CN110372005B - Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions - Google Patents
Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions Download PDFInfo
- Publication number
- CN110372005B CN110372005B CN201910593146.4A CN201910593146A CN110372005B CN 110372005 B CN110372005 B CN 110372005B CN 201910593146 A CN201910593146 A CN 201910593146A CN 110372005 B CN110372005 B CN 110372005B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- source
- aluminum phosphate
- hierarchical pore
- phosphate molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 86
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 40
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000011737 fluorine Substances 0.000 title claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 30
- -1 fluorine ions Chemical class 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 10
- 230000023556 desulfurization Effects 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 239000012153 distilled water Substances 0.000 description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 19
- 239000003921 oil Substances 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 9
- 229940011182 cobalt acetate Drugs 0.000 description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910017119 AlPO Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- URXQDXAVUYKSCK-UHFFFAOYSA-N hexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH+](C)C URXQDXAVUYKSCK-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical group 0.000 description 1
- 239000007800 oxidant agent 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates [APO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of chemical catalysts, and particularly relates to a method for synthesizing a hierarchical porous aluminum phosphate molecular sieve by using fluoride ions. Mixing an aluminum source, a phosphorus source, a metal source and water according to a certain molar ratio, respectively adding a microporous template agent, a mesoporous template agent and a fluorine source to prepare a molecular sieve synthetic solution, aging at room temperature, and then placing in a high-pressure reaction kettle for crystallization to prepare the hierarchical pore aluminum phosphate molecular sieve. The method reduces the dosage of the mesoporous template agent by utilizing a fluorine ion system, and the prepared hierarchical pore aluminum phosphate molecular sieve shows higher desulfurization effect in the catalytic oxidation desulfurization reaction.
Description
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to a method for synthesizing a hierarchical porous aluminum phosphate molecular sieve by using fluoride ions and related application.
Background
The synthesis of aluminum phosphate molecular sieves was first reported by Wilson et al in 1982. The aluminum phosphate molecular sieve is composed of aluminum oxide tetrahedron and phosphorus oxide tetrahedron, and the crystal framework of the aluminum phosphate molecular sieve is electrically neutral and has weak surface acidity. The introduction of hetero atoms makes the skeleton produce negative charge, increases the acidity of the molecular sieve and raises its catalytic performance. The heteroatom aluminum phosphate molecular sieve is generally six-membered to twelve-membered ring, and the pore diameter is 0.3-0.8nm. The microporous aluminum phosphate molecular sieve has a small pore passage, so that the diffusion resistance is large in the catalytic reaction, the mass transfer rate is slow, and the conversion rate and the selectivity of reactants are reduced. To overcome the shortcomings of single microporous molecular sieve, a hierarchical pore aluminum phosphate molecular sieve is prepared. The hierarchical pore aluminum phosphate molecular sieve has the advantages of the hierarchical pore structure and the grading advantages which are not possessed by the single pore structure. The existence of a plurality of pore canals weakens the space diffusion limit of macromolecules, increases the intra-crystal diffusion speed of molecules, improves the reaction rate of catalytic reaction, inhibits the occurrence of side reaction, and reduces the carbon deposition phenomenon, thereby prolonging the catalytic life of the molecular sieve.
The existing methods for synthesizing the hierarchical pore molecular sieve are more, and can be divided into a top-down method and a bottom-up method from the crystallization direction. The "top-down" method is a method of introducing mesopores by post-treating the original molecular sieve, and the method includes a molecular sieve skeleton dealumination method, a desilication method, a recrystallization method using a surfactant as a template, a seed crystal method and the like. The "bottom-up" method refers to the synthesis of hierarchical pores by simultaneously introducing micropores and mesopores on a molecular sieve. The method includes a hard template method, a soft template method, a template-free self-assembly method and the like.
