CN113546669B - Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material with high specific surface area, and preparation method and application thereof - Google Patents
Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material with high specific surface area, and preparation method and application thereof Download PDFInfo
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- CN113546669B CN113546669B CN202010332236.0A CN202010332236A CN113546669B CN 113546669 B CN113546669 B CN 113546669B CN 202010332236 A CN202010332236 A CN 202010332236A CN 113546669 B CN113546669 B CN 113546669B
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- China
- Prior art keywords
- specific surface
- surface area
- catalytic cracking
- phosphotungstic acid
- mesoporous material
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 105
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 104
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 62
- 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 62
- 239000011148 porous material Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 40
- 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 40
- 239000010457 zeolite Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 22
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 23
- 230000001965 increasing effect Effects 0.000 abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/615—
-
- B01J35/633—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
Abstract
The invention relates to the field of petrochemical industry, and discloses a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with high specific surface area, and a preparation method and application thereof. Wherein the catalytic cracking auxiliary agent comprises a zeolite molecular sieve with high silicon-aluminum ratio and a phosphotungstic acid modified mesoporous material with high specific surface area, wherein the phosphotungstic acid modified mesoporous material with high specific surface area is spherical, and the specific surface area is 810-1100m 2 And/g, wherein the pore volume is 0.4-1mL/g, the average pore diameter is 2-3nm, and the content of the phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area. The catalytic cracking auxiliary agent provided by the invention is used in the catalytic cracking process, so that the propylene concentration in the liquefied gas can be greatly improved under the condition of not increasing the yield of the catalytic cracked liquefied gas, and meanwhile, the octane number of the catalytic cracked gasoline can be also improved.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with high specific surface area, and a preparation method and application thereof.
Background
In recent years, the deterioration of crude oil has limited naphtha as a steam cracking feed, and has severely affected the increase in propylene yield. Therefore, the catalytic cracking device with wider raw material sources and lower operation cost is more economical and convenient for increasing propylene production, and the general attention of people is obtained. In addition, most FCC conventional catalytic crackers use catalytic cracking aids to increase propylene yield while reducing gasoline octane number.
FCC catalytic cracking assistants generally comprise zeolite molecular sieves having an MFI framework structure as the main component, especially ZSM-5 molecular sieves. The conventional ZSM-5 molecular sieve has stronger cracking activity due to more surface acid centers, is easy to generate hydrogen transfer reaction, and further has poorer propylene yield increasing effect. To overcome this drawback, researchers have made various improvements in the synthesis technology of molecular sieves. However, the inherent pore structure of microporous molecular sieves is difficult to change. The ZSM-5 molecular sieve has relatively narrow pore canal, if the reactant molecules are larger, the reactant molecules are difficult to enter the pore canal for reaction, so that the effective utilization rate of the catalytic cracking auxiliary agent is lower; in addition, because the molecular sieve pore channel is narrow, partial product molecules are difficult to diffuse out, deep dehydrogenation is easy to cause to form coking, and the molecular sieve deactivation is promoted. Compared with zeolite molecular sieve, the all-silicon mesoporous material has highly ordered mesoporous pore canal, large specific surface area, large pore diameter, large pore volume and thicker pore wall, and can maintain higher mechanical strength and good catalytic performance and adsorption performance. However, all-silicon mesoporous molecular sieves are not acidic in nature and are difficult to be used alone as catalysts for hydrocarbon conversion reactions.
Therefore, research and development of a catalytic cracking additive suitable for increasing propylene yield has important significance.
Disclosure of Invention
The invention aims to overcome the defects of low propylene selectivity and low octane number of cracked gasoline of a catalytic cracking additive in the prior art, and provides a catalytic cracking additive containing a phosphotungstic acid modified mesoporous material with high specific surface area, and a preparation method and application thereof. The invention has the advantages that the auxiliary agent provided by the invention is used in the catalytic cracking process, can greatly improve the propylene concentration in the liquefied gas without increasing the yield of the catalytic cracked liquefied gas, and can also improve the octane number of the catalytic cracked gasoline.
In order to achieve the above object, a first aspect of the present invention provides a catalytic cracking aid containing a phosphotungstic acid modified high specific surface area mesoporous material, wherein the catalytic cracking aid comprises a high silica alumina zeolite molecular sieve and a phosphotungstic acid modified high specific surface area mesoporous material, wherein the phosphotungstic acid modified high specific surface area mesoporous material is spherical, and the specific surface area is 810-1100m 2 And/g, wherein the pore volume is 0.4-1mL/g, the average pore diameter is 2-3nm, and the content of the phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area.
The second aspect of the invention provides a preparation method of a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with high specific surface area, wherein the method comprises the following steps:
(1) Mixing and pulping a zeolite molecular sieve with high silicon-aluminum ratio, a phosphotungstic acid modified mesoporous material with high specific surface area, an adhesive and deionized water to obtain first slurry;
(2) Mixing and pulping the first slurry and the metal salt aqueous solution to obtain second slurry;
(3) Grinding the second slurry, and sequentially carrying out spray drying and roasting treatment to obtain a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with high specific surface area;
wherein the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 810-1100m 2 And/g, wherein the pore volume is 0.4-1mL/g, the average pore diameter is 2-3nm, and the content of the phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area.
The third aspect of the invention provides a catalytic cracking additive containing a phosphotungstic acid modified mesoporous material with high specific surface area, which is prepared by the method.
The fourth aspect of the invention provides an application of the catalytic cracking additive containing the phosphotungstic acid modified mesoporous material with high specific surface area in hydrocarbon oil catalytic cracking reaction.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The catalytic cracking auxiliary agent for increasing the yield of propylene provided by the invention can be directly used for the existing catalytic cracking production device, does not need to change the process conditions, does not need to change the production raw materials, and is simple to operate;
(2) The main components of the catalytic cracking auxiliary agent for increasing propylene yield provided by the invention are zeolite molecular sieve with high silicon-aluminum ratio and phosphotungstic acid modified mesoporous material with high specific surface area, and the catalytic cracking auxiliary agent has low raw material cost and simple preparation method.
(3) The catalytic cracking auxiliary agent for increasing propylene yield provided by the invention is used for catalytic cracking reaction, can greatly improve the propylene concentration in liquefied gas under the condition of unchanged liquefied gas yield, and can improve the octane number of gasoline products.
(4) The preparation method of the catalytic cracking auxiliary agent for increasing propylene yield has the advantages of simple process, easy control of conditions and good product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an XRD spectrum of the phosphotungstic acid modified mesoporous material A with high specific surface area prepared in example 1;
FIG. 2 is an SEM image of the high specific surface area mesoporous material A prepared in example 1;
fig. 3 is an SEM scanning electron microscope image of the phosphotungstic acid modified high specific surface area mesoporous material a prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Zeolite molecular sieves are various in variety, and have clear pore channel structure characteristics, including one-dimensional straight-through pore channels, two-dimensional crossed pore channels, three-dimensional solid pore channels and multidimensional pore channels. Because the pore canal structure of the zeolite molecular sieve is ordered in a short distance, the pore diameter is generally smaller than 2.0nm, and the zeolite molecular sieve can show better shape-selective effect in small molecular catalytic reaction and adsorption separation. Therefore, in the prior art, typical FCC catalytic cracking additives generally use zeolite molecular sieves (mainly ZSM-5 molecular sieves) as the main components. Because the hydrogen zeolite molecular sieve has an acidic site, the activation capability is stronger, but because the pore size is smaller, the diffusion of reaction raw materials and products is easily affected, and further, the propylene selectivity is lower and the catalyst stability is poorer. Researchers modify and modify the surface characteristics of zeolite molecular sieves to improve the catalytic performance of the catalytic cracking aid to a certain extent. However, the modification and modification of zeolite molecular sieves can only change the surface characteristics, but cannot change the basic framework structure of the molecular sieves, and the problem of diffusion of raw materials and products is difficult to solve. Therefore, it is difficult to greatly improve propylene selectivity by modifying zeolite molecular sieves.
The inventor of the invention finds that if a certain amount of all-silicon mesoporous material is mixed with zeolite molecular sieve and modified to prepare the catalytic cracking auxiliary agent when the catalytic cracking auxiliary agent is prepared, the pore channel structure of the auxiliary agent can be effectively improved to be more beneficial to rapid diffusion of reactant molecules and product molecules, thereby effectively inhibiting side reaction and improving propylene selectivity. However, all-silicon mesoporous materials do not have an acidic center themselves, and it is difficult to catalyze the conversion of hydrocarbon feedstocks in cracking reactions. If phosphotungstic acid is used as a modifier to modify the all-silicon mesoporous material, an acid center can be introduced to the surface of the mesoporous material. A certain amount of phosphotungstic acid modified mesoporous material with high specific surface area is mixed with zeolite molecular sieve and modified to prepare the catalytic cracking auxiliary agent, so that the conversion rate of raw materials, the propylene selectivity and the octane number of cracked gasoline can be greatly improved.
