CN114570420A - Catalytic system for preparing propylene by catalyzing cracking of long-chain olefin and application thereof - Google Patents
Catalytic system for preparing propylene by catalyzing cracking of long-chain olefin and application thereof Download PDFInfo
- Publication number
- CN114570420A CN114570420A CN202210331234.9A CN202210331234A CN114570420A CN 114570420 A CN114570420 A CN 114570420A CN 202210331234 A CN202210331234 A CN 202210331234A CN 114570420 A CN114570420 A CN 114570420A
- Authority
- CN
- China
- Prior art keywords
- catalyst system
- molecular sieve
- sapo
- zeolite molecular
- propylene
- 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.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 56
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 42
- 238000005336 cracking Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010457 zeolite Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 4
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 230000005496 eutectics Effects 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 abstract description 23
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 238000004227 thermal cracking Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CZXDHMZKNAOPHQ-VOTSOKGWSA-N [(5e)-10-propyltrideca-5,9-dienyl] acetate Chemical compound CCCC(CCC)=CCC\C=C\CCCCOC(C)=O CZXDHMZKNAOPHQ-VOTSOKGWSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a catalytic system for preparing propylene by catalyzing cracking of long-chain olefin and application thereof, belonging to the technical field of propylene production. The catalyst system prepared by the invention is composed of a zeolite molecular sieve and an inert material modification layer, wherein the inert material coating layer is one or two of silicon oxide and aluminum oxide, and accounts for 0.01-5 wt% of the weight of the catalyst, and the zeolite molecular sieve is one or more than two of SAPO-5, SAPO-11, SAPO-31 and SAPO-41. The catalyst system for preparing olefin by catalytic cracking of long-chain olefin prepared by the invention has high olefin cracking conversion rate and high propylene selectivity. The catalyst system for preparing olefin by catalytic cracking of long-chain olefin prepared by the invention has very high stability and has wide industrial application prospect.
Description
Technical Field
The invention relates to a catalytic system for preparing propylene by catalyzing cracking of long-chain olefin and application thereof, belonging to the technical field of propylene production.
Background
Propylene is one of important petrochemical basic organic raw materials, and is mainly used for producing chemical products such as polypropylene, acrylonitrile, propylene oxide and the like. Since 2017, its global production has exceeded 100 million tons/year, with the expectation that its demand will exceed 150 million tons/year by 2050. The industrial production process of propylene can be divided into two processes, namely a thermal cracking process and a catalytic cracking process, and a special process for producing propylene. To date, catalytic cracking process technology is the most economical way to produce propylene, with 90% of the propylene worldwide coming from FCC and thermal cracking, with 60% of thermal cracking. The main product of conventional steam cracking is ethylene, while propylene is a by-product. However, with the reduction of ethane costs in the middle east region, shale gas ethane is increasingly used in north america as a feedstock, inhibiting the development of thermal cracking processes, resulting in a continuous decline in propylene production. However, the demand for propylene has increased dramatically due to the rapid development of the downstream propylene industry, and an increase of 56 million tons/year is expected from 2014 to 2030. Thus, the conventional processes have been unable to meet the increasing demand for propylene.
Propylene has a great market potential and many scholars are working on developing propylene production routes, such as: olefin disproportionation, propane dehydrogenation, methanol to propylene, olefin cracking, ethylene to propylene, and the like. These new techniques for the production of propylene are of great importance in meeting the needs of propylene supply. The olefin catalytic cracking process is extremely competitive and accords with the national conditions of China, and is an important way for producing propylene. Although olefins are not present in crude oil and natural gas, the refinery process produces more olefins, such as steam cracking and catalytic cracking. Compared with thermal cracking, the olefin catalytic cracking reaction has lower temperature and higher flexibility, and can be combined by multiple processes to improve the selectivity of propylene. The fixed bed is mostly used as a reactor for the catalytic cracking of the olefin, so that the investment cost is greatly reduced, and the recovery rate is higher. At the same time, the formation of ethylene and butene is accompanied in the course of the reaction.