Snc-z M, manj Lo-san A, D I, et al crystal Growth&Design,2013,13 (6): 2476) synthesizes AFI type molecular sieve with complex multilevel pore canals and doped with Co by taking BP2000 carbon black as a hard template, and roasting to remove carbon nano particles can communicate characteristic micropores of AFI and intercrystalline mesopores parallel to the micropores. Ryoo et al (Choi M, srivastava R, ryoo R. Chemical Communications,2006,42 (42): 4380) add [ 3-trimethoxysilylpropyl ] to the synthesis]Cetyl dimethyl ammonium chloride is used as a soft template agent, and the hierarchical porous AlPO is synthesized by hydrothermal assembly 4 -5 and AlPO 4 -11 molecular sieves. Perez et al (Verboekend D, milina M, perez-Ramirez J. Chemistry Materials,2014, 26 (15): 4552) post-treat microporous SAPO-11 molecular sieves with a base to prepare corresponding hierarchical pore Materials, and the external surface area and pore volume of the SAPO-11 molecular sieves are increased by a factor of 4 by modification with an organic base. Murthy et al (Murthy K, kulkarni S J, masthane S K. Microporous)&Mesoporous Materials,2001,43 (2): 201) studied the synthesis of hierarchical pore SAPO-5, SAPO-11, meAPO-5, meAPO-11 molecular sieves without a template, which suggested that the generation of the pore structure in the molecular sieves was related to the volatilization of water vapor, the directional movement of cations, and the change in the structure of the molecular sieves due to carbon oxidation during template removal during calcination. The AEL and AFI forms with an intercrystalline mesoporous structure were synthesized by Xiao et al (Xi D, sun Q, chen X, et al chemical Communications,2015,51 (60): 11987) using a solventless method with tetramethylguanidine, a conventional micropore structure directing agentA molecular sieve. Whether it is an organosilane surfactant, a long-chain alkyl ammonium bromide and alkyl phosphoric acid, or a polyamine surfactant, it is expensive, so that the synthesis cost of the multi-pore aluminum phosphate molecular sieve is much higher than that of the corresponding microporous molecular sieve. In order to reduce the cost, the post-treatment method utilizes a method of extracting skeleton atoms by acid-base corrosion to form pores, but the quality loss of products is serious; most of the materials obtained by the template-free method are zeolite nanocrystal aggregates, the mesopores of the zeolite nanocrystals are usually intercrystalline mesopores, and the mechanical stability of the mesopores is poor.
Disclosure of Invention
The invention aims to provide a method for synthesizing a hierarchical porous aluminum phosphate molecular sieve. By adding fluorinion, the dosage of the mesoporous template agent is reduced, the cost is reduced, and the hierarchical pore aluminum phosphate molecular sieve with high crystallinity is synthesized.
The technical scheme of the invention comprises the following specific steps: stirring and mixing an aluminum source, a phosphorus source, a metal source and water according to a molar ratio of 1-2 to 0.05-0.5, respectively adding a microporous template, a mesoporous template and a fluorine source to prepare a molecular sieve synthetic solution, stirring at room temperature for 1-2h, aging for 2-3h, placing in a high-pressure reaction kettle, crystallizing at 160-200 ℃ for 12-48h, performing suction filtration, washing with deionized water, drying at 100-120 ℃, and roasting at 400-600 ℃ for 4-6h to prepare the hierarchical porous aluminum phosphate molecular sieve.
The mesoporous template in the technical scheme can be optionally added or not added, and if the mesoporous template is not added, the consumption of a fluorine source needs to be increased.
In the technical scheme, the microporous template and the mesoporous template are ammonium salts.
Preferably, the microporous template agent is triethylamine, and the mesoporous template agent is hexadecyl trimethyl ammonium bromide.
The mol ratio of the micropore template to the aluminum source in the technical scheme is 1.0-2.0.
The fluorine source in the technical scheme is hydrofluoric acid, ammonium fluoride, fluosilicic acid and ammonium hexafluorosilicate so as to provide fluoride ions.
