and dme etc.) is co-fed, and alkylated reaction takes place on catalyzer, generates the hydrocarbon products that comprises propylene.
Discover, alkene can and methyl alcohol between alkylated reaction takes place, make that the carbon number of alkene increases (Svelle etc., J.Catal.224 (2004), 115-123, J.Catal.234 (2005), 385-400):
CH
3OH+C
nH
2n＝C
n+1H
2n+2+H
2O
The alkylated reaction of above type also can be at alkene or/and take place between the alkylating reagents such as dme.Especially, the reaction of ethene and alkylating reagent can generate propylene.Such reaction is that the production of propylene provides a new approach.The advantage of this approach is: a carbon atom that generates propylene comes from relatively cheap methyl alcohol or/and dme, has reduced the cost of production of propylene.If adopt low value ethylene raws such as catalytic pyrolysis dry gas, then the economy of this method can further improve.
U.S. Pat 3906054 discloses a kind of technology of olefin alkylation, and alkene is contacted with catalyzer in the presence of alkylating reagent, and catalyzer is that silica alumina ratio is at least 12 zeolite, adopts the P modification, and P content is minimum to be 0.78%.Can carry out alkylating alkene and comprise ethene, propylene, butene-2 and iso-butylene, the available alkylating reagent is methyl alcohol, dme and methyl chloride.
World patent WO2005/056504 A1 disclose a kind of from ethene and methyl alcohol or/and dme, the method for efficient production propylene generates propylene with ethene and methyl alcohol or/and dme reacts in the presence of catalyzer.It is characterized in that, be less than the ethene amount that in reaction system, adds by effusive ethene amount in the reaction system.Simultaneously, calculate with the mole number of the methyl alcohol that gets into reaction system or 2 times dme mole number, propene yield can reach more than the 40mol%.
One Chinese patent application 200610112555.0 discloses a kind of method of producing propylene; The method is characterized in that: the raw material that contains ethene is in the presence of methylating reagent; Under specific reaction conditions, be that the catalyzer of the molecular sieve of 0.3-0.5nm contacts, generate the product that contains propylene with containing micropore size.The propylene selectivity can reach more than 70% in the product.
Above-mentioned two kinds of methods also generate other by products when generating propylene.The process of number of carbons hydro carbons cracking producing light olefins generates more ethylene by-product thing, and the separation of ethene and purification can only rely on cryogenic unit, relate to huge construction investment, thereby greatly reduce the economy of whole process.Ethene and methyl alcohol produce propylene or/and alkylating reagents such as dme can alkylated reaction take place on an acidic catalyst surface; But; Other multiple reactions also can take place on same catalyzer, as, the product propylene also can generate butylene with the alkylating reagent reaction; Equally, the butylene of generation can further generate C with the alkylating reagent reaction again
5Above hydro carbons; The generation of these number of carbons hydro carbons makes the economy variation of this process.
Summary of the invention
The object of the present invention is to provide a kind of method of producing propylene.
For realizing above-mentioned purpose, the method for producing propylene provided by the invention is characterized in that at least two reaction zones are set, and comprising:
A) at first reaction zone, carbon number is not less than 4 hydro carbons catalytic cracking reaction takes place on solid acid catalyst, is converted into the hydrocarbon product that comprises ethene and propylene;
B) at second reaction zone, methyl alcohol (or/and dme) and the gas that contains ethene react on solid acid catalyst, are converted into to contain the propylene and the product of number of carbons hydro carbons more;
C) in the product of first reaction zone, at least a portion ethene is as the raw material of second reaction zone, and in the product of second reaction zone, at least a portion carbon number is not less than 4 the hydro carbons raw material as first reaction zone;
Wherein the reaction conditions of first reaction zone is: temperature of reaction is 350-750 ℃, and temperature of reaction is 400-700 ℃ preferably, and reaction pressure is 0.01-0.8MPa, and reaction pressure is 0.1-0.45MPa preferably;
Wherein the reaction conditions of second reaction zone is: temperature of reaction is 300-600 ℃; Temperature of reaction is 350-550 ℃ preferably; Reaction pressure is 0.01-0.8MPa; Low good reaction pressure is 0.1-0.45MPa, and the dme mol ratio of ethene/methyl alcohol or ethene/2 times is 0.05-5, and mol ratio is 0.1-5 preferably.
