CN114570420B - Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof - Google Patents
Catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis and application thereof Download PDFInfo
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- CN114570420B CN114570420B CN202210331234.9A CN202210331234A CN114570420B CN 114570420 B CN114570420 B CN 114570420B CN 202210331234 A CN202210331234 A CN 202210331234A CN 114570420 B CN114570420 B CN 114570420B
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- molecular sieve
- zeolite molecular
- olefin
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- inert material
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 55
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- 238000000197 pyrolysis Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- 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
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- 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 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 32
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture 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
- 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
- 239000003795 chemical substances by application 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000013078 crystal Substances 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
- 239000002243 precursor Substances 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
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 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
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 238000004227 thermal cracking Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 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
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 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
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- 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
- 229910004298 SiO 2 Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect 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
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method 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
- 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
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- 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 long-chain olefin pyrolysis and application thereof, and belongs 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, accounting for 0.01-5wt% 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 can have 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 wide industrial application prospect.
Description
Technical Field
The invention relates to a catalytic system for preparing propylene by catalyzing long-chain olefin pyrolysis 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, epoxypropane and the like. Since 2017, its global production exceeds 100 ten thousand tons/year, and its demand is expected to exceed 150 ten thousand tons/year in 2050. The industrial propylene producing process includes two kinds, including thermal cracking and catalytic cracking, and special propylene producing process. Heretofore, catalytic cracking process technology is the most economical way to produce propylene, 90% of which worldwide comes from FCC and thermal cracking, with a thermal cracking rate of 60%. The main product of conventional steam cracking is ethylene, while propylene is a by-product. However, as the cost of ethane in the middle eastern region decreases, shale gas ethane is increasingly used as a feedstock in north america, inhibiting the development of thermal cracking processes, resulting in a continuous decrease in propylene production. However, due to the rapid development of the downstream propylene industry, the demand for propylene has increased substantially, and it is expected that 56 ten thousand tons per year will increase from 2014 to 2030. Thus, the conventional process has failed to meet the increasing demand for propylene.
Propylene has tremendous market potential and many scholars are working on developing propylene production routes such as: disproportionation of olefin, dehydrogenation of propane, preparation of propylene from methanol, cracking of olefin, preparation of propylene from ethylene, and the like. These new technologies for the production of propylene have a critical role in meeting the propylene supply requirements. The olefin catalytic cracking process has high competitiveness and accords with the national conditions of China, and is an important way for producing propylene. Although no olefins are 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 catalytic cracking reaction temperature of olefin is lower, the flexibility is higher, and the selectivity of propylene can be improved by combining multiple processes. The catalytic cracking of olefin mostly uses a fixed bed as a reactor, so that the investment cost is greatly reduced, and the recovery rate is higher. Simultaneously, the reaction process is accompanied by the generation of ethylene and butene.
At present, several olefin cracking processes are being developed and are in various stages of commercialization, such as the Propylur process from Ludgkin, the PCC process from Exxon Mobil, the OCC process from medium petroleum, and the Superflex process and ACO process from KBR. Light olefin is used as raw material, and the traditional catalytic cracking device is modified, so that the yield of olefin can be improved to the maximum extent. However, the biggest disadvantage of the modified FCC process is the inability to break the thermodynamic equilibrium of the device and the associated design investment costs associated with multiple processes. The catalytic cracking reaction of olefin is a process of cracking olefin at high temperature (450-600 ℃) and low pressure (1-2 Bar) to prepare light olefin, and simultaneously light aromatic hydrocarbon and alkane are also produced. The presence of a catalyst during the cracking process may reduce the cracking activation energy. Thus, the reaction temperature of catalytic cracking of olefins is greatly reduced compared to thermal cracking. The olefin molecules can be activated into carbonium ions on the active site of the catalyst, and then are cracked into smaller olefin molecules, and the cracked products are mainly propylene and butylene. Catalysts currently used in catalytic cracking of olefins are various types of molecular sieves. The SAPO-34 molecular sieve can improve propylene selectivity, and the pore structure of the molecular sieve is composed of a 0.67 multiplied by 0.11nm big cage and a 0.38 multiplied by 0.38nm small hole (8-MR) which are connected, so that the molecular sieve can prevent the formation of long-chain or branched-chain hydrocarbon and inhibit secondary reaction. SAPO-34 can inhibit the formation of isobutene, thereby increasing the yields of ethylene and propylene, compared to ZSM-5 molecular sieves. However, SAPO-34 molecular sieves have poor stability because larger aromatics cannot pass through the small pores of SAPO-34, eventually forming carbon deposits covering the acidic sites. Therefore, it is a key point to develop a catalyst having high propylene selectivity and good stability.