Currently, several olefin cracking processes are being developed and are in different stages of commercialization, such as the Propylur process by Lurgi, the PCC process by Exxon Mobil, the OCC process by medium petroleum, and the Superflex process and ACO process by KBR. The light olefin is used as raw material, and the traditional catalytic cracking device is modified, so that the yield of the olefin can be improved to the maximum extent. However, the biggest disadvantage of the modified FCC process is that the thermodynamic equilibrium of the plant cannot be broken and the investment cost of the related design due to the multiple processes is not enough. The olefin catalytic cracking reaction is a process for preparing light olefins by cracking olefins at high temperature (450-600 ℃) and low pressure (1-2Bar), and is accompanied with the production of light aromatics and alkanes. The presence of a catalyst during the cracking process may reduce the cracking activation energy. Therefore, the reaction temperature for catalytic cracking of olefins is greatly reduced compared to thermal cracking. Olefin molecules can be activated into carbonium ions on active sites of the catalyst, and then are cracked into smaller olefin molecules, and the cracked products are mainly propylene and butylene. The catalysts currently used in catalytic cracking reactions of olefins are molecular sieves of various types. Wherein, the SAPO-34 molecular sieve can improve the selectivity of propylene, and the pore structure thereof consists of a large cage with the size of 0.67 multiplied by 0.11nm and a small pore (8-MR) with the size of 0.38 multiplied by 0.38nm which are connected, thereby preventing the formation of long-chain or branched-chain hydrocarbon and inhibiting secondary reaction. SAPO-34 suppresses the formation of isobutylene, thereby increasing the yield of ethylene and propylene, as compared to ZSM-5 molecular sieves. However, SAPO-34 molecular sieve has poor stability because the larger aromatic hydrocarbons cannot pass through the small pores of SAPO-34, and carbon deposits are formed to cover the acid sites. Therefore, the development of a catalyst having high propylene selectivity and good stability is a key point.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
At present, the main problems of the catalyst prepared by catalytic cracking of long-chain olefin are that the selectivity of propylene and the stability of the catalyst can not be ensured at the same time, and the potential industrial application of the reaction is limited.
[ technical solution ] A
The invention provides a catalyst system for preparing propylene from long-chain olefin and a preparation method thereof, aiming at simultaneously obtaining high conversion rate of long-chain olefin, high catalyst stability and high propylene selectivity. The catalyst prepared by the method has high activity, high olefin selectivity and high stability. Therefore, the catalyst prepared by the invention has excellent catalytic performance and stability.
The invention provides a catalyst system for catalyzing long-chain olefin to prepare propylene, wherein the catalyst system is a zeolite molecular sieve or an inert material coated zeolite molecular sieve;
the zeolite molecular sieve is prepared by the following method:
uniformly mixing a silicon source, an aluminum source, a phosphorus source, a template agent and a solvent, placing the mixture in a hydrothermal kettle to form a mixed system, and then crystallizing the mixed system for 2 to 24 days at the temperature of 104-; cooling to room temperature after the reaction is finished, centrifuging, collecting the solid, washing, drying, and roasting at 200-700 ℃ for 1-24 hours; wherein the template agent is one or more than two of di-n-propylamine, oleylamine, di-n-butylamine, triethylamine and ethylenediamine.
In one embodiment of the invention, the zeolite molecular sieve is any one crystal form of SAPO-5, SAPO-11, SAPO-31 and SAPO-41, or eutectic crystal of more than two kinds of the zeolite molecular sieve.
In one embodiment of the present invention, the silicon source is one or more of silicon dioxide, sodium silicate, propyl orthosilicate, hexamethyldisiloxane, ethyl orthosilicate, and isopropyl orthosilicate.
In one embodiment of the present invention, the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum isopropoxide, and pseudo-boehmite.
In one embodiment of the present invention, the phosphorus source is one or more of phosphoric acid, sodium phosphate, sodium monohydrogen phosphate, and sodium dihydrogen phosphate.
In one embodiment of the present invention, the solvent is water or a mixed system of water and toluene. However, when the solvent is a mixed system of water and toluene, the molar ratio of water to toluene is 5: 1.
In one embodiment of the present invention, the molar ratio of each component in the mixed system is (0.3-1.0) SiO2:1.0Al2O3:1.0P2O5The template agent (1-3) and the solvent (50-60).
In one embodiment of the present invention, the inert material coating layer in the zeolite molecular sieve coated with the inert material is one or two of silicon oxide and aluminum oxide; the inert material coating layer accounts for 0.01 wt% -5 wt% of the weight of the catalyst system.
In one embodiment of the present invention, the molecular sieve in the catalyst system for preparing propylene from long-chain olefin is prepared by the following method:
uniformly mixing a silicon source, an aluminum source, a phosphorus source, a template agent and water, placing the mixture in a hydrothermal kettle, and crystallizing the mixture for 2 to 24 days at the temperature of 104-; then cooling to room temperature, centrifuging, collecting solid, washing, drying at 50-150 ℃ for 1-24 hours, and roasting at 200-700 ℃ for 1-24 hours to prepare the SAPO molecular sieve.
In one embodiment of the present invention, the inert material coated zeolite molecular sieve is prepared by the following steps:
dipping the zeolite molecular sieve in an aqueous solution containing an inert material precursor, continuously stirring for 0-24 hours, carrying out hydrothermal reaction for 5-100 hours at 50-200 ℃, then cooling to room temperature, centrifuging and washing, drying for 1-24 hours at 50-150 ℃, and roasting for 1-24 hours at 200-700 ℃.
In one embodiment of the present invention, the inert material precursor is one or more of tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, aluminum isopropoxide, and pseudo-boehmite.
In one embodiment of the invention, the atomic ratio of silicon to aluminum in the zeolite molecular sieve is between (0.1-10):1 and the atomic ratio of aluminum to phosphorus is between (0.1-10): 1.
The invention also provides a method for preparing propylene, which utilizes the catalyst system to catalyze long-chain olefin to carry out cracking reaction.
In one embodiment of the present invention, the long-chain olefin is an olefin having 5 to 15 carbon atoms.
In one embodiment of the present invention, the temperature of the reaction is 300-700 ℃; the reaction pressure is 0.1-2 MPa; the space velocity of the reaction is 500-100000 mL/g/h.
The invention has the beneficial technical effects that:
the catalyst system for preparing olefin by catalytic cracking of long-chain olefin prepared by the invention has high olefin cracking conversion rate and high propylene selectivity.
The catalyst system for preparing olefin by catalytic cracking of long-chain olefin prepared by the invention has very high stability and has wide industrial application prospect.
Drawings
Fig. 1 is an XRD pattern of catalyst A, D, C.
Detailed Description
The technical details of the present invention are explained in detail by the following examples.
The catalyst evaluation is carried out on a continuous fixed bed reactor device, and the reaction device mainly comprises a raw material supply system, a fixed bed reaction evaluation system, a temperature control system and a product online detection system. Firstly, catalyst is tableted and sieved, 40-60 meshes of sample particles are taken and dried in a 120 ℃ oven for 30min to remove water absorbed by a molecular sieve, and 0.5g of sample is weighed and loaded into a U-shaped quartz reaction tube. Heating to 550 ℃ at a speed of 10 ℃/min under the argon atmosphere for activation for 1h, and then bringing the long-chain olefin raw material into the reactor. The cleavage product is incubated at 160 ℃. Finally, the cracked product was subjected to an on-line gas chromatograph (GC-14B) equipped with a Flame Ionization Detector (FID) to allow quantitative analysis of the product. The column was a capillary column model 19091P-M15, and the organic product was analyzed using a Flame Ionization Detector (FID) according to the following chromatographic procedure: maintaining at 45 deg.C for 3min, increasing the temperature to 110 deg.C at 5 deg.C/min, maintaining at 110 deg.C for 15min, increasing the temperature to 190 deg.C at 20 deg.C/min, and maintaining at 190 deg.C for 35min
Long olefin conversion rate (mole of inlet olefin feed-mole of outlet olefin feed)/mole of inlet olefin feed x 100%;
product selectivity is the number of moles of product at the outlet x the number of carbon atoms in the product molecules/(moles of olefin feed at the inlet-moles of olefin feed at the outlet)/number of carbon atoms in the feed molecules x 100%.
The catalyst system for catalytic cracking of long-chain olefin and the preparation method thereof are as follows:
example 1
Weighing 36g of water in a 100ml beaker, adding a certain amount of phosphoric acid, mixing and stirring for 10min, then slowly adding a certain amount of pseudo-boehmite under vigorous stirring, and finally adding a certain amount of ethyl orthosilicate and di-n-butylamine (DBA) and stirring uniformly to finally form gel, wherein the molar composition is as follows: 1.0SiO2:1.0Al2O3:1.0P2O5:1.4DBA:50H2And O. And sealing the final gel in a 100ml polytetrafluoroethylene lining, crystallizing for 7 days at 180 ℃, taking out the gel from the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging, washing, drying and roasting to obtain the molecular sieve A, wherein the molecular sieve crystal form is SAPO-5 (shown in figure 1).
Example 2
2.0g of the molecular sieve A in example 1 is taken and soaked in 10mL of solution of tetraethoxysilane and water with the mass ratio of 0.2:1, and is continuously stirred for 12 hours, and then the mixture is placed in a hydrothermal kettle for reaction for 24 hours at the temperature of 150 ℃; cooling, taking out, separating, drying at 120 deg.C for 12 hr, and calcining at 500 deg.C for 5 hr to obtain SiO2Coated catalysts B, SiO2The mass fraction of the coating layer (2) was 0.84 wt%.
Example 3
The first crystallization time in example 1 was changed to 14 days, and the other steps were not changed to obtain catalyst C having a molecular sieve form of SAPO-41/5 (as shown in fig. 1).
Example 4
The aluminum source, the phosphorus source and the silicon source are respectively aluminum isopropoxide, phosphoric acid, gas phase silicon dioxide and di-n-propylamine (Pr)2NH) and oleylamine (OAm) as templating agents. First, 16.4g of Toluene (TL) was weighed out in a 100ml beaker, stirred for 30min with a fixed amount of oleylamine, then with a fixed amount of aluminum isopropoxide and stirred for a further 2h to form solution A. Another 100ml beaker16g of water was weighed, a predetermined amount of phosphoric acid was added thereto, and the mixture was stirred for 30 minutes, followed by addition of predetermined amounts of fumed silica and di-n-propylamine, and stirring was carried out for 4 hours to obtain a solution B. Finally, the solution A and the solution B are transferred into a 100ml polytetrafluoroethylene lining to form a mixed system, and the mixed system is crystallized for 2 days at the temperature of 200 ℃. And after the crystallization is completed, taking out the high-pressure reaction kettle, naturally cooling to room temperature, centrifuging, washing, drying and roasting to obtain the SAPO-41 molecular sieve (shown in figure 1), which is the catalyst D.
The molar composition in the mixed system of the embodiment is as follows: 0.3SiO2:1.0Al2O3:1.0P2O5:2.2Pr2NH:50H2O:10TL:0.8OAm。
Example 5
2.0g of the molecular sieve in example 4 is taken and soaked in 10mL of solution of tetraethoxysilane and water with the mass ratio of 0.2:1, and the solution is continuously stirred for 12 hours and then placed in a hydrothermal kettle for reaction for 24 hours at the temperature of 150 ℃; cooling, taking out, separating, drying at 120 deg.C for 12 hr, and calcining at 500 deg.C for 5 hr to obtain SiO2Coated catalysts E, SiO2The mass fraction of the coating layer (2) was 1.12 wt%.
Application of catalyst system for catalytic cracking of long-chain olefin in catalytic cracking of long-chain olefin
Example 6
Placing the catalysts A-E in a fixed bed reactor, reacting 1-hexene with the following reaction conditions: the reaction is continuously carried out for 300 hours at 550 ℃, 0.1MPa and space velocity of hexene of 5000 mL/g/h. The average conversion and the individual product selectivity or distribution results are shown in table 1.
TABLE 1 catalytic cracking behaviour of different catalysts (A-E) on 1-hexene
As can be seen from the results in Table 1, the conversion rate of the catalytic system prepared by the catalyst preparation method of the invention to the catalytic cracking of 1-hexene can reach more than 95%, the propylene selectivity reaches about 90%, and the total selectivity of C2-C4 olefins reaches 93-97%. More importantly, the hexene conversion and the propylene selectivity of the catalyst are kept basically unchanged in 300 hours of reaction, and the catalyst shows good stability.
Example 7
Placing the catalysts A-E in a fixed bed reactor, wherein the reaction raw material is 1-octene, and the reaction conditions are as follows: the reaction was continued at 550 ℃ and 0.1MPa at a space velocity of 5000mL/g/h for 300 hours. The average conversion and the individual product selectivity or distribution results are shown in Table 2.
TABLE 2 catalytic cracking Performance of different catalysts (A-E) on 1-octene
It can be seen from table 2 that the catalyst of the present invention still has near 100% conversion rate for 1-octene with increased carbon number, propylene selectivity is about 40%, and total selectivity of C2-C4 olefins reaches 70-80%, at which time the catalyst still has better stability.
Comparative example 1
The first crystallization time in example 1 was changed to 1 day, and the other steps were not changed, to obtain catalyst F, which was applied to the reaction of 1-hexene and 1-octene at 550 deg.C, 0.1MPa and a space velocity of 5000mL/g/h for 10 hours, and the results are shown in Table 3.
Comparative example 2
SiO in example 22The mass fraction of the coating was increased to 6.5 wt% to obtain catalyst G, which was applied to 1-hexene and 1-octene at 550 deg.C, 0.1MPa and space velocity of 5000mL/G/h for 10 hours, and the results are shown in Table 3.
TABLE 3 catalytic cracking Performance of comparative examples 1-2 catalysts (F-G) on 1-hexene and 1-octene
As can be seen from the results in table 3, the catalysts of the comparative examples all exhibited inferior catalytic performance, the olefin selectivity was low, and the activity of the catalyst rapidly decreased from about 95% initially to 80% or less within 10 hours, showing very poor stability of the catalyst.
Comparative example 3
The template agent in example 1 was replaced with an equimolar amount of N, N-Dimethylcyclohexylamine (DMCHA), and the rest was unchanged to produce the corresponding molecular sieve H having a crystalline form of SAPO-34.
Comparative example 4
The template agent in example 1 is replaced by N, N-diisopropylethylamine with equal molar amount, and the rest is unchanged, so that the corresponding molecular sieve I is prepared, and the crystal form of the molecular sieve is SAPO-18.
The catalysts obtained in comparative examples 3 to 4 were applied to 1-hexene and reacted at 550 ℃ and 0.1MPa at a space velocity of 5000mL/g/h for 20 hours, and the results are shown in Table 4.
TABLE 4 catalytic cracking Performance of comparative examples 3-4 catalysts (H-I) on 1-octene
As can be seen from table 4, SAPO molecules of different crystal forms significantly affect the olefin cracking performance and the catalyst stability. The synthesized comparative sample had very much decreased activity after 20 hours of reaction; at the same time, the selectivity of propylene is obviously reduced.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A catalyst system for catalyzing long-chain olefin to prepare propylene is characterized in that the catalyst system is a zeolite molecular sieve or a zeolite molecular sieve coated by inert materials;
the zeolite molecular sieve is prepared by the following method:
uniformly mixing a silicon source, an aluminum source, a phosphorus source, a template agent and a solvent, placing the mixture in a hydrothermal kettle to form a mixed system, and then crystallizing the mixed system for 2 to 24 days at the temperature of 104-; cooling to room temperature after the reaction is finished, centrifuging, collecting the solid, washing, drying, and roasting at 200-700 ℃ for 1-24 hours; wherein the template agent is one or more than two of di-n-propylamine, oleylamine, di-n-butylamine, triethylamine and ethylenediamine.
2. The catalyst system of claim 1, wherein the zeolite molecular sieve is any one crystal form of SAPO-5, SAPO-11, SAPO-31, SAPO-41, or a eutectic crystal of two or more kinds.
3. The catalyst system of claim 1, wherein the silicon source is one or more of silicon dioxide, sodium silicate, propyl orthosilicate, hexamethyldisiloxane, ethyl orthosilicate, and isopropyl orthosilicate.
4. The catalyst system of claim 1, wherein the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum isopropoxide and pseudo-boehmite.
5. The catalyst system of claim 1, wherein the phosphorus source is one or more of phosphoric acid, sodium phosphate, sodium monohydrogen phosphate, and sodium dihydrogen phosphate.
6. The catalyst system of claim 1, wherein the solvent is water or a mixed system of water and toluene.
7. The catalyst system of claim 1, wherein the inert material coating layer in the inert material coated zeolite molecular sieve is one or two of silicon oxide and aluminum oxide; the inert material coating layer accounts for 0.01 wt% -5 wt% of the weight of the catalyst system.
8. The catalyst system of any one of claims 1-7, wherein the inert material coated zeolite molecular sieve is prepared by immersing a zeolite molecular sieve in an aqueous solution containing an inert material precursor for hydrothermal reaction; the inert material precursor is one or more than two of tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, aluminum isopropoxide and pseudo-boehmite.
9. A process for the production of propylene, wherein the process is used to catalyze the cracking of long chain olefins using a catalyst system according to any of claims 1 to 8.
10. The method as claimed in claim 9, wherein the reaction temperature is 300-700 ℃; the reaction pressure is 0.1-2 MPa; the space velocity of the reaction is 500-100000 mL/g/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210331234.9A CN114570420B (en) | 2022-03-30 | 2022-03-30 | Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210331234.9A CN114570420B (en) | 2022-03-30 | 2022-03-30 | Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114570420A true CN114570420A (en) | 2022-06-03 |
| CN114570420B CN114570420B (en) | 2023-09-08 |
Family
ID=81784321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210331234.9A Active CN114570420B (en) | 2022-03-30 | 2022-03-30 | Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114570420B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991018851A2 (en) * | 1990-06-07 | 1991-12-12 | Exxon Chemical Patents Inc. | Process for catalytic conversion of olefins |
| CN1305445A (en) * | 1998-05-05 | 2001-07-25 | 埃克森美孚化学专利公司 | Hydrocarbon conversion to propylene |
| CN1915936A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Production method for increasing production of propylene, ethene |
| CN1927783A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Method of preparing propylene by catalytic cracking |
| CN101884936A (en) * | 2010-06-30 | 2010-11-17 | 神华集团有限责任公司 | Method for preparing silicoaluminophosphate (SAPO)-34 molecular sieve molded catalyst, product prepared by method and application of product |
| JP2012020209A (en) * | 2010-07-12 | 2012-02-02 | Toyota Motor Corp | Method for manufacturing propylene |
| CN109569704A (en) * | 2018-12-25 | 2019-04-05 | 江南大学 | A kind of catalyst directly preparing alkene and aromatic hydrocarbons for synthesis gas and its application |
| CN112871200A (en) * | 2021-02-03 | 2021-06-01 | 江南大学 | Catalyst system for preparing light aromatic hydrocarbon from synthesis gas and application thereof |
-
2022
- 2022-03-30 CN CN202210331234.9A patent/CN114570420B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991018851A2 (en) * | 1990-06-07 | 1991-12-12 | Exxon Chemical Patents Inc. | Process for catalytic conversion of olefins |