In the technical scheme, the fluorine source is hydrofluoric acid and ammonium fluoride, and a hierarchical pore aluminum phosphate molecular sieve is synthesized; the fluorine source is fluosilicic acid and ammonium hexafluorosilicate, and the synthesized porous silicoaluminophosphate molecular sieve is a hierarchical pore.
In the technical scheme, the mesoporous template is not added, and the molar ratio of the fluorine ions to the aluminum source is 1.0-2.0.
In the technical scheme, the mesoporous template is added, and the molar ratio of the mesoporous template to the aluminum source is 0.05-1.0; the molar ratio of the fluorine source to the aluminum source is 0.05-1.0 when the fluorine source is hydrofluoric acid, 0.05-0.2 when the fluorine source is ammonium fluoride, 0.01-0.15 when the fluorine source is fluosilicic acid, and 0.05-0.1 when the fluorine source is ammonium hexafluorosilicate.
In the method, when the fluorine source is fluosilicic acid or ammonium hexafluorosilicate, the fluorine source not only plays roles of mineralization and structure guidance of conventional fluorine ions, but also provides a silicon source for silicon in the fluorine source, so that the synthesized molecular sieve is a hierarchical pore silicoaluminophosphate molecular sieve.
The application of the hierarchical pore aluminum phosphate molecular sieve obtained by the preparation method comprises the following steps: the hierarchical pore aluminum phosphate molecular sieve is used for oxidation desulfurization reaction:
the desulfurization experimental method comprises the following steps: reacting in a constant-temperature water bath stirrer at 30-60 ℃ for 20-60min, and performing an experiment of removing sulfides in the simulated oil by catalytic oxidation of a hierarchical-pore aluminum phosphate molecular sieve; and (3) taking a certain amount of upper-layer oil sample after liquid separation and centrifugation, and measuring the content of sulfur in the simulated oil before and after reaction by adopting an ultraviolet fluorescence sulfur analyzer to obtain the desulfurization rate.
Compared with the prior art, the invention has the following advantages:
(1) The method adopts a method of synthesizing the hierarchical porous aluminum phosphate molecular sieve under a fluorine ion system. Because the ionic radius and the electronic structure of the fluorine ions and the oxygen ions are different, the existence of the fluorine ions in the framework forces metal atoms to deviate from the equilibrium position of the metal atoms, so that the synthesized hierarchical pore aluminum phosphate molecular sieve has stronger acidity.
(2) The addition of the fluorinion in the method can reduce the addition of the mesoporous template agent, so that the particle size distribution of the prepared hierarchical pore aluminum phosphate molecular sieve is more uniform.
(3) Fluorine ions are added in the process of synthesizing the molecular sieve, so that the mineralization effect is achieved, the structure guiding effect can be exerted, and the time for forming crystal nuclei is shortened. In a fluorine-containing system, the existence of fluorine ions balances the positive charge on the template agent, thereby reducing the defects of the molecular sieve crystal and being beneficial to forming the molecular sieve crystal with high quality.
(4) The hierarchical pore aluminum phosphate molecular sieve synthesized by the method is used in the oxidation desulfurization reaction, and has the advantages of high selectivity, easy recovery, no pollution and high desulfurization rate. Compared with the conventional system, the product synthesized by adding HF has enhanced crystallinity and acidity, and the catalytic performance is improved.
Drawings
FIG. 1 is an XRD small angle diagram of a hierarchical pore aluminum phosphate molecular sieve D-CoAPO-5-F or D-CoAPO-5 prepared with or without the use of a fluoride ion system in example 1 of the present invention and comparative example 1.
FIG. 2 is an XRD pattern of a hierarchical pore aluminum phosphate molecular sieve D-CoAPO-5-F or D-CoAPO-5 prepared with or without the use of a fluoride ion system in inventive example 1 and comparative example 1.
FIG. 3N of a hierarchical porous aluminophosphate molecular sieve D-CoAPO-5-F prepared using a fluoride ion system in accordance with example 1 of the present invention 2 Adsorption-desorption isotherms and pore size profiles.
FIG. 4 is a graph showing the N content of a multi-stage porous aluminophosphate molecular sieve D-CoAPO-5 prepared without adding fluoride ions in comparative example 1 of the present invention 2 Adsorption-desorption isotherms and pore size profiles.
FIG. 5 shows pyridine adsorption IR spectra of the multi-stage porous aluminophosphate molecular sieves D-CoAPO-5-F and D-CoAPO-5 prepared using the fluoride ion system or without adding fluoride ions in inventive example 1 and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Preparing a hierarchical pore aluminum phosphate molecular sieve:
hydrating 2.96g of pseudoboehmite with 16mL of distilled water, magnetically stirring at 25 ℃ for 12h, adding 4.62g of phosphoric acid solution, stirring for 0.5h, weighing 0.50g of cobalt acetate, dissolving with 10mL of distilled water, adding to the mixture, and stirring for 0.5h. Adding 2.02g of triethylamine, continuing stirring for 2h, adding 3.31g of CTAB and 10mL of distilled water, stirring for 2h, continuing adding 0.40g of hydrofluoric acid aqueous solution (the mass fraction is 40%) into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 24h at 180 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 110 ℃, and roasting for 6h at 550 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve, which is marked as D-CoAPO-5-F.
Removing sulfides in the simulated oil by catalytic oxidation:
thiophene, benzothiophene and dibenzothiophene are respectively dissolved in n-heptane to prepare 1000 mu g/g of simulated oil, wherein sodium hypochlorite is used as an oxidizing agent, acetonitrile is used as an extracting agent, V (simulated oil) is 1.0. Stirring and reacting for 45min at 40 ℃ in a constant-temperature water bath stirrer, separating liquid, centrifuging, taking a certain amount of upper oil sample, and measuring the sulfur content in the simulated oil before and after the reaction by adopting a TS-3000 ultraviolet fluorescence sulfur analyzer to obtain the removal rates of the thiophene, the benzothiophene and the dibenzothiophene of 75.4%, 81.6% and 86.7% respectively.
Example 2
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 5.78g of phosphoric acid solution was added, and after stirring for 0.5 hour, 0.50g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 3.03g of triethylamine, continuing stirring for 2h, adding 3.31g of CTAB and 10mL of distilled water, stirring for 2h, continuing adding 0.16g of ammonium fluoride dissolved by water into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 24h at 200 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 105 ℃, and roasting for 4h at 600 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve.
The removal rate of the sulfide in the simulated oil by catalytic oxidation is 74.3 percent, 79.8 percent and 85.9 percent respectively as in example 1.
Example 3
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 5.08g of phosphoric acid solution was added, and after stirring for 0.5 hour, 0.50g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 2.02g of triethylamine, continuously stirring for 2h, adding 3.31g of CTAB and 10mL of distilled water, stirring for 2h, continuously adding 1.24g of fluosilicic acid aqueous solution (the mass fraction is 35%) into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 36h at 190 ℃, carrying out suction filtration, washing with deionized water to be neutral, drying at 100 ℃, and roasting for 5h at 550 ℃ to obtain the multistage pore CoAPO-5 molecular sieve.
The removal rate of the sulfide in the simulated oil by catalytic oxidation is 73.5 percent, 78.9 percent and 84.6 percent respectively as in example 1.
Example 4
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 4.62g of phosphoric acid solution was added, and after stirring was continued for 0.5 hour, 1.00g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 2.02g of triethylamine, continuing stirring for 2h, adding 4.97g of CTAB and 10mL of distilled water, stirring for 2h, continuing adding 0.18g of ammonium hexafluorosilicate dissolved by water into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 48h at 170 ℃, performing suction filtration, washing with deionized water to be neutral, drying at 120 ℃, and roasting for 6h at 550 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve.
The removal rate of the sulfide in the simulated oil by catalytic oxidation is 77.3 percent, 82.5 percent and 88.4 percent respectively as in example 1.
Example 5
Hydrating 2.96g of pseudoboehmite with 16mL of distilled water, magnetically stirring at 25 ℃ for 12h, adding 4.62g of phosphoric acid solution, stirring for 0.5h, weighing 1.00g of cobalt acetate, dissolving with 10mL of distilled water, adding to the mixture, and stirring for 0.5h. Adding 2.02g of triethylamine, continuing stirring for 2h, adding 3.31g of CTAB and 10mL of distilled water, stirring for 2h, continuing adding 0.36g of ammonium hexafluorosilicate dissolved by water into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 12h at 170 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 120 ℃, and roasting for 6h at 550 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve.
The removal rate of sulfide in the simulated oil by catalytic oxidation is 75.3%, 82.1% and 86.4% respectively as in example 1.
Example 6
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 4.62g of phosphoric acid solution was added, and after stirring was continued for 0.5 hour, 1.0g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 2.02g of triethylamine, stirring for 2h, continuously adding 2.50g of hydrofluoric acid diluted by water into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 24h at 200 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 110 ℃, and roasting for 6h at 550 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve.
The removal rate of sulfide in the simulated oil by catalytic oxidation is 72.5%, 79.1% and 84.4% respectively as in example 1.
Example 7
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 5.08g of phosphoric acid solution was added, and after stirring for 0.5 hour, 1.00g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 3.03g of triethylamine, stirring for 2h, continuously adding 1.82g of ammonium hexafluorosilicate diluted by water into the mixed solution to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution into a reaction kettle, crystallizing for 48h at 180 ℃, performing suction filtration, washing to be neutral by using deionized water, drying at 110 ℃, and roasting for 6h at 450 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve.
The removal rate of the sulfide in the simulated oil by catalytic oxidation is 75.4 percent, 80.7 percent and 85.8 percent respectively as in example 1.
Comparative example 1
This example used a hierarchical porous aluminum phosphate molecular sieve synthesized without the addition of fluoride ions.
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 4.62g of phosphoric acid solution was added, and after stirring was continued for 0.5 hour, 0.50g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 2.02g of triethylamine, continuing stirring for 2h, adding 3.31g of CTAB and 10mL of distilled water to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution to a reaction kettle, crystallizing for 24h at 180 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 110 ℃, and roasting for 6h at 550 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve, which is marked as D-CoAPO-5.
The experimental conditions for removing the sulfide in the simulated oil by catalytic oxidation are the same as those of example 1, and the removal rates of thiophene, benzothiophene and dibenzothiophene are respectively 72.9%, 76.6% and 83.4% by using the prepared hierarchical pore CoAPO-5 molecular sieve as a catalyst.
Comparative example 2
2.96g of pseudo-boehmite was hydrated with 16mL of distilled water, and after magnetic stirring at 25 ℃ for 12 hours, 4.62g of phosphoric acid solution was added, and after stirring was continued for 0.5 hour, 1.00g of cobalt acetate was weighed, dissolved in 10mL of distilled water, added to the mixture, and stirred for 0.5 hour. Adding 2.02g of triethylamine, continuing stirring for 2h, adding 4.97g of CTAB and 10mL of distilled water to prepare a molecular sieve synthetic solution, stirring and aging for 3h, transferring the synthetic solution to a reaction kettle, crystallizing for 48h at 170 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 120 ℃, and roasting for 6h at 550 ℃ to obtain the hierarchical pore CoAPO-5 molecular sieve.
The removal rate of sulfide in the simulated oil by catalytic oxidation is 74.0%, 79.3% and 85.7% respectively as in example 1.
The multi-stage pore CoAPO-5 molecular sieve prepared in example 1 and comparative example 1 is used as a catalyst, thiophene, benzothiophene and dibenzothiophene in the simulated oil are subjected to oxidation removal, and the removal rates are respectively 75.4%, 81.6%, 86.7% and 72.9%, 76.6% and 83.4%. Therefore, the multi-stage pore aluminum phosphate molecular sieve synthesized by adopting the fluorine ion system has better effect on removing sulfides in the simulated oil by oxidation compared with the multi-stage pore aluminum phosphate molecular sieve synthesized by a fluorine ion-free system.
Claims (5)
1. A method for synthesizing a hierarchical pore aluminum phosphate molecular sieve by using fluoride ions is characterized by comprising the following steps: the synthesis method comprises the following steps: mixing an aluminum source, a phosphorus source, a metal source and water according to a molar ratio of 1-2 to 0.05-0.5, respectively adding a microporous template, a mesoporous template and a fluorine source to prepare a molecular sieve synthetic solution, stirring at room temperature for 1-2h, aging for 2-3h, placing in a high-pressure reaction kettle, crystallizing at 160-200 ℃ for 12-48h, performing suction filtration, washing with deionized water, drying at 100-120 ℃, and roasting at 400-600 ℃ for 4-6h to prepare the hierarchical pore aluminum phosphate molecular sieve; the fluorine source is fluosilicic acid or ammonium hexafluorosilicate;
when the adding amount of the mesoporous template is 0, the molar ratio of the fluorine source to the aluminum source is 1.0-2.0;
when the molar ratio of the mesoporous template to the aluminum source is 0.05-1.0; when the fluorine source is fluosilicic acid, the molar ratio of the fluorine source to the aluminum source is 0.01-0.15, and when the fluorine source is ammonium hexafluorosilicate, the molar ratio of the fluorine source to the aluminum source is 0.05-0.1;
the hierarchical pore aluminum phosphate molecular sieve is used for oxidation desulfurization reaction.
2. The method of synthesizing a hierarchical pore aluminum phosphate molecular sieve using fluoride ions according to claim 1, wherein: the micropore template and the mesopore template are ammonium salts.
3. The method of synthesizing a hierarchical pore aluminophosphate molecular sieve using fluoride ions of claim 1, wherein: the microporous template agent is triethylamine, and the molar ratio of the triethylamine to the aluminum source is 1.0-2.0.
4. The method of synthesizing a hierarchical pore aluminum phosphate molecular sieve using fluoride ions according to claim 1, wherein: the mesoporous template agent is cetyl trimethyl ammonium bromide, and the molar ratio of the cetyl trimethyl ammonium bromide to the aluminum source is 0-1.0.
5. The method of synthesizing a hierarchical pore aluminum phosphate molecular sieve using fluoride ions according to claim 1, wherein: the oxidation desulfurization reaction is an experiment of removing sulfides in the simulated oil through catalytic oxidation by using a multi-stage pore aluminum phosphate molecular sieve in a constant-temperature water bath stirrer, then taking an upper oil sample after liquid separation and centrifugation, and measuring the content of sulfur in the simulated oil before and after the reaction by using an ultraviolet fluorescence sulfur analyzer to obtain the desulfurization rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910593146.4A CN110372005B (en) | 2019-07-03 | 2019-07-03 | Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910593146.4A CN110372005B (en) | 2019-07-03 | 2019-07-03 | Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110372005A CN110372005A (en) | 2019-10-25 |
| CN110372005B true CN110372005B (en) | 2022-10-28 |
Family
ID=68251750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910593146.4A Active CN110372005B (en) | 2019-07-03 | 2019-07-03 | Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110372005B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113428872B (en) * | 2021-07-27 | 2022-06-07 | 武汉工程大学 | Method for synthesizing SAPO-34 molecular sieve by using fluosilicic acid as industrial phosphate fertilizer byproduct and application thereof |
| CN114054082B (en) * | 2021-11-10 | 2022-11-08 | 南昌大学 | Nano hierarchical pore SAPO-11 molecular sieve and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
| CN104030315A (en) * | 2014-06-25 | 2014-09-10 | 常州大学 | Method for synthesizing heteroatom aluminophosphate molecular sieve by utilizing natural ore |
| CN107777702A (en) * | 2017-11-09 | 2018-03-09 | 常州大学 | A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening |
| CN107915237A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of 34 molecular sieves of twin SAPO and its synthetic method and a kind of method of methanol-to-olefins |
-
2019
- 2019-07-03 CN CN201910593146.4A patent/CN110372005B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786063A (en) * | 2012-08-10 | 2012-11-21 | 中国海洋石油总公司 | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure |
| CN104030315A (en) * | 2014-06-25 | 2014-09-10 | 常州大学 | Method for synthesizing heteroatom aluminophosphate molecular sieve by utilizing natural ore |
| CN107915237A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of 34 molecular sieves of twin SAPO and its synthetic method and a kind of method of methanol-to-olefins |
| CN107777702A (en) * | 2017-11-09 | 2018-03-09 | 常州大学 | A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening |
Non-Patent Citations (1)
| Title |
|---|
| 多级孔CoAPo-5分子筛液相催化氧化糠醛制备马来酸;陆杨等;《石油学报》;20181130;第34卷(第6期);第1075-1081页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110372005A (en) | 2019-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6430303B2 (en) | Manufacturing method of AFX type zeolite | |
| CN102745708B (en) | Synthetic method of mesoporous-microporous molecular sieve with improved hydrothermal stability | |
| CN102491366B (en) | Method for preparing hollow zeolite socony mobil-5 (ZSM-5) nanometer zeolite | |
| CN110372005B (en) | Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions | |
| JP4964150B2 (en) | Microporous crystalline zeolitic material (zeolite ITQ-32), process for producing the material and use of the material | |
| CN106799202B (en) | Molecular sieve for gas separation and preparation and application thereof | |
| CN111659251A (en) | Low-cost hierarchical pore SAPO-34 molecular sieve and preparation method and application thereof | |
| CN109775716B (en) | Hierarchical pore Y-type molecular sieve rich in L acid and preparation method thereof | |
| CN104971770B (en) | A kind of preparation method of the solid super-strong acid containing zirconium | |
| CN109250728A (en) | The Cu-SAPO molecular sieve and application of Cu-SAPO Zeolite synthesis method and synthesis | |
| CN106495125A (en) | A kind of preparation method and application of petroleum coke base mesoporous carbon | |
| CN105540608A (en) | Y-Beta composite molecular sieve having double mesoporous structure, and preparation method thereof | |
| CN113086990A (en) | Preparation method of mesoporous molecular sieve | |
| CN103055805B (en) | Synthesis method of interface micro-pore sequence structure LSX (low-silica X-zeolite) molecular sieve for spatially dividing oxygen-enriched adsorbent | |
| CN110240178B (en) | Selective molecular adsorption sieve and preparation method thereof | |
| CN103274429B (en) | Preparation method of CoSAPO-11 molecular sieve | |
| CN103121688B (en) | Synthesis method of MOR (Mordenite)-BEA (Beta Zeolite) core-shell zeolite | |
| CN102502685A (en) | Preparation method of mesoporous LTA zeolite | |
| CN111348662A (en) | Ultra-large pore silicate molecular sieve NUD-6 and preparation method thereof | |
| CN112850742B (en) | Hierarchical pore Y-type molecular sieve and synthesis method thereof | |
| Utchariyajit et al. | Structural aspects of mesoporous AlPO4-5 (AFI) zeotype using microwave radiation and alumatrane precursor | |
| JP2002001107A (en) | Zeolite for treating nonaqueous electrolyte and method for manufacturing nonaqueous electrolyte | |
| CN103964463B (en) | Preparation method of Y-type molecular sieve | |
| CN114162832B (en) | Synthesis method and application of SSZ-13 molecular sieve in ultra-low template system | |
| CN115448324B (en) | MFI structure molecular sieve hierarchical pore material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |