CN113198530A - Au-Mg/SAPO-11 molecular sieve catalyst, and preparation method and application thereof - Google Patents
Au-Mg/SAPO-11 molecular sieve catalyst, and preparation method and application thereof Download PDFInfo
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- CN113198530A CN113198530A CN202110504195.3A CN202110504195A CN113198530A CN 113198530 A CN113198530 A CN 113198530A CN 202110504195 A CN202110504195 A CN 202110504195A CN 113198530 A CN113198530 A CN 113198530A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 109
- 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 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000008098 formaldehyde solution Substances 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000003852 triazoles Chemical class 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 4
- 229910020252 KAuCl4 Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 54
- 239000011777 magnesium Substances 0.000 description 53
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000000967 suction filtration Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 125000006281 4-bromobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Br)C([H])([H])* 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 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
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- -1 silicon-phosphorus-aluminum Chemical compound 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an Au-Mg/SAPO-11 molecular sieve catalyst, which relates to the field of chemical materials and is prepared from an SAPO-11 molecular sieve and a composite nano metal Au-Mg. The Au-Mg/SAPO-11 molecular sieve catalyst provided by the invention is an environment-friendly catalyst, and compared with the traditional catalyst, the catalyst has the advantages of high catalytic efficiency, mild reaction conditions and high repeated utilization rate; meanwhile, the invention also provides a preparation method of the Au-Mg/SAPO-11 molecular sieve catalyst and application of the Au-Mg/SAPO-11 molecular sieve catalyst prepared by the preparation method in bisphenol F synthesis and alcohol oxidation reaction.
Description
Technical Field
The invention relates to the field of chemical materials, in particular to an Au-Mg/SAPO-11 molecular sieve catalyst, and a preparation method and application thereof.
Background
SAPO-11 has one-dimensional ten-ring elliptic pore canal structure, belongs to silicon-phosphorus-aluminum molecular Sieve (SAPOs), and is composed of PO4，AlO4And SiO4The three tetrahedral structure units are formed by a microwave synthesis method, a hydrothermal synthesis method and the like. By virtue of weak acidity, good shape selectivity and special pore channel structure, the catalyst can be used as an adsorbent, an acid catalyst and a catalyst carrier. Can be used in petrochemical reactions such as alkane isomerization and the like.
The nano material has unique crystal structure and size effect and has higher catalytic activity in catalytic reaction. Meanwhile, in different catalytic reaction processes, metal atoms at different positions of the crystal show different catalytic activities, so that the existence mode of the metal nano-catalyst on the carrier also has certain influence on the reaction. The number of atoms on the surface of the support increases sharply as the size of the metal nanoparticles decreases, thereby causing other properties of the metal nanoparticles to change. Moreover, the increase of the number of atoms on the surface of the carrier also leads to the enlargement of the specific surface area of the particle, the increase of the surface energy, the reduction of the coordination number of the surface atoms and the generation of a plurality of hole centers, and finally leads to the great change of the physical and chemical properties of the nano material compared with the traditional material.
The epoxy resin has the characteristics of alkali resistance, heat resistance, electrical insulation and the like, and is more and more widely applied in various industries, such as the fields of chemical industry, machinery, electrical industry and the like, and plays an important role in national economy. Bisphenol A type epoxy resin in the market is about 70 percent of epoxy resin as general resin, and the bisphenol F type epoxy resin has all excellent characteristics of the bisphenol A type epoxy resin, and also has unique performance, particularly has viscosity lower than that of the bisphenol A type epoxy resin, and is easy to process, so that the application range of the bisphenol F type epoxy resin is expanded, and bisphenol F products have good research value and application prospect. In the preparation method for synthesizing bisphenol F, the catalyst in the prior art is utilized, and the obtained product contains a plurality of isomers, so that various performances of the bisphenol F type epoxy resin are reduced.
In the organic synthesis industry, carbonyl compounds have a great importance, such as medicine, fine chemical engineering and the like, and therefore, the acceleration of the synthesis of carbonyl compounds is very important, and the carbonyl compounds are mainly realized by oxidizing alcohol by a strong oxidant; however, most of the conventional oxidants have super-strong oxidizability, which easily causes equipment corrosion and environmental pollution, so it is very important to develop an environment-friendly catalyst to realize the oxidation of different alcohols into corresponding carbonyl compounds.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the problems in the prior art, an Au-Mg/SAPO-11 molecular sieve catalyst, a preparation method and application thereof are provided.
The technical scheme adopted for solving the technical problems is as follows: the Au-Mg/SAPO-11 molecular sieve catalyst is prepared from a SAPO-11 molecular sieve and a composite nano metal Au-Mg.
The preparation method of the Au-Mg/SAPO-11 molecular sieve catalyst comprises the following steps:
1) synthesis of SAPO-11 molecular sieve
Mixing an aluminum source, a phosphorus source and a silicon source to form an aqueous solution, adding a template agent into the aqueous solution to perform reaction, and separating and purifying to obtain the SAPO-11 molecular sieve, wherein the molar ratio of the aluminum source to the phosphorus source to the silicon source is as follows: an aluminum source: a phosphorus source: silicon source 1: (1.2-1.5): (0.1-0.3);
2) preparation of Au-Mg/SAPO-11 molecular sieve catalyst
Adding an