| CN1305445A (en) * | 1998-05-05 | 2001-07-25 | 埃克森美孚化学专利公司 | Hydrocarbon conversion to propylene |
| CN1915936A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Production method for increasing production of propylene, ethene |
| CN1927783A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Method of preparing propylene by catalytic cracking |
| CN101884936A (en) * | 2010-06-30 | 2010-11-17 | 神华集团有限责任公司 | Method for preparing silicoaluminophosphate (SAPO)-34 molecular sieve molded catalyst, product prepared by method and application of product |
| JP2012020209A (en) * | 2010-07-12 | 2012-02-02 | Toyota Motor Corp | Method for manufacturing propylene |
| CN109569704A (en) * | 2018-12-25 | 2019-04-05 | 江南大学 | A kind of catalyst directly preparing alkene and aromatic hydrocarbons for synthesis gas and its application |
| CN112871200A (en) * | 2021-02-03 | 2021-06-01 | 江南大学 | Catalyst system for preparing light aromatic hydrocarbon from synthesis gas and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOLING ZHAO等: "Interface mediated crystallization of plate-like SAPO-41 crystals to promote catalytic hydroisomerization", 《APPLIED CATALYSIS A》 * |
| 吕忠媛等: "SAPO-18分子筛在丁烯催化裂解反应中催化性能的研究", 《能源化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114570420B (en) | 2023-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8518370B2 (en) | Metalloaluminophosphate molecular sieves with lamellar crystal morphology and their preparation | |
| Álvaro-Muñoz et al. | Aluminium chloride: A new aluminium source to prepare SAPO-34 catalysts with enhanced stability in the MTO process | |
| US7785554B2 (en) | Process for manufacture of silicoaluminophosphate molecular sieves | |
| EP2121543B1 (en) | Mto process based on meapo molecular sieves combined with an ocp process to make olefins | |
| EP1970351A1 (en) | Method of preparing metalloaluminophosphate (Meapo) molecular sieve | |
| EP2027918A1 (en) | Mixtures of molecular sieves comprising MeAPO, their use in conversion of organics to olefins | |
| EP0891227A1 (en) | Use of alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts in oxygenate conversion | |
| CN113498360B (en) | Catalyst for producing light olefins from C4-C7 hydrocarbons | |
| US6906233B2 (en) | Modified metalloaluminophosphate molecular sieves | |
| CN105174286B (en) | A kind of preparation method of the eutectic molecular sieves of AEI/CHA at high proportion | |
| WO2001060746A1 (en) | Treatment of molecular sieves with silicon containing compounds | |
| EP1246775B1 (en) | Synthesis of crystalline silicoaluminophosphates | |
| EP1451106B1 (en) | Process for manufacture of molecular sieves | |
| CN101121531A (en) | Phosphorus modifying method for pinhole phosphorus-silicon-aluminum molecular sieve | |
| US20060293547A1 (en) | Process for manufacture of silicoaluminophosphate molecular sieves | |
| WO2009117186A1 (en) | Synthesis and use of aei structure-type molecular sieves | |
| EP0293914B1 (en) | Oligomerization processes and catalysts | |
| MXPA02008221A (en) | Catalyst pretreatment in an oxygenate to olefins reaction system. | |
| CN114570420B (en) | Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof | |
| CN104445267A (en) | Method for synthesizing silicoaluminophosphate molecular sieve | |
| KR101719755B1 (en) | silicoaluminophosphate molecular sieve(SAPO)-34 catalyst for the synthesis of propylene from ethylene and manufacturing method of the same | |
| CN104226364B (en) | The method preparing molecular sieve fluid bed catalyst | |
| CN104226363B (en) | The preparation method of oxygenatedchemicals olefin hydrocarbon molecules sieve fluid catalyst | |
| CN107954811B (en) | Process for converting oxygen-containing organic compounds to carbon-tetrads | |
| CN111302353A (en) | SAPO-34 molecular sieve with composite meso-microporous structure and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |