CN113546669A - 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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- CN113546669A CN113546669A CN202010332236.0A CN202010332236A CN113546669A CN 113546669 A CN113546669 A CN 113546669A CN 202010332236 A CN202010332236 A CN 202010332236A CN 113546669 A CN113546669 A CN 113546669A
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- Prior art keywords
- surface area
- specific surface
- catalytic cracking
- phosphotungstic acid
- mesoporous material
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 108
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 107
- 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 107
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 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 51
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 42
- 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 42
- 239000010457 zeolite Substances 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 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
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 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
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 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
- 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
- 229910001648 diaspore 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000243 solution Substances 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
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 238000004939 coking 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
- 239000002245 particle Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 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
- 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
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000921 elemental analysis 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
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier 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
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Images
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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 a high specific surface area, and a preparation method and application thereof. Wherein the catalytic cracking auxiliary agent comprises a zeolite molecular sieve with a high silica-alumina ratio and a phosphotungstic acid modified mesoporous material with a high specific surface area, wherein the phosphotungstic acid modified mesoporous material with a high specific surface area is spherical, and the specific surface area is 810-1100m2Per g, pore volume of 0.4-1mL/gThe 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 assistant provided by the invention is used in the catalytic cracking process, can greatly improve the concentration of propylene in liquefied gas under the condition of not increasing the yield of catalytic cracking liquefied gas, and can also improve the octane number of catalytic cracking gasoline.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material with high specific surface area, and a preparation method and application thereof.
Background
In recent years, crude oil deterioration has limited the steam cracking of raw naphtha, and has severely affected the increase in propylene production. Therefore, the catalytic cracking unit with wider raw material source and lower operation cost can increase the propylene more economically and conveniently, and is generally concerned by people. In addition, most FCC conventional catalytic cracking units use catalytic cracking promoters to increase propylene yield while reducing gasoline octane.
The FCC catalytic cracking promoter generally comprises a zeolite molecular sieve having an MFI framework structure as a main component, particularly a ZSM-5 molecular sieve. 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 yield-increasing effect on propylene. In order to overcome this drawback, researchers have made various improvements to the synthesis techniques 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 channels, and if the reactant molecules are larger, the reactant molecules are difficult to enter the pore channels for reaction, so that the effective utilization rate of the catalytic cracking auxiliary agent is lower; in addition, because the pore channels of the molecular sieve are narrow, partial product molecules are difficult to diffuse out, deep dehydrogenation is easy to cause to form coking, and the inactivation of the molecular sieve is promoted. Compared with zeolite molecular sieve, the all-silicon mesoporous material has highly ordered mesoporous channels, large specific surface area, large pore diameter, large pore volume and thicker pore wall, and can keep higher mechanical strength and good catalytic performance and adsorption performance. However, the all-silicon mesoporous molecular sieve itself is not acidic, and it is difficult to be used alone as a catalyst for hydrocarbon conversion reaction.
Therefore, the research and development of the catalytic cracking auxiliary agent suitable for increasing the yield of propylene are of great 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 aid in the prior art, and provides a catalytic cracking aid containing a phosphotungstic acid modified mesoporous material with a 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, the concentration of propylene in liquefied gas can be greatly improved under the condition of not increasing the yield of catalytic cracking liquefied gas, and the octane number of catalytic cracking gasoline can also be improved.
In order to achieve the above object, the invention provides a catalytic cracking assistant containing a phosphotungstic acid modified mesoporous material with a high specific surface area, wherein the catalytic cracking assistant comprises a zeolite molecular sieve with a high silica-alumina ratio and a phosphotungstic acid modified mesoporous material with a high specific surface area, wherein the phosphotungstic acid modified mesoporous material with a high specific surface area is spherical, and the specific surface area is 810-2The 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 invention provides a preparation method of a catalytic cracking assistant containing a phosphotungstic acid modified mesoporous material with a high specific surface area, wherein the method comprises the following steps:
(1) mixing and pulping a zeolite molecular sieve with a high silica-alumina ratio, a phosphotungstic acid modified mesoporous material with a high specific surface area, an adhesive and deionized water to obtain first slurry;
(2) mixing and pulping the first slurry and the aqueous solution of the metal salt to obtain second slurry;
(3) grinding the second slurry, and then sequentially carrying out spray drying and roasting treatment to obtain a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with a high specific surface area;
wherein the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 810-1100m2The 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 assistant containing a phosphotungstic acid modified mesoporous material with a high specific surface area, which is prepared by the method.
The fourth aspect of the invention provides an application of the catalytic cracking assistant containing the phosphotungstic acid modified mesoporous material with high specific surface area in catalytic cracking reaction of hydrocarbon oil.
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 in the existing catalytic cracking production device, does not need to change process conditions or change production raw materials, and is simple to operate;
(2) the catalytic cracking assistant for increasing the yield of propylene provided by the invention mainly comprises the components of the zeolite molecular sieve with high silica-alumina ratio and the phosphotungstic acid modified mesoporous material with high specific surface area, and has the advantages of low raw material price and simple preparation method.
(3) The catalytic cracking assistant for increasing the yield of propylene provided by the invention is used for catalytic cracking reaction, can greatly improve the concentration of propylene in liquefied gas under the condition of unchanged yield of liquefied gas, and simultaneously improves the octane number of a gasoline product.
(4) The preparation method of the catalytic cracking assistant for increasing the yield of propylene, provided by the invention, has the advantages of simple process, easily controlled 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 a phosphotungstic acid modified mesoporous material A with high specific surface area prepared in example 1;
FIG. 2 is an SEM scanning electron micrograph of a mesoporous material A with a high specific surface area prepared in example 1;
FIG. 3 is an SEM scanning electron microscope image of the phosphotungstic acid modified mesoporous material A with high specific surface area prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The zeolite molecular sieves are various in types and have clear pore channel structure characteristics, wherein the zeolite molecular sieves comprise one-dimensional straight-through pore channels, two-dimensional cross pore channels, three-dimensional pore channels and multi-dimensional pore channels. Because the pore channel structure of the zeolite molecular sieve is short-range ordered, the aperture is generally less than 2.0nm, and the zeolite molecular sieve can show better shape selection effect in small molecular catalytic reaction and adsorption separation. Therefore, in the prior art, typical FCC cracking aids generally use zeolite molecular sieves (mainly ZSM-5 molecular sieves) as the main component. The hydrogen type zeolite molecular sieve has an acid site and has strong activation capability, but because the pore size is small, the diffusion of reaction raw materials and products is easily influenced, and further, the propylene selectivity is low and the catalyst stability is poor. In order to improve the catalytic performance of the zeolite molecular sieve, researchers modify and modify the surface characteristics of the zeolite molecular sieve, so that the performance of the catalytic cracking assistant is improved to a certain extent. However, the zeolite molecular sieve treated by modification can only change the surface characteristics, but can not change the basic framework structure of the molecular sieve, and the problem of diffusion of raw materials and products is difficult to solve. Therefore, it is difficult to greatly improve the propylene selectivity by modifying the zeolite molecular sieve.
The inventor of the invention discovers that when a certain amount of all-silicon mesoporous material is mixed with the zeolite molecular sieve and modified to prepare the catalytic cracking aid, the pore structure of the aid can be effectively improved, so that the aid is more beneficial to rapid diffusion of reactant molecules and product molecules, side reactions are effectively inhibited, and the propylene selectivity is improved. However, the all-silicon mesoporous material does not have an acid center, and is difficult to catalyze the conversion of hydrocarbon raw materials in a cracking reaction. If phosphotungstic acid is used as a modifier to modify the all-silicon mesoporous material, an acid center can be introduced on the surface of the mesoporous material. A certain amount of phosphotungstic acid modified mesoporous material with high specific surface area is mixed with a zeolite molecular sieve and modified to prepare a catalytic cracking auxiliary agent, so that the conversion rate of raw materials, the selectivity of propylene and the octane number of cracked gasoline can be greatly improved.
The invention provides a catalytic cracking assistant containing a phosphotungstic acid modified mesoporous material with a high specific surface area, wherein the catalytic cracking assistant comprises a zeolite molecular sieve with a high silica-alumina ratio and a phosphotungstic acid modified mesoporous material with a high specific surface area, wherein the phosphotungstic acid modified mesoporous material with a high specific surface area is spherical, and the specific surface area is 810-2The 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 814-908m2The 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 limited content can be used for better modifying the mesoporous material with high specific surface area, namely, acid centers can be introduced into the surface of the mesoporous material with high specific surface area.
According to the invention, the zeolite molecular sieve with high silica-alumina ratio is a high-silica ZSM-5 molecular sieve and/or a high-silica ZRP molecular sieve; preferably, the Si/Al molar ratio of the high-Si/Al ratio zeolite molecular sieve is 100-800, more preferably 150-600, and further preferably 200-500.
According to the invention, the weight ratio of the zeolite molecular sieve with high silica-alumina 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, based on the total weight of the catalytic cracking assistant, the content of the zeolite molecular sieve with high silica-alumina ratio is 45-65 wt%, and the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 20-30 wt%; preferably, based on the total weight of the catalytic cracking assistant, the content of the zeolite molecular sieve with high silica-alumina ratio is 50-60 wt%, and the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 20-28 wt%; more preferably, based on the total weight of the catalytic cracking assistant, the content of the zeolite molecular sieve with high silica-alumina 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%.
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 condition that a template agent and polyethylene glycol octyl phenyl ether exist, a silicon source is contacted with an acidic aqueous solution, and a mixture obtained after the contact is crystallized, washed, filtered, dried and subjected to template agent removal treatment to obtain a mesoporous material with a high specific surface area;
(b) and mixing and ball-milling the mesoporous material with high specific surface area and phosphotungstic acid to obtain the phosphotungstic acid modified mesoporous material with high specific surface area.
According to the invention, the specific surface area of the mesoporous material with high specific surface area is 1207-1281m2Per g, pore volume of 0.8-0.9mL/g, average pore diameter of 2.6-3 nm.
According to the invention, the weight ratio of the mesoporous material with high specific surface area to the phosphotungstic acid is (4.26-11.5): 1, preferably (4-9): 1.
according to the invention, the template agent 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, and is preferably ethyl orthosilicate.
According to the invention, the silicon source: polyethylene glycol octyl phenyl ether (Triton X-100): the template agent is: 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 said contact comprise: the temperature is 25-60 ℃, and the time is 0.5-2 h; the contacting may be performed under agitation conditions, wherein the agitation conditions include: the stirring rate was 200 and 900 rpm.
According to the invention, the crystallization conditions comprise: the temperature is 25-60 ℃ and the time is 10-40 h.
According to the present invention, the washing method is not particularly limited, and may be a method well known to those skilled in the art. Preferably: and mixing the solid obtained by separation with deionized water, stirring and pulping for 2 hours, standing for 3 hours, and separating. The above washing process was repeated 6-10 times.
According to the invention, the suction filtration separation is a well-known way of separating liquid from solid particles, which is to separate liquid from solid particles or a mixture of liquid and liquid by using air pressure.
According to the invention, the drying conditions are preferably: the drying temperature is 70-150 ℃, and the drying time is 3-20 h.
According to the present invention, the conditions for removing the template agent include: roasting in air atmosphere at 400-700 deg.c for 5-40 hr;
according to the invention, the ball milling conditions include: the temperature is 15-70 ℃, and the time is 0.5-30 h; preferably, the temperature is 20-70 ℃ and the time is 1-30 h.
According to the present invention, the catalytic cracking aid further comprises a first oxide; preferably, the first oxide is an oxide obtained by roasting a binder, and is preferably alumina and/or silica; more preferably, the binder is selected from one or more of silica sol, alumina sol, pseudoboehmite, and diaspore.
According to the present 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 assistant; preferably, 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 assistant.
In the invention, when the catalytic cracking assistant comprises a zeolite molecular sieve with high silica-alumina ratio, a phosphotungstic acid modified mesoporous material with high specific surface area, a first oxide and a second oxide, the sum of the total contents of the components is 100 wt%.
The second aspect of the invention provides a preparation method of the catalytic cracking assistant 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 a high silica-alumina ratio, a phosphotungstic acid modified mesoporous material with a high specific surface area, an adhesive and deionized water to obtain first slurry;
(2) mixing and pulping the first slurry and the aqueous solution of the metal salt to obtain second slurry;
(3) grinding the second slurry, and then sequentially carrying out spray drying and roasting treatment to obtain a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with a high specific surface area;
wherein the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 810-1100m2The 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 814-908m2Per g, pore volume of 0.5-0.7mL/g, average pore diameter of 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 the step (1), the beating time is 0.5-5 h.
According to the invention, in the step (2), the beating time is 0.5-2 h.
According to the invention, in the step (3), the obtained slurry is continuously ground at 15-100 ℃ for 2-40h and is subjected to spray drying at 150-600 ℃; the dried product is roasted for 3-15h at the temperature of 450-650 ℃.
According to the invention, the metal salt is a nitrate of a metal; preferably, the metal is one or more of an alkaline earth metal, a transition metal and a rare earth metal, more preferably, the metal is selected from one or more of magnesium, calcium, strontium, barium, zinc, cerium and lanthanum.
According to the invention, relative to 100g of water, the dosage of the zeolite molecular sieve with high silica-alumina ratio is 100-2000 parts by weight, the dosage of the phosphotungstic acid modified mesoporous material with high specific surface area is 50-1200 parts by weight, the dosage of the binder is 200-2500 parts by weight, and the dosage of the metal salt is 30-100 parts by weight.
The third aspect of the invention provides a catalytic cracking assistant containing a phosphotungstic acid modified mesoporous material with a high specific surface area, which is prepared by the method.
According to the invention, the specific surface area of the catalytic cracking aid is 320-400m2Per g, pore volume of 0.4-0.55cm3(ii)/g; preferably, the specific surface area is 329-2Per g, pore volume of 0.43-0.51cm3/g。
The fourth aspect of the invention provides an application of the catalytic cracking assistant containing the phosphotungstic acid modified mesoporous material with high specific surface area in catalytic cracking reaction of hydrocarbon oil.
When the catalytic cracking assistant provided by the invention is used in a catalytic cracking process, the catalytic cracking assistant can be independently added into a catalytic cracking reactor, and can also be mixed with a catalytic cracking catalyst for use. In general, the catalytic cracking aid provided by the present invention comprises 2 to 15 wt%, preferably 5 to 10 wt% of the total weight of the catalytic cracking aid provided by the present invention of the FCC catalyst.
The catalytic cracking assistant provided by the invention can be used for processing various hydrocarbon oils, and the hydrocarbon oils are selected from various petroleum fractions, such as crude oil, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight-run wax oil, coking 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 conditions of the hydrocarbon oil are conventional catalytic cracking conditions. Generally, the hydrocarbon oil catalytic cracking conditions are: the reaction temperature is 400-600 ℃, preferably 450-550 ℃; the weight hourly space velocity is 10-120h-1Preferably 10-80h-1(ii) a The weight ratio of the solvent to the oil is 1-20, preferably 3-15.
The catalytic cracking assistant provided by the invention can be used for various existing catalytic cracking reactors, such as fixed bed reactors, fluidized bed reactors, riser reactors and the like.
The zeolite molecular sieve with high silica-alumina 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 builders of high silica to alumina ratio have improved propylene selectivity and stability, but the improvement is limited. The catalytic cracking assistant provided by the invention adopts the mixture of the zeolite molecular sieve with high silica-alumina ratio and the phosphotungstic acid modified mesoporous material with high specific surface area as the main active component, and introduces a proper amount of at least one of alkaline earth metal oxide, transition metal oxide and rare earth metal oxide, so that the selectivity of the catalytic cracking reaction process to propylene can be obviously improved, the concentration of the 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, the pore structure parameter analysis of the samples was carried out on an adsorption apparatus available from Micromeritics, USA, model ASAP2020-M + C; x-ray diffraction analysis of the samples was performed on an X-ray diffractometer, model D8 Advance, available from Bruker AXS, Germany; the scanning electron microscope picture of the sample is obtained on an XL-30 type field emission environment scanning electron microscope produced by FEI company in America; the elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., Ltd, and is of a type DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
The ZSM-5 sieves of different silica to alumina ratios used in the examples and comparative examples were obtained from Shanghai Korea molecular sieves Co., Ltd; the ZRP zeolite molecular sieve is purchased from Hezhong Biochemical manufacturing company, Inc. in Wuhan City; the alumina sol and the silica sol are purchased from Zibo Jiarun chemical Co., Ltd; pseudoboehmite was purchased from Zibo Hengqi powder New Material Co., Ltd; other reagents were purchased from the national pharmaceutical group chemical reagents, ltd.
Example 1
This example illustrates a catalytic cracking assistant containing a phosphotungstic acid modified mesoporous material with a 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 (0.04mol) of cetyltrimethylammonium bromide as a template and 13.8g of Triton-X100 (0.022mol) 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 (0.1mol) of ethyl orthosilicate is added into the solution, the solution is stirred for 60min at 40 ℃, and then the solution is kept stand for 24h for crystallization at 40 ℃. Washing the solid product obtained by filtering with deionized water for 6 times, and drying at 110 ℃ for 10h after suction filtration to obtain the mesoporous material raw powder. And roasting the mesoporous material raw powder for 24 hours at 500 ℃ in an air atmosphere to remove the template agent, thereby obtaining the mesoporous material A with high specific surface area.
The specific surface area of the mesoporous material A with high specific surface area is 1254m2Pore volume of 0.8mL/g, and average pore diameter of 2.8 nm.
And (3) putting 7 g of the mesoporous material A with the high specific surface area and 1g of phosphotungstic acid into a 100mL ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3-15mm, the number of the grinding balls is 30, and the rotating speed is 400 rpm. And (3) sealing the ball milling tank, and carrying out ball milling for 6h in the ball milling tank at the temperature of 40 ℃ to obtain the phosphotungstic acid modified mesoporous material A with the high specific surface area.
The phosphotungstic acid modified mesoporous material A with high specific surface area is spherical, and the specific surface area is 872m2The pore volume is 0.6mL/g, the average pore diameter is 2.3nm, and the weight content of phosphotungstic acid is 12.5 percent. After the spherical mesoporous material A with high specific surface is loaded with heteropoly acid phosphotungstic acid by 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 channels.
Fig. 1 is an XRD spectrogram 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 spectral peak appears in the XRD spectrogram, indicating that the material has a typical mesoporous channel 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 FIGS. 2 and 3, the microscopic morphology of the spherical mesoporous material A with high specific surface is mesoporous spheres with the granularity of 5-10 μm; the microstructure of the phosphotungstic acid modified mesoporous material A with high specific surface area still keeps spherical basically, and the granularity is 5-10 mu m.
(2) Preparation of catalytic cracking assistant
Mixing the phosphotungstic acid modified mesoporous material A250g with high specific surface area prepared in the step with 550g of ZSM-5 molecular sieve (the Si/Al molar ratio is 200), adding 50g of deionized water and 536g of 28% alumina sol, and pulping for 2 hours; adding 91g of calcium nitrate and 48g of cerous nitrate hexahydrate under the stirring condition, and continuously pulping the mixture for 1 hour; then continuously grinding the obtained slurry for 30h at 50 ℃; spray drying the ground slurry at the inlet temperature of 500 ℃ and the tail gas temperature of 180 ℃; and roasting the dried product at 550 ℃ for 8h to obtain the catalytic cracking assistant A.
The specific surface area of the catalytic cracking assistant A is 352m2(ii)/g; pore volume of 0.48cm3/g。
The catalytic cracking assistant A comprises the following components in percentage by weight: ZSM-5 molecular sieve 55%, phosphotungstic acid modified mesoporous material with high specific surface area 25%, and binderAlumina 15%, and CaO 3.1% and CeO from metal salts21.9％。
Examples 2 to 5
This example illustrates a catalytic cracking assistant containing a phosphotungstic acid modified mesoporous material with a high specific surface area prepared by the method of the present invention.
By 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 assistant in the embodiment 1, the phosphotungstic acid modified mesoporous material with high specific surface area, B1, C1, D1 and E1 and the catalytic cracking assistant B, C, D and E are respectively obtained by carrying out the embodiments 2 to 5.
Table 1 lists various parameters in the preparation process of the phosphotungstic acid modified mesoporous material with high specific surface area and structural parameters of the phosphotungstic acid modified mesoporous material with high specific surface area.
Table 2 shows the compositions of the catalytic cracking aids obtained in the examples and comparative examples.
Comparative example 1
A catalytic cracking assistant D1 was prepared according to the method of example 1, except that the ZSM-5 molecular sieve (Si/Al molar ratio of 200) in step (2) was replaced with the ZSM-5 molecular sieve (Si/Al molar ratio of 25), and the results are shown in tables 1 and 2.
Comparative example 2
Auxiliary D2 was prepared according to the method of example 1, except that step (1) was eliminated and only step (2) was retained, as follows:
mixing 800g of ZSM-5 molecular sieve (the Si/Al molar ratio is 200), 50g of deionized water and 536g of 28 percent alumina sol and pulping for 2 hours; adding 91g of calcium nitrate and 48g of cerous nitrate hexahydrate under the stirring condition, and continuously pulping the mixture for 1 hour; then continuously grinding the obtained slurry for 30h at 50 ℃; spray drying the ground slurry at the inlet temperature of 500 ℃ and the tail gas temperature of 180 ℃; and roasting the dried product at 550 ℃ for 8h to obtain the catalytic cracking assistant D2.
Compared with zeolite molecular sieves, the phosphotungstic acid modified mesoporous material with high specific surface area has the characteristics of large specific surface area, large average pore diameter and large pore volume. Different from the assistant A, the assistant D2 has no phosphotungstic acid added to modify the mesoporous material with high specific surface area, and the specific surface area and the pore volume are obviously reduced. The result shows that the phosphotungstic acid modified mesoporous material with high specific surface area can effectively improve the pore channel structure by adding the phosphotungstic acid into the auxiliary agent.
The results are shown in tables 1 and 2.
Comparative examples 3 to 4
The 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 assistant in example 1 were changed, and comparative example 3 and comparative example 4 were carried out to obtain the phosphotungstic acid modified mesoporous material with high specific surface area and the catalytic cracking assistants D3 and D4, respectively, and the results are shown in tables 1 and 2.
Test example 1
The reaction result of the catalytic cracking assistant provided by the invention is illustrated by taking a fixed fluidized bed reactor as an example.
30 g of an auxiliary agent A, an auxiliary agent B, an auxiliary agent C, an auxiliary agent D, an auxiliary agent E, a comparative example auxiliary agent D1, a comparative example auxiliary agent D2, a comparative example auxiliary agent D3 and a comparative example auxiliary agent D4 are aged for 8 hours under the conditions of 800 ℃ and 10% of water vapor atmosphere, and the aged auxiliary agents are mixed with an industrial FCC equilibrium 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 carried out on the feedstock oil (properties of the feedstock oil are shown in Table 3), and the test results are shown in Table 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Comparing the data of the additive A and the additive D1 in Table 4, it can be seen that, under the premise of similar conversion rate, when the additive A is used, the concentration of propylene in the liquefied gas product is obviously higher than that of the additive D1, and the octane number of the gasoline product is also obviously higher than that of the additive D1. This shows that the use of a high-silicon ZSM-5 zeolite molecular sieve (Si/Al ═ 200) in the adjuvant works better than the use of a low-silicon ZSM-5 zeolite molecular sieve (Si/Al ═ 25).
Aid D2 performed less well in catalytic cracking reactions than aid a. The method proves that the phosphotungstic acid modified mesoporous material with high specific surface area can effectively improve the propylene selectivity and the gasoline octane number by properly adding the phosphotungstic acid into the auxiliary agent.
The performance of the assistants D3 and D4 in the catalytic cracking reaction was poorer than that of the assistant A. The change of the 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 assistant in example 1 is fully explained, and the performance of the result is poor.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. The catalytic cracking assistant containing the phosphotungstic acid modified mesoporous material with the high specific surface area is characterized by comprising a zeolite molecular sieve with the high silica-alumina ratio and a phosphotungstic acid modified mesoporous material with the high specific surface area, wherein the phosphotungstic acid modified mesoporous material with the high specific surface area is spherical, and the specific surface area is 810-1100 m-2The 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.
2. The catalytic cracking assistant according to claim 1, wherein the specific surface area of the phosphotungstic acid modified high specific surface area mesoporous material is 814-908m2The 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.
3. The catalytic cracking aid of claim 1, wherein the high silica to alumina ratio zeolite molecular sieve is a high silica ZSM-5 molecular sieve and/or a high silica ZRP molecular sieve; preferably, the Si/Al molar ratio of the high-silica-alumina-ratio zeolite molecular sieve is 100-800, more preferably 150-600;
preferably, the weight ratio of the zeolite molecular sieve with high silica-alumina ratio to the phosphotungstic acid modified mesoporous material with high specific surface area is (1.5-3.5): 1.
4. the catalytic cracking assistant of any one of claims 1 to 3, wherein the content of the zeolite molecular sieve with high silica-alumina ratio is 45-65 wt%, and the content of the phosphotungstic acid modified mesoporous material with high specific surface area is 20-30 wt%, based on the total weight of the catalytic cracking assistant.
5. The catalytic cracking assistant according to any one of claims 1 to 4, wherein the preparation method of the phosphotungstic acid modified mesoporous material with high specific surface area comprises the following steps:
(a) under the condition that a template agent and polyethylene glycol octyl phenyl ether exist, a silicon source is contacted with an acidic aqueous solution, and a mixture obtained after the contact is crystallized, washed, filtered, dried and subjected to template agent removal treatment to obtain a mesoporous material with a high specific surface area;
(b) and mixing and ball-milling the mesoporous material with high specific surface area and phosphotungstic acid to obtain the phosphotungstic acid modified mesoporous material with high specific surface area.
6. The catalytic cracking aid of claim 5, wherein the templating agent is cetyltrimethylammonium bromide;
preferably, the acidic aqueous solution is a hydrochloric acid aqueous solution prepared from water and hydrogen chloride;
preferably, the silicon source is selected from one or more of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol;
preferably, the silicon source: polyethylene glycol octyl phenyl ether: the template agent is: 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.
7. The catalytic cracking aid of claim 5, wherein the contacting conditions are: the temperature is 25-60 ℃, and the time is 0.5-2 h;
preferably, the crystallization conditions include: the temperature is 25-60 ℃, and the time is 10-40 h;
preferably, the conditions for removing the template agent include: roasting in air atmosphere at 400-700 deg.c for 5-40 hr;
preferably, the ball milling conditions include: the temperature is 15-70 ℃ and the time is 0.5-30 h.
8. The catalytic cracking aid of any one of claims 1 to 7, wherein the catalytic cracking aid further comprises a first oxide;
preferably, the first oxide is an oxide obtained by roasting a binder, and is preferably alumina and/or silica;
more preferably, the binder is selected from one or more of silica sol, alumina sol, pseudoboehmite, and diaspore.
9. The catalytic cracking aid of any one of claims 1 to 8, wherein 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.
10. The catalytic cracking promoter according to claim 8 or 9, wherein the first oxide is present in an amount of 10 to 20 wt% and the second oxide is present in an amount of 1 to 9 wt%, based on the total weight of the catalytic cracking promoter.
11. A preparation method of a catalytic cracking assistant containing phosphotungstic acid modified mesoporous material with high specific surface area is characterized by comprising the following steps:
(1) mixing and pulping a zeolite molecular sieve with a high silica-alumina ratio, a phosphotungstic acid modified mesoporous material with a high specific surface area, an adhesive and water to obtain first slurry;
(2) mixing and pulping the first slurry and the aqueous solution of the metal salt to obtain second slurry;
(3) grinding the second slurry, and then sequentially carrying out spray drying and roasting treatment to obtain a catalytic cracking auxiliary agent containing a phosphotungstic acid modified mesoporous material with a high specific surface area;
wherein the specific surface area of the phosphotungstic acid modified mesoporous material with high specific surface area is 810-1100m2The 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.
12. The method of claim 11, wherein the metal salt is a nitrate salt of a metal;
preferably, the metal is one or more of an alkaline earth metal, a transition metal and a rare earth metal, more preferably, the metal is selected from one or more of magnesium, calcium, strontium, barium, zinc, cerium and lanthanum;
preferably, the amount of the zeolite molecular sieve with high silica-alumina ratio is 100-2000 parts by weight, the amount of the phosphotungstic acid modified mesoporous material with high specific surface area is 50-1200 parts by weight, the amount of the binder is 200-2500 parts by weight, and the amount of the metal salt is 30-100 parts by weight, relative to 100 parts by weight of water.
13. The method of claim 11, wherein the firing conditions include: the temperature is 450-650 ℃, and the time is 3-15 h.
14. The catalytic cracking assistant containing the phosphotungstic acid modified mesoporous material with high specific surface area prepared by the method of any one of claims 11 to 13.
15. Use of the catalytic cracking aid containing the phosphotungstic acid modified mesoporous material with high specific surface area as claimed in any one of claims 1 to 10 and 14 in catalytic cracking reaction of hydrocarbon oil.
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