The first aspect of the invention provides a modified high specific surface containing phosphotungstic acidThe catalytic cracking auxiliary agent of the mesoporous material comprises a zeolite molecular sieve with high silicon-aluminum ratio and a phosphotungstic acid modified mesoporous material with high specific surface area, wherein the phosphotungstic acid modified mesoporous material with high specific surface area is spherical and has a specific surface area of 810-1100m 2 And/g, wherein the pore volume is 0.4-1mL/g, the average pore diameter is 2-3nm, and the content of the phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area.
According to the invention, the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is preferably 814-908m 2 And/g, wherein the pore volume is 0.5-0.7mL/g, the average pore diameter is 2.2-2.5nm, and the content of the phosphotungstic acid is 10-15 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area. In the invention, the phosphotungstic acid with the content limited by the above can be used for better modifying the mesoporous material with high specific surface area, namely, introducing acid centers on the surface of the mesoporous material with high specific surface area.
According to the invention, the zeolite molecular sieve with high silicon-aluminum ratio is a high silicon ZSM-5 molecular sieve and/or a high silicon ZRP molecular sieve; preferably, the high silica to alumina ratio zeolite molecular sieve has a Si/Al molar ratio of 100 to 800, more preferably 150 to 600, still more preferably 200 to 500.
According to the invention, the weight ratio of the zeolite molecular sieve with high silicon-aluminum ratio to the phosphotungstic acid modified mesoporous material with high specific surface area is (1.5-3.5): 1, preferably (1.8-2.2): 1.
according to the invention, the content of the zeolite molecular sieve with high silicon-aluminum ratio is 45-65 wt% based on the total weight of the catalytic cracking auxiliary agent, and the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 20-30 wt%; preferably, the content of the zeolite molecular sieve with high silicon-aluminum ratio is 50-60 wt% and the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 20-28 wt% based on the total weight of the catalytic cracking auxiliary agent; more preferably, the content of the zeolite molecular sieve with high silicon-aluminum ratio is 50-60 wt% and the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 25-27.78 wt% based on the total weight of the catalytic cracking auxiliary agent.
According to the invention, the preparation method of the phosphotungstic acid modified mesoporous material with high specific surface area comprises the following steps:
(a) Under the existence of a template agent and polyethylene glycol octyl phenyl ether, a silicon source is contacted with an acidic aqueous solution, and the mixture obtained after the contact is crystallized, washed, filtered, dried and template agent removed to obtain a mesoporous material with high specific surface area;
(b) And mixing and ball milling the high specific surface area mesoporous material and phosphotungstic acid to obtain the phosphotungstic acid modified high specific surface area mesoporous material.
According to the invention, the specific surface area of the mesoporous material with high specific surface area is 1207-1281m 2 Per gram, the pore volume is 0.8-0.9mL/g, and the average pore diameter is 2.6-3nm.
According to the invention, the weight ratio of the high specific surface area mesoporous material to the phosphotungstic acid is (4.26-11.5): 1, preferably (4-9): 1.
according to the invention, the template is cetyltrimethylammonium bromide.
According to the invention, the acidic aqueous solution is an aqueous hydrochloric acid solution prepared from water and hydrogen chloride.
According to the invention, the silicon source is selected from one or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, preferably ethyl orthosilicate.
According to the invention, the silicon source: polyethylene glycol octyl phenyl ether (triton X-100): the template agent comprises the following components: hydrogen chloride: the molar ratio of water is 1:0.1-0.5:0.1-0.6:5-50:100-500, preferably 1:0.2-0.4:0.2-0.5:10-30:150-400.
According to the invention, the conditions of the contact include: the temperature is 25-60 ℃ and the time is 0.5-2h; the contacting may be performed under stirring conditions, wherein the stirring conditions include: the stirring rate is 200-900 rpm.
According to the present invention, the crystallization conditions include: the temperature is 25-60 ℃ and the time is 10-40h.
The washing method according to the present invention is not particularly limited and may be a method well known to those skilled in the art. Preferably, it is: mixing the separated solid with deionized water, stirring and pulping for 2h, standing for 3h, and separating. The above washing process was repeated 6 to 10 times.
According to the invention, the suction filtration separation is a well known way of separating liquid from solid particles by means of air pressure or a mixture of liquid and liquid.
According to the invention, the drying conditions are preferably: the drying temperature is 70-150 ℃ and the drying time is 3-20h.
According to the invention, the conditions for removing the template agent comprise: roasting in air atmosphere at 400-700 deg.c for 5-40 hr;
according to the present invention, the conditions for ball milling include: the temperature is 15-70 ℃ and the time is 0.5-30h; preferably, the temperature is 20-70 ℃ and the time is 1-30h.
According to the invention, the catalytic cracking promoter further comprises a first oxide; preferably, the first oxide is an oxide obtained by roasting a binder, preferably aluminum oxide and/or silicon oxide; more preferably, the binder is selected from one or more of silica sol, alumina sol, pseudo-boehmite and diaspore.
According to the invention, the catalytic cracking aid further comprises a second oxide; preferably, the second oxide is one or more of an alkaline earth metal oxide, a transition metal oxide, and a rare earth metal oxide; more preferably, the second oxide is selected from one or more of magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, cerium oxide, and lanthanum oxide.
According to the invention, the content of the first oxide is 10-20 wt% and the content of the second oxide is 1-9 wt%, based on the total weight of the catalytic cracking aid; preferably, the first oxide is contained in an amount of 12 to 18 wt% and the second oxide is contained in an amount of 3 to 7 wt% based on the total weight of the catalytic cracking aid.
In the invention, the catalytic cracking auxiliary agent comprises a zeolite molecular sieve with high silicon-aluminum ratio, a phosphotungstic acid modified mesoporous material with high specific surface area, a first oxide and a second oxide, wherein the sum of the total contents of the components is 100 weight percent.
The second aspect of the invention provides a preparation method of the catalytic cracking additive containing the phosphotungstic acid modified mesoporous material with high specific surface area, wherein the method comprises the following steps:
(1) Mixing and pulping a zeolite molecular sieve with high silicon-aluminum ratio, a phosphotungstic acid modified mesoporous material with high specific surface area, an adhesive and deionized water to obtain first slurry;
(2) Mixing and pulping the first slurry and the metal salt aqueous solution to obtain second slurry;
(3) Grinding the second slurry, and sequentially carrying out spray drying and roasting treatment to obtain a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with high specific surface area;
wherein the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 810-1100m 2 And/g, wherein the pore volume is 0.4-1mL/g, the average pore diameter is 2-3nm, and the content of the phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area.
According to the invention, the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is preferably 814-908m 2 And/g, wherein the pore volume is 0.5-0.7mL/g, the average pore diameter is 2.2-2.5nm, and the content of the phosphotungstic acid is 10-15 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area.
According to the invention, in step (1), the beating time is 0.5-5h.
According to the invention, in step (2), the beating time is 0.5-2h.
According to the invention, in step (3), the slurry obtained is continuously ground for 2-40 hours at 15-100 ℃ and spray-dried at 150-600 ℃; roasting the dried product at 450-650 ℃ for 3-15h.
According to the invention, the metal salt is a nitrate of a metal; preferably, the metal is one or more of alkaline earth metal, transition metal and rare earth metal, more preferably, the metal is one or more selected from magnesium, calcium, strontium, barium, zinc, cerium and lanthanum.
According to the invention, the high silica alumina ratio zeolite molecular sieve is used in an amount of 100 to 2000 parts by weight, the phosphotungstic acid modified high specific surface area mesoporous material is used in an amount of 50 to 1200 parts by weight, the binder is used in an amount of 200 to 2500 parts by weight, and the metal salt is used in an amount of 30 to 100 parts by weight, relative to 100g of water.
The third aspect of the invention provides a catalytic cracking additive containing a phosphotungstic acid modified mesoporous material with high specific surface area, which is prepared by the method.
According to the invention, the specific surface area of the catalytic cracking auxiliary agent is 320-400m 2 Per gram, pore volume of 0.4-0.55cm 3 /g; preferably, the specific surface area is 329-394m 2 Per gram, pore volume of 0.43-0.51cm 3 /g。
The fourth aspect of the invention provides an application of the catalytic cracking additive containing the phosphotungstic acid modified mesoporous material with high specific surface area in hydrocarbon oil catalytic cracking reaction.
When the catalytic cracking auxiliary agent provided by the invention is used in the catalytic cracking process, the catalytic cracking auxiliary agent can be added into a catalytic cracking reactor independently or can be mixed with a catalytic cracking catalyst for use. In general, the catalytic cracking aid provided by the present invention comprises from 2 to 15 wt%, preferably from 5 to 10 wt%, of the total weight of the catalytic cracking aid provided by the present invention, based on the FCC catalyst.
The catalytic cracking auxiliary agent provided by the invention can be used for processing various hydrocarbon oils, wherein the hydrocarbon oils are selected from various petroleum fractions, such as crude oil, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, straight-run wax oil, coker wax oil and the like.
The catalytic cracking auxiliary agent provided by the invention is used in the catalytic cracking process, and the catalytic cracking condition of hydrocarbon oil is conventional catalytic cracking condition. In general, the hydrocarbon oil catalytic cracking conditions are: the reaction temperature is 400-600 ℃, preferably 450-550 ℃; weight hourly space velocity of 10-120h -1 Preferably 10-80h -1 The method comprises the steps of carrying out a first treatment on the surface of the The weight ratio of the agent to the oil is 1-20, preferably 3-15.
The catalytic cracking auxiliary agent provided by the invention can be used for various existing catalytic cracking reactors, such as a fixed bed reactor, a fluidized bed reactor, a riser reactor and the like.
The zeolite molecular sieve with high silicon-aluminum ratio has the advantage of high activity when being used as an auxiliary agent in catalytic cracking reaction, but has low propylene selectivity and poor stability. In contrast, zeolite molecular sieve adjuvants with high silica to alumina ratios have improved propylene selectivity and stability, but limited improvement. The catalytic cracking auxiliary agent provided by the invention adopts the mixture of the zeolite molecular sieve with high silicon-aluminum ratio and the phosphotungstic acid modified mesoporous material with high specific surface area as main active components, and at least one of alkaline earth metal oxide, transition metal oxide and rare earth metal oxide is introduced in a proper amount, so that the selectivity of the catalytic cracking reaction process to propylene can be obviously improved, the concentration of propylene in liquefied gas can be greatly improved, and the octane number of gasoline products can be effectively increased.
In the following examples and comparative examples, analysis of pore structure parameters of samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. of U.S.A.; the X-ray diffraction analysis of the samples was performed on an X-ray diffractometer model D8 Advance from Bruker AXS company, germany; scanning electron microscope pictures of the samples are obtained on an XL-30 type field emission environment scanning electron microscope manufactured by FEI company in the United states; elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The ZSM-5 molecular sieves of varying silica to alumina ratios used in the examples and comparative examples were all purchased from Shanghai Fuxu molecular sieves limited; ZRP zeolite molecular sieves were purchased from Wohan Hezhong Biochemical manufacturing Co., ltd; aluminum sol and silica sol are available from Zibo good wetting chemical Co., ltd; pseudo-boehmite was purchased from new materials, inc. of the body Ji Fen, boheng; other reagents were purchased from national pharmaceutical group chemical reagent limited.
Example 1
This example is a description of a catalytic cracking aid containing a phosphotungstic acid modified mesoporous material of high specific surface area prepared by the method of the present invention.
(1) Preparation of phosphotungstic acid modified mesoporous material with high specific surface area
14.6g (0.04 mol) of cetyltrimethylammonium bromide as a template and 13.8g of triton-X100 (0.022 mol) were added to 498g of aqueous hydrochloric acid (containing 1.3mol of HCl) and stirred at 40℃until P123 was completely dissolved; then, 20.8g (0.1 mol) of ethyl orthosilicate was added to the above solution, stirring was continued at 40℃for 60 minutes, and then, the mixture was allowed to stand at 40℃for 24 hours for crystallization. Washing the solid product obtained by filtration with deionized water for 6 times, and drying at 110 ℃ for 10 hours after suction filtration to obtain mesoporous material raw powder. And (3) roasting the mesoporous material raw powder at 500 ℃ for 24 hours in an air atmosphere to remove the template agent, so as to obtain the mesoporous material A with high specific surface area.
The specific surface area of the mesoporous material A with high specific surface area is 1254m 2 Per g, pore volume was 0.8mL/g and average pore diameter was 2.8nm.
7 g of the mesoporous material A with high specific surface area and 1g of phosphotungstic acid are put into a 100mL ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of the grinding balls is 3-15mm, the number of the grinding balls is 30, and the rotating speed is 400rpm. And (3) sealing the ball milling tank, and ball milling for 6 hours at the temperature of 40 ℃ in the ball milling tank to obtain the phosphotungstic acid modified mesoporous material A with high specific surface area.
The phosphotungstic acid modified mesoporous material A with high specific surface area is spherical, and the specific surface area is 872m 2 Per gram, the pore volume is 0.6mL/g, the average pore diameter is 2.3nm, and the weight content of the phosphotungstic acid is 12.5%. After the spherical mesoporous material A with high specific surface is loaded with heteropoly acid phosphotungstic acid by using a ball milling method, the pore volume, the average pore diameter and the specific surface area are all reduced. This indicates that phosphotungstic acid is not only present on the outer surface of the mesoporous molecular sieve, but also enters the mesoporous pore canal.
Fig. 1 is an XRD spectrum of the phosphotungstic acid modified mesoporous material a with high specific surface area prepared in example 1, and it can be clearly seen from fig. 1 that a small-angle spectrum peak appears in the XRD spectrum, which indicates that the material has a typical mesoporous pore structure.
Fig. 2 is an SEM scanning electron microscope image of the high specific surface area mesoporous material a prepared in example 1, and fig. 3 is an SEM scanning electron microscope image of the phosphotungstic acid modified high specific surface area mesoporous material a prepared in example 1; as can be seen from fig. 2 and 3, the high specific surface spherical mesoporous material a has a microstructure of mesoporous spheres with a granularity of 5-10 μm; the micro morphology of the phosphotungstic acid modified mesoporous material A with high specific surface area still basically keeps the spherical shape, and the granularity is 5-10 mu m.
(2) Preparation of catalytic cracking aid
Mixing 250g of the phosphotungstic acid modified mesoporous material A with high specific surface area with 550g of ZSM-5 molecular sieve (the molar ratio of Si/Al is 200), adding 50g of deionized water and 536g of 28% alumina sol, and pulping for 2 hours; 91g of calcium nitrate and 48g of cerium nitrate hexahydrate are added under stirring, and the mixture is continuously pulped for 1h; then grinding the obtained slurry continuously for 30 hours at 50 ℃; spray drying the ground slurry at an inlet temperature of 500 ℃ and a tail gas temperature of 180 ℃; roasting the dried product at 550 ℃ for 8 hours to obtain the catalytic cracking auxiliary A.
The specific surface area of the catalytic cracking auxiliary A is 352m 2 /g; pore volume of 0.48cm 3 /g。
The catalytic cracking auxiliary A comprises the following components in percentage by weight: 55% of ZSM-5 molecular sieve, 25% of phosphotungstic acid modified mesoporous material with high specific surface area, 15% of alumina from a binder, 3.1% of CaO from metal salt and CeO 2 1.9％。
Examples 2 to 5
This example is a description of a catalytic cracking aid containing a phosphotungstic acid modified mesoporous material of high specific surface area prepared by the method of the present invention.
Examples 2-5 were conducted by changing the parameters in the preparation process of the phosphotungstic acid modified high specific surface area mesoporous material and the preparation process of the catalytic cracking auxiliary agent in example 1 to obtain phosphotungstic acid modified high specific surface area mesoporous materials B1, C1, D1 and E1 and catalytic cracking auxiliary agents B, C, D and E, respectively.
Table 1 shows the structural parameters of the phosphotungstic acid modified mesoporous material with high specific surface area.
Table 2 shows the compositions of the catalytic cracking assistants obtained in the examples and comparative examples.
Comparative example 1
A catalytic cracking aid D1 was prepared in the same manner as in example 1 except that the ZSM-5 molecular sieve in step (2) (Si/Al molar ratio: 200) was replaced with ZSM-5 molecular sieve (Si/Al molar ratio: 25), and the results are shown in tables 1 and 2.
Comparative example 2
Auxiliary D2 was prepared as in example 1, except that step (1) was omitted and only step (2) was retained, as follows:
800g of ZSM-5 molecular sieve (Si/Al molar ratio of 200), 50g of deionized water and 536g of 28% alumina sol are mixed and pulped for 2 hours; 91g of calcium nitrate and 48g of cerium nitrate hexahydrate are added under stirring, and the mixture is continuously pulped for 1h; then grinding the obtained slurry continuously for 30 hours at 50 ℃; spray drying the ground slurry at an inlet temperature of 500 ℃ and a tail gas temperature of 180 ℃; roasting the dried product at 550 ℃ for 8 hours to obtain the catalytic cracking auxiliary D2.
Compared with zeolite molecular sieve, the phosphotungstic acid modified mesoporous material with high specific surface area has the characteristics of larger specific surface area, larger average pore diameter and larger pore volume. Unlike the assistant A, the assistant D2 is not added with phosphotungstic acid modified mesoporous material with high specific surface area, and the specific surface area and the pore volume are obviously reduced. This shows that the addition of phosphotungstic acid modified mesoporous material with high specific surface area in the auxiliary agent can effectively improve the pore structure.
The results are shown in tables 1 and 2.
Comparative examples 3 to 4
Comparative examples 3 and 4 were conducted by changing the parameters in the preparation process of the phosphotungstic acid modified high specific surface area mesoporous material and the preparation process of the catalytic cracking aid in example 1, respectively, to obtain the phosphotungstic acid modified high specific surface area mesoporous material and the catalytic cracking aids D3 and D4, and the results are shown in tables 1 and 2.
Test example 1
Taking a fixed fluidized bed reactor as an example, the reaction result of the catalytic cracking auxiliary agent provided by the invention is illustrated.
30 g of an auxiliary A, an auxiliary B, an auxiliary C, an auxiliary D, an auxiliary E, a comparative auxiliary D1, a comparative auxiliary D2, a comparative auxiliary D3 and a comparative auxiliary D4 are respectively subjected to aging treatment for 8 hours at 800 ℃ under the condition of 10% water vapor atmosphere, and the aged auxiliary is mixed with an industrial FCC balance catalyst to obtain a catalyst mixture. The catalyst mixture was charged into a reactor of a small-sized fixed fluidized bed reactor apparatus, and a catalytic cracking reaction was performed on a raw oil (raw oil properties are shown in table 3), and test results are shown in table 4.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from comparing the data of the auxiliary A and the auxiliary D1 in the table 4, when the auxiliary A is used, the propylene concentration in the liquefied gas product is obviously higher than the auxiliary D1, and the octane number of the gasoline product is also obviously higher than the auxiliary D1 on the premise of similar conversion rate. This shows that the use of high silica ZSM-5 zeolite molecular sieve (Si/al=200) in the promoter works better than the use of low silica ZSM-5 zeolite molecular sieve (Si/al=25).
Compared with the auxiliary A, the auxiliary D2 has poorer performance in the catalytic cracking reaction. The method shows that the propylene selectivity and the gasoline octane number can be effectively improved by properly adding the phosphotungstic acid modified mesoporous material with high specific surface area into the auxiliary agent.
Compared with the auxiliary A, the auxiliary D3 and the auxiliary D4 have poorer performance in the catalytic cracking reaction. Fully illustrates that the performance is poor as a result of changing various parameters in the preparation process of the phosphotungstic acid modified mesoporous material with high specific surface area and the preparation process of the catalytic cracking auxiliary agent in the embodiment 1.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (18)
1. The catalytic cracking auxiliary agent containing the phosphotungstic acid modified mesoporous material with high specific surface area is characterized by comprising a zeolite molecular sieve with high silicon-aluminum ratio, the phosphotungstic acid modified mesoporous material with high specific surface area, a first oxide and a second oxide;
the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 814-908m 2 Per gram, the pore volume is 0.5-0.7mL/g, the average pore diameter is 2.2-2.5nm, and the content of phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area;
the high silica alumina ratio zeolite molecular sieve is a high silica ZSM-5 molecular sieve and/or a high silica ZRP molecular sieve, and the Si/Al molar ratio of the high silica alumina ratio zeolite molecular sieve is 100-800;
the first oxide is alumina and/or silica;
the second oxide is selected from one or more of magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, cerium oxide and lanthanum oxide;
the content of the zeolite molecular sieve with high silicon-aluminum ratio is 50-60 wt%, the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 25-27.78 wt%, the content of the first oxide is 12-18 wt%, and the content of the second oxide is 3-7 wt%, based on the total weight of the catalytic cracking auxiliary agent.
2. The catalytic cracking aid according to claim 1, wherein the content of phosphotungstic acid is 10-15% by weight based on the total weight of the phosphotungstic acid modified high specific surface area mesoporous material.
3. The catalytic cracking aid of claim 1, wherein the high silica to alumina zeolite molecular sieve has a Si/ai molar ratio of 150-600.
4. A catalytic cracking aid according to any one of claims 1-3, wherein the preparation method of the phosphotungstic acid modified high specific surface area mesoporous material comprises the following steps:
(a) Under the existence of a template agent and polyethylene glycol octyl phenyl ether, a silicon source is contacted with an acidic aqueous solution, and the mixture obtained after the contact is crystallized, washed, filtered, dried and template agent removed to obtain a mesoporous material with high specific surface area;
(b) And mixing and ball milling the high specific surface area mesoporous material and phosphotungstic acid to obtain the phosphotungstic acid modified high specific surface area mesoporous material.
5. The catalytic cracking aid according to claim 4, wherein the template agent is cetyltrimethylammonium bromide.
6. The catalytic cracking aid according to claim 4, wherein the acidic aqueous solution is an aqueous hydrochloric acid solution prepared from water and hydrogen chloride.
7. The catalytic cracking aid of claim 4, wherein the silicon source is selected from one or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate, and silica sol.
8. The catalytic cracking aid of claim 4, wherein the silicon source: polyethylene glycol octyl phenyl ether: the template agent comprises the following components: hydrogen chloride: the molar ratio of water is 1:0.1-0.5:0.1-0.6:5-50:100-500.
9. The catalytic cracking aid of claim 8, wherein the silicon source: polyethylene glycol octyl phenyl ether: the template agent comprises the following components: hydrogen chloride: the molar ratio of water is 1:0.2-0.4:0.2-0.5:10-30:150-400.
10. The catalytic cracking aid of claim 4, wherein the contacting conditions are: the temperature is 25-60 ℃ and the time is 0.5-2h.
11. The catalytic cracking aid of claim 4, wherein the crystallization conditions comprise: the temperature is 25-60 ℃ and the time is 10-40h.
12. The catalytic cracking aid of claim 4, wherein the conditions for removing the templating agent comprise: roasting in air atmosphere at 400-700 deg.c for 5-40 hr.
13. The catalytic cracking aid of claim 4, wherein the ball milling conditions comprise: the temperature is 15-70 ℃ and the time is 0.5-30h.
14. A method for preparing the catalytic cracking aid containing the phosphotungstic acid modified mesoporous material with high specific surface area according to any one of claims 1 to 13, which is characterized in that the method comprises the following steps:
(1) Mixing and pulping a zeolite molecular sieve with high silicon-aluminum ratio, a phosphotungstic acid modified mesoporous material with high specific surface area, an adhesive and water to obtain first slurry;
(2) Mixing and pulping the first slurry and the metal salt aqueous solution to obtain second slurry; the metal salt is nitrate of metal; the metal is one or more of alkaline earth metal, transition metal and rare earth metal;
(3) Grinding the second slurry, and sequentially carrying out spray drying and roasting treatment to obtain a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with high specific surface area;
wherein the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 814-908m 2 Per gram, the pore volume is 0.5-0.7mL/g, the average pore diameter is 2.2-2.5nm, and the content of phosphotungstic acid is 8-19 wt% based on the total weight of the phosphotungstic acid modified mesoporous material with high specific surface area;
the high silicon aluminum ratio zeolite molecular sieve is used in an amount of 100-2000 parts by weight, the phosphotungstic acid modified high specific surface area mesoporous material is used in an amount of 50-1200 parts by weight, the binder is used in an amount of 200-2500 parts by weight, and the metal salt is used in an amount of 30-100 parts by weight relative to 100 parts by weight of water.
15. The method of claim 14, wherein the metal is selected from one or more of magnesium, calcium, strontium, barium, zinc, cerium, and lanthanum.
16. The method of claim 14, wherein the firing conditions include: the temperature is 450-650 ℃ and the time is 3-15h.
17. A catalytic cracking aid comprising a phosphotungstic acid modified high specific surface area mesoporous material prepared by the method of any one of claims 14-16.
18. Use of a catalytic cracking aid containing a phosphotungstic acid modified mesoporous material with high specific surface area according to any one of claims 1 to 13 and 17 in catalytic cracking reactions of hydrocarbon oils.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049284A (en) * | 2009-10-30 | 2011-05-11 | 中国石油天然气股份有限公司 | Catalytic cracking propylene additive and preparation method thereof |
| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
| CN103586059A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phospho-tungstic acid catalyst, preparation method thereof, applications thereof and preparation method of ethyl acetate |
| CN104248976A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and cyclohexanone glyceryl ketal preparation method |
| CN106552665A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking and its preparation method and application |
| CN108484376A (en) * | 2018-04-27 | 2018-09-04 | 宿迁科思化学有限公司 | A kind of production technology of the solid acid catalysis synthesis to substituent group acetophenone compounds |
| CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2863913B1 (en) * | 2003-12-23 | 2006-12-29 | Inst Francais Du Petrole | ZEOLITHIC CATALYST, SILICO-ALUMINUM MATRIX AND ZEOLITE BASE, AND METHOD FOR HYDROCRACKING HYDROCARBON LOADS |
| US10441944B2 (en) * | 2015-06-30 | 2019-10-15 | Hindustan Petroleum Corporation Ltd. | Catalyst composition for isomerization of paraffins |
-
2020
- 2020-04-24 CN CN202010332236.0A patent/CN113546669B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049284A (en) * | 2009-10-30 | 2011-05-11 | 中国石油天然气股份有限公司 | Catalytic cracking propylene additive and preparation method thereof |
| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
| CN103586059A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phospho-tungstic acid catalyst, preparation method thereof, applications thereof and preparation method of ethyl acetate |
| CN104248976A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and cyclohexanone glyceryl ketal preparation method |
| CN106552665A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking and its preparation method and application |
| CN108484376A (en) * | 2018-04-27 | 2018-09-04 | 宿迁科思化学有限公司 | A kind of production technology of the solid acid catalysis synthesis to substituent group acetophenone compounds |
| CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
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