Disclosure of Invention
[ problem ]
At present, long-chain olefin catalytic cracking is adopted, and the main problems of the catalyst are that propylene selectivity and catalyst stability can not be ensured at the same time, so that potential industrial application of the reaction is limited.
[ technical solution ]
In order to simultaneously obtain high long-chain olefin conversion rate, high catalyst stability and high propylene selectivity, the invention provides a catalyst system for preparing propylene from long-chain olefin and a preparation method thereof. The catalyst prepared by the invention not only has high activity and high olefin selectivity, but also has high stability. Therefore, the catalyst prepared by the invention has excellent catalytic performance and stability.
The invention provides a catalyst system for preparing propylene by catalyzing long-chain olefin, wherein 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 crystallizing the mixed system at 104-250 ℃ for 2-24 days; cooling to room temperature after finishing, centrifuging, collecting solid, washing, drying, and roasting at 200-700 ℃ for 1-24 hours; wherein the template agent is one or more 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 more than two eutectic crystals.
In one embodiment of the present invention, the silicon source is one or more of silicon dioxide, sodium silicate, propyl orthosilicate, hexamethyldisiloxane, ethyl orthosilicate, 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 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 invention, the molar ratio of the components in the mixed system is (0.3-1.0) SiO 2 :1.0Al 2 O 3 :1.0P 2 O 5 1-3 template agent (50-60) solvent.
In one embodiment of the present invention, 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 0.01-5wt% of the weight of the catalyst system.
In one embodiment of the present invention, the molecular sieve in the catalyst system for the production of propylene from long chain olefins is prepared by the following process:
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 at 104-250 ℃ for 2-24 days; and then cooling to room temperature, centrifuging, collecting solids, washing, drying at 50-150 ℃ for 1-24 hours, and roasting at 200-700 ℃ for 1-24 hours to obtain the SAPO molecular sieve.
In one embodiment of the present invention, the inert material-coated zeolite molecular sieve is prepared by the steps of:
soaking zeolite molecular sieve in water solution containing inert material precursor, stirring for 0-24 hr, hydrothermal reaction at 50-200 deg.c for 5-100 hr, cooling to room temperature, centrifuging and washing, drying at 50-150 deg.c for 1-24 hr, and roasting at 200-700 deg.c for 1-24 hr.
In one embodiment of the present invention, the inert material precursor is one or more than two of tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, aluminum isopropoxide, and pseudo-boehmite.
In one embodiment of the invention, the zeolite molecular sieve has a silicon to aluminum atomic ratio of between (0.1 and 10) and an aluminum to phosphorus atomic ratio of between (0.1 and 10) and 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 invention, the temperature of the reaction is 300-700 ℃; the pressure of the reaction is 0.1-2MPa; the space velocity of the reaction is 500-100000mL/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 can have 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 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 described in detail by the following examples.
The catalyst evaluation is carried out on a continuous fixed bed reactor device which mainly comprises a raw material supply system, a fixed bed reaction evaluation system, a temperature control system and a product on-line detection system. Firstly, tabletting and sieving the catalyst, taking 40-60 mesh sample particles, drying in a baking oven at 120 ℃ for 30min to remove adsorbed moisture of the molecular sieve, weighing 0.5g of sample, and loading the sample into a U-shaped quartz reaction tube. The long-chain olefin feedstock was then brought into the reactor after activation under argon at 10 ℃/min to 550 ℃ for 1 hour. The cleavage product is incubated at 160 ℃. Finally, the cracked product enters an online gas chromatograph (GC-14B) which is provided with a hydrogen Flame Ion Detector (FID) and can be quantitatively analyzed. The chromatographic column is 19091P-M15 capillary column, the organic product is analyzed by hydrogen Flame Ion Detector (FID), and the chromatographic procedure is: maintaining at 45deg.C for 3min,5 deg.C/min up to 110deg.C, 110 deg.C for 15min,20 deg.C/min up to 190 deg.C, 190 deg.C for 35min
Long-chain olefin conversion= (moles of inlet feed olefin-moles of outlet feed olefin)/moles of inlet feed olefin x 100%;
product selectivity = number of moles of product exiting x number of carbon atoms in product molecule/(number of moles of olefin entering feedstock-number of moles of olefin exiting) number of carbon atoms in feedstock molecule x 100%.
Catalyst system for catalytic cracking of long-chain olefins and a process for its preparation:
example 1
36g of water is weighed by a 100ml beaker, added with quantitative phosphoric acid, mixed and stirred for 10min, then slowly added with quantitative pseudo-boehmite under vigorous stirring, finally added with a certain amount of tetraethoxysilane and di-n-butylamine (DBA) and stirred until uniform, and finally gel is formed, wherein the molar composition is as follows: 1.0SiO 2 :1.0Al 2 O 3 :1.0P 2 O 5 :1.4DBA:50H 2 O. And (3) sealing the final gel in a polytetrafluoroethylene lining of 100ml, crystallizing for 7 days at 180 ℃, taking out of 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 molecular sieve A in example 1 is immersed in 10mL of solution with the mass ratio of tetraethoxysilane to water being 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 150 ℃; cooling, taking out, separating, drying at 120deg.C for 12 hr, and calcining at 500deg.C for 5 hr to obtain SiO-containing powder 2 Coated catalyst B, siO 2 The mass fraction of the coating was 0.84wt%.
Example 3
The crystallization time of the first step in example 1 was changed to 14 days, and the other steps were unchanged, to obtain catalyst C, the molecular sieve was 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 and fumed silica, and di-n-propylamine (Pr 2 NH) and oleylamine (OAm) as templating agents. First, 16.4g of Toluene (TL) was weighed out in a 100ml beaker, a quantitative amount of oleylamine was added and stirred for 30 minutes, then a quantitative amount of aluminum isopropoxide was added and stirred for 2 hours to form a solution A. Another 100ml beaker was weighed 16g of water, added with quantitative phosphoric acid, mixed and stirred for 30min, then added with quantitative fumed silica and di-n-propylamine, and stirred for 4h to form solution B. Finally, transferring the solution A and the solution B into a polytetrafluoroethylene lining of 100ml to form a mixed system, and crystallizing at 200 ℃ for 2 days. And taking out the high-pressure reaction kettle after crystallization is completed, naturally cooling to room temperature, centrifuging, washing, drying and roasting to obtain the SAPO-41 molecular sieve (shown in figure 1) serving as the catalyst D.
The molar composition in the mixed system of this example is: 0.3SiO 2 :1.0Al 2 O 3 :1.0P 2 O 5 :2.2Pr 2 NH:50H 2 O:10TL:0.8OAm。
Example 5
2.0g of the molecular sieve of example 4 was immersed in 10mL of ethyl orthosilicateThe mass ratio of the ester to the water is 0.2:1, and the mixture is continuously stirred for 12 hours, and then the mixture is placed in a hydrothermal kettle for reaction for 24 hours at 150 ℃; cooling, taking out, separating, drying at 120deg.C for 12 hr, and calcining at 500deg.C for 5 hr to obtain SiO-containing powder 2 Coated catalyst E, siO 2 The mass fraction of the coating is 1.12% by weight.
Application of catalyst system for catalytic cracking of long-chain olefin in catalytic cracking of long-chain olefin
Example 6
Catalysts A-E are placed in a fixed bed reactor, and the reaction raw material 1-hexene is reacted under the conditions that: the reaction was continued for 300 hours at 550℃and a hexene space velocity of 5000 mL/g/h. The average conversion and the individual product selectivities or distributions are shown in Table 1.
TABLE 1 catalytic cracking Properties 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 to the catalytic cracking of 1-hexene can be up to 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 rate and the propylene selectivity of the catalyst are kept basically unchanged within 300 hours of reaction, and the catalyst has good stability.
Example 7
Catalysts A-E are placed in a fixed bed reactor, the reaction raw materials are 1-octene, and the reaction conditions are as follows: the reaction was continued for 300 hours at 550℃under 0.1MPa and a space velocity of 5000 mL/g/h. The average conversion and the individual product selectivities or distributions are shown in Table 2.
TABLE 2 catalytic cracking Properties of different catalysts (A-E) on 1-octene
As can be seen from Table 2, the catalyst of the invention has a conversion rate of nearly 100% for 1-octene with increased carbon number, a propylene selectivity of about 40%, and a total C2-C4 olefin selectivity of 70-80%, and has better stability.
Comparative example 1
The crystallization time of the first step in example 1 was changed to 1 day, and the other steps were unchanged, to obtain a catalyst F, which was applied to the reaction of 1-hexene and 1-octene at 550℃and 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 2 2 The mass fraction of the coating layer of (C) was increased to 6.5wt% to give catalyst G, which was used for 1-hexene and 1-octene reactions at 550℃and 0.1MPa and a space velocity of 5000mL/G/h for 10 hours, and the results are shown in Table 3.
TABLE 3 catalytic cracking Properties 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 showed inferior catalytic performance, olefin selectivity was relatively low, and the activity of the catalyst rapidly decreased from about 95% at the beginning to less than 80% within 10 hours, showing very poor stability of the catalyst.
Comparative example 3
The template in example 1 was replaced with equimolar amounts of N, N-Dimethylcyclohexylamine (DMCHA), the others being unchanged, to give the corresponding molecular sieve H, which was in the form of SAPO-34.
Comparative example 4
The template in example 1 was replaced with equimolar amounts of N, N-diisopropylethylamine, the others being unchanged, to give the corresponding molecular sieve I, which was in the form of SAPO-18.
The catalysts obtained in comparative examples 3 to 4 were used for the reaction of 1-hexene at 550℃under 0.1MPa and at a space velocity of 5000mL/g/h for 20 hours, and the results are shown in Table 4.
TABLE 4 catalytic cracking Properties of comparative examples 3-4 catalyst (H-I) on 1-octene
It can be seen from table 4 that SAPO molecules of different crystal forms significantly affect olefin cracking performance and catalyst stability. The activity of the synthesized comparative sample was very much reduced after 20 hours of reaction; at the same time, the propylene selectivity is significantly reduced.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and 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 (8)
1. A method for preparing propylene, which is characterized in that a catalyst system is utilized to catalyze long-chain olefin to carry out cracking reaction; the long-chain olefin is 1-hexene; 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 crystallizing the mixed system at 104-250 ℃ for 2-24 days; cooling to room temperature after finishing, centrifuging, collecting 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;
the zeolite molecular sieve is any one crystal form or two eutectic forms of SAPO-5 and SAPO-41;
the inert material coating layer accounts for 0.01-5wt% of the weight of the catalyst system.
2. The method of claim 1, wherein the silicon source is one or more of silicon dioxide, sodium silicate, propyl orthosilicate, hexamethyldisiloxane, ethyl orthosilicate, isopropyl orthosilicate.
3. The method of claim 1, wherein the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum isopropoxide, and pseudo-boehmite.
4. The method of claim 1, wherein the phosphorus source is one or more of phosphoric acid, sodium phosphate, sodium monohydrogen phosphate, and sodium dihydrogen phosphate.
5. The method according to claim 1, wherein the solvent is water or a mixed system of water and toluene.
6. The method of claim 1, wherein the inert material coating in the inert material coated zeolite molecular sieve is one or both of silica and alumina.
7. The method of any one of claims 1-6, wherein the inert material-coated zeolite molecular sieve is prepared by hydrothermal reaction of a zeolite molecular sieve impregnated with an aqueous solution containing an inert material precursor; the inert material precursor is one or more than two of tetraethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, aluminum isopropoxide and pseudo-boehmite.
8. The method according to claim 1, wherein the temperature of the reaction is 300-700 ℃; the pressure of the reaction is 0.1-2MPa; the space velocity of the reaction is 500-100000mL/g/h.
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