Described method; Wherein, Solid acid catalyst at least aly has tart Si-Al molecular sieve or aluminium silicophosphate molecular sieve for containing, or meets the element modified product that obtain of above-mentioned characteristic molecular sieve beyond the skeleton component, or the multiple mixture that meets the molecular sieve of above-mentioned characteristic.
Described method, wherein, the molecular sieve content of solid acid catalyst is 10 weight %-90 weight %.
Described method, wherein, solid acid catalyst adopts and comprises one or more molding bondeds in silicon oxide, aluminum oxide or the clay adhesive.
Described method, wherein, the reactor types of first reaction zone and second reaction zone all adopts fluidized-bed.
Described method, wherein, it is liquefied gas, petroleum naphtha, gasoline, white oil, solar oil, hydrogenation tail oil or kerosene that carbon number is not less than 4 hydro carbons, or carbon number is not less than 4 hydrocarbon product in the conversion process of claim 1.
Described method, the gas that wherein contains ethene in second reaction zone is for from the product that contains ethene in the ethene of processes such as hydrocarbon cracking, ethane dehydrogenation or methanol conversion system alkene generation or the conversion process from the mixture of the ethene of said process and C1-C3 hydro carbons or oxycarbide or claim 1.
Described method, wherein, the first reaction zone carbon number be not less than 4 hydro carbons or/and the ethene of second reaction zone respectively or all from the product in the conversion process of claim 1.
Embodiment
According to the present invention; To be two different conversion processes of purpose product with the propylene, promptly the co-fed system propylene of number of carbons hydro carbons preparing propylene by catalytic cracking and ethene and methyl alcohol (or/and dme) combines; At least a portion is as the raw material of another process in the by product that each process is obtained; Make full use of the by product that obtains in these two processes, improved utilization ratio of raw materials, final highly selective obtains propylene product.The advantage of this method also is, two processes can shared some equipment, for example; Though the reaction conversion process can be carried out in different reactor drums or reaction zone; But product separates and can in same set of separation system, carry out, and simultaneously, the most of ethene that produces in the process further is converted into propylene; The productive rate of ethene is very low in the final product, can not reclaim refining, need not to build cryogenic separation device.Can reduce investment outlay, cut down the consumption of energy, improve the economy of whole process so greatly.
According to the present invention, at least two reaction zones are set, comprising: a) at first reaction zone, carbon number is not less than 4 hydro carbons catalytic cracking reaction takes place on solid acid catalyst, is converted into the hydrocarbon product that comprises ethene and propylene; B) at second reaction zone, methyl alcohol (or/and dme) and the gas that contains ethene react on solid acid catalyst, are converted into to contain the propylene and the product of number of carbons hydro carbons more; C) in the product of first reaction zone, at least a portion ethene is as the raw material of second reaction zone, and in the product of second reaction zone, at least a portion carbon number is not less than 4 the hydro carbons raw material as first reaction zone.
In described method; Catalyzer contains at least a have tart Si-Al molecular sieve or aluminium silicophosphate molecular sieve; Or meet the element modified product that obtain of above-mentioned characteristic molecular sieve beyond the skeleton component, or the multiple mixture that meets the molecular sieve of above-mentioned characteristic.
In described method, the molecular sieve content of catalyzer can be 10 weight %-90 weight %.
In described method, catalyzer can adopt one or more molding bondeds in the tackiness agents such as comprising silicon oxide, aluminum oxide or clay.
In described method, the reactor types of first reaction zone and second reaction zone all can adopt fluidized-bed.
In described method, the first reaction zone carbon number is not less than 4 hydro carbons can be liquefied gas, petroleum naphtha, gasoline, white oil, solar oil, hydrogenation tail oil or kerosene, or carbon number is not less than 4 hydrocarbon product in the conversion process of the present invention.
In described method, the gas that contains ethene in second reaction zone can be for the ethene that produces from processes such as hydrocarbon cracking, ethane dehydrogenation or methanol conversion system alkene or from the product that contains ethene in the mixture of the ethene of said process and C1-C3 hydro carbons or oxycarbide or the conversion process of the present invention.
In described method, the first reaction zone carbon number be not less than 4 hydro carbons or/and the ethene of second reaction zone respectively or all from the product in the conversion process of the present invention.
In described method, the reaction conditions of first reaction zone can for: temperature of reaction is that temperature of reaction is 350-750 ℃, is preferably 400-700 ℃, and reaction pressure is 0.01-0.8MPa, is preferably 0.1-0.45MPa.
In described method, the reaction conditions of second reaction zone can for: temperature of reaction is 300-600 ℃, is preferably 350-550 ℃; Reaction pressure is 0.01-0.8MPa; Be preferably 0.1-0.45MPa, ethene/methyl alcohol (or dme of 2 times) mol ratio is 0.05-10, is preferably 0.1-5;
Below through embodiment the present invention is made detailed description, but the present invention is not limited to these embodiment.
Embodiment 1
Catalyst A: adopt ZSM-5 molecular sieve (Fushun Petrochemical Company catalyst plant); Mixing to be incorporated in being dispersed into slurry in the water with clay, aluminium colloidal sol and silicon sol (all available from Zhejiang Province Yuda Chemical Co., Ltd), is the microballoon of 20-100 micron for size distribution behind the spray shaping.Above-mentioned microballoon heated 10 hours down and under the steam atmosphere at 800 ℃ through 600 ℃ of roastings 4 hours then, was catalyst A.ZSM-5 content is 30 weight % in the catalyzer.
The butylene catalytic cracking reaction carries out in miniature fluidized bed reaction.Reaction conditions is following: loaded catalyst is 10g, and temperature of reaction is 600 ℃, and raw material adopts Fushun Petrochemical Company butene-2 (purity 98%, suitable, anti-butene-2 respectively accounts for 50 weight %), charging air speed 1.0hr
-1, reaction pressure is 0.1MPa, adopts water vapour to be the reaction carrier gas, the charge proportion of water and butene-2 is 1.5: 1.Reaction product adopts Varian CP-3800 gc, Plot post and hydrogen flame detector analysis, and sampling time point is 6 minutes.
The result is as shown in table 1 for the butylene scission reaction.Under above-mentioned reaction conditions, butene conversion is 79.9%, and the selectivity of propylene is 34.72 weight % in the product.
The reaction result of butylene catalytic pyrolysis among table 1: the embodiment 1
| Yield/weight % | Ethene 22.46 | Propylene 34.72 | C1-C3 alkane 8.48 | CH 4 2.5 | C 5 6.04 | C 6 + 8.2 |
| Transformation efficiency (%) | 79.9 | |||||
Embodiment 2
Catalyst B: adopting SAPO-34 molecular sieve (Dalian Chemical Physics Research Institute) to mix to be incorporated in clay, aluminium colloidal sol and silicon sol (all available from Zhejiang Province Yuda Chemical Co., Ltd) and be dispersed into slurry in the water, is the microballoon of 20-100 micron for size distribution behind the spray shaping.Above-mentioned microballoon is catalyst B through 600 ℃ of roastings 4 hours.SAPO-34 content is 30 weight % in the catalyzer.
Co-fed being reflected in the miniature fluidized bed reaction of ethene and methyl alcohol carried out.Reaction conditions is following: loaded catalyst is 10g, and temperature of reaction is 400 ℃, and raw material adopts methyl alcohol (analytical pure, the federal chemical reagent work in Shenyang) and ethene (purity 99.5%, bright special gas institute of the Ministry of Chemical Industry) mixture.Raw material consists of ethene: methyl alcohol=0.52: 0.48 (carbon number ratio), the charging air speed is counted 1.0hr with methyl alcohol
-1, reaction pressure is 0.1MPa.Reaction product adopts Varian CP-3800 gc, Plot post and hydrogen flame detector analysis, and sampling time point is 6 minutes.
The co-fed reaction result of ethene and methyl alcohol is as shown in table 2.Under above-mentioned reaction conditions, conversion of ethylene is 33.98%, and methanol conversion is 100%, and the yield of propylene is 61.75% (C counts %, in methyl alcohol) in the product.
The co-fed reaction result of ethene and methyl alcohol among table 2: the embodiment 2
| Yield (C counts %, in methyl alcohol) | ?CH 4?0.62 | ?C 2H 6?1.33 | ?C 3H 6?61.75 | ?C 3H 8?11.32 | ?C 4?41.23 | ?C 5?14.02 | C 6 + 6.73 |
| Conversion of ethylene (%) methanol conversion (%) | ?33.98?100 | ||||||
Embodiment 3:
Employing methyl alcohol or dme and carbon number are that the mixed olefins of 4-5 is the scheme of raw material system propylene, and its device form is designed to two reaction zones and all adopts fluidized-bed-regenerator system, adopts catalyst A and catalyst B respectively.The differential responses district product can adopt same separation system to separate.Duration of contact and embodiment 1 and 2 basically identicals in each reaction zone, so its feed stock conversion and selectivity of product calculate according to embodiment 1 and 2, and ignore coke yield.
At first reaction zone; Flow is that 80 tons/hour carbon number is that the mixed olefin feedstock (29.6 tons of/hour products from second reaction zone wherein, 20.8 tons/hour is extra additional raw material for use unconverted raw material and this reaction zone carbon number through partitioning cycle as the product of 4-5,29.6 tons/hour) of 4-5 contacts with catalyst A.Temperature of reaction is 600 ℃, charging air speed 0.3-0.5hr
-1, reaction pressure is 0.25MPa, adopts water vapour to be the reaction carrier gas, water and material feeding ratio are 1.5: 1.Flow out the propylene that obtains 27.8 tons/hour after the feed separation of this reaction zone, 18 tons/hour ethene, 6.8 tons/hour C1-C3 alkane, and hydro carbons (comprising that unconverted raw material and the carbon number that this reaction zone generates are the hydro carbons of 4-5) and 6.6 tons of carbon numbers that 20.8 tons of/hour carbon numbers are 4-5 are not less than 6 hydrocarbon products.Therein ethylene all gets into second reaction zone, and carbon number is that the hydro carbons of 4-5 all turns back in the raw material of this reaction zone.
At second reaction zone, flow is that 52 tons/hour ethene (wherein 34 tons/hour for the unconverted raw material that uses through partitioning cycle, 18 tons/hour from first reaction zone) contacts with catalyst B with 110 tons of/hour methyl alcohol (or 79 tons of/hour dme) jointly.Temperature of reaction is 400 ℃, and the charging air speed is counted 0.6-0.9hr with dme
-1, reaction pressure is 0.25MPa.Flow out the propylene that obtains 30 tons/hour after the feed separation of this reaction zone, 34 tons/hour unconverted raw material ethene, 6.4 tons/hour C1-C3 alkane, and 29.6 tons of/hour carbon numbers are not less than 4 hydro carbons (being mainly the hydro carbons that carbon number is 4-5).Therein ethylene all turns back in the raw material of this reaction zone, and carbon number is not less than 4 whole first reaction zones that get into of hydro carbons.
It is following to install whole material balance: the hydro carbons that 29.6 tons of/hour carbon numbers of inflow device are 4-5 and 110 tons of/hour methyl alcohol (or 79 tons of/hour dme), 57.8 tons of/hour propylene of bleeder, 6.6 tons of/hour carbon numbers are not less than hydro carbons and 13.2 tons of/hour C1-C3 alkane of 6.The whole process propene yield is 74.5 carbon number %.
Comparative Examples 1
Carbon number is that the mixed olefins of 4-5 is the scheme of raw material system propylene, and its device form is designed to fluidized-bed-regenerator system, adopts catalyst A.Duration of contact and embodiment 1 basically identical in reaction zone, so its feed stock conversion and selectivity of product be according to embodiment 1, and ignore coke yield.
Flow is that 100 tons/hour carbon number is that the mixed olefin feedstock (wherein 26 tons/hour is extra additional raw material for use unconverted raw material and carbon number through partitioning cycle as the product of 4-5,74 tons/hour) of 4-5 contacts with catalyzer.Temperature of reaction is 600 ℃, charging air speed 0.3-0.5hr
-1, reaction pressure is 0.25MPa, adopts water vapour to be the reaction carrier gas, water and material feeding ratio are 1.5: 1.Flow out the propylene that obtains 34.8 tons/hour after the feed separation of this reaction zone, 22.5 tons/hour ethene, 8.5 tons/hour C1-C3 alkane, and hydro carbons (comprising that unconverted raw material and the carbon number that this reaction zone generates are the hydro carbons of 4-5) and 8.2 tons of carbon numbers that 26 tons of/hour carbon numbers are 4-5 are not less than 6 hydrocarbon products.Wherein carbon number is that the hydro carbons of 4-5 all turns back in the raw material.
It is following to install whole material balance: the alkene that 74 tons of/hour carbon numbers of inflow device are 4-5, and the propylene that bleeder is 34.8 tons/hour, 22.5 tons/hour ethene, 8.5 tons/hour C1-C3 alkane, and 8.2 tons of carbon numbers are not less than 6 hydrocarbon products.The whole process propene yield is 47 carbon number %.
Claims (10)
1. a method of producing propylene is characterized in that at least two reaction zones are set, and comprising:
A) at first reaction zone, carbon number is not less than 4 hydro carbons catalytic cracking reaction takes place on solid acid catalyst, is converted into the hydrocarbon product that comprises ethene and propylene;
B) at second reaction zone, methyl alcohol is converted into and contains the propylene and the product of number of carbons hydro carbons more or/and dme reacts on solid acid catalyst with the gas that contains ethene;
C) in the product of first reaction zone, at least a portion ethene is as the raw material of second reaction zone, and in the product of second reaction zone, at least a portion carbon number is not less than 4 the hydro carbons raw material as first reaction zone;
Wherein the reaction conditions of first reaction zone is: temperature of reaction is 350-750 ℃, and reaction pressure is 0.01-0.8MPa;
Wherein the reaction conditions of second reaction zone is: temperature of reaction is 300-600 ℃, and reaction pressure is 0.01-0.8MPa, and the dme mol ratio of ethene/methyl alcohol or ethene/2 times is 0.05-5.
2. the described method of claim 1; Wherein, Solid acid catalyst is for containing at least a have tart Si-Al molecular sieve or aluminium silicophosphate molecular sieve; Or meet the element modified product that obtain of above-mentioned characteristic molecular sieve beyond the skeleton component, or the multiple mixture that meets the molecular sieve of above-mentioned characteristic.
3. the described method of claim 2, wherein, the molecular sieve content of solid acid catalyst is 10 weight %-90 weight %.
4. the described method of claim 1, wherein, solid acid catalyst adopts and comprises one or more molding bondeds in silicon oxide, aluminum oxide or the clay adhesive.
5. the described method of claim 1, wherein, the reactor types of first reaction zone and second reaction zone all adopts fluidized-bed.
6. the described method of claim 1, wherein, it is liquefied gas, petroleum naphtha, gasoline, white oil, solar oil, hydrogenation tail oil or kerosene that carbon number is not less than 4 hydro carbons, or carbon number is not less than 4 hydrocarbon product in the conversion process of claim 1.
7. the described method of claim 1, the gas that wherein contains ethene in second reaction zone is for from the product that contains ethene in the ethene of hydrocarbon cracking, ethane dehydrogenation or the generation of methanol conversion system olefin hydrocarbon or the conversion process from the mixture of the ethene of said process and C1-C3 hydro carbons or oxycarbide or claim 1.
8. the described method of claim 1, wherein, the first reaction zone carbon number be not less than 4 hydro carbons or/and the ethene of second reaction zone respectively or all from the product in the conversion process of claim 1.
9. the described method of claim 1, wherein, the reaction conditions of first reaction zone is: temperature of reaction is 400-700 ℃, reaction pressure is 0.1-0.45MPa.
10. the described method of claim 1, wherein, the reaction conditions of second reaction zone is: temperature of reaction is 350-550 ℃, and reaction pressure is 0.1-0.45MPa, and the dme mol ratio of ethene/methyl alcohol or ethene/2 times is 0.1-5.
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| CN102875297B (en) * | 2011-07-12 | 2015-09-09 | 中国石油化工股份有限公司 | The method of low-carbon alkene is prepared with methyl alcohol and petroleum naphtha |
| CN102875299A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for producing low-carbon olefins by using methanol and naphtha |
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| CN114605213B (en) * | 2020-12-09 | 2023-01-31 | 中国科学院大连化学物理研究所 | Method for producing propylene from synthesis gas and dimethyl ether |
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| CN1915934A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing propylene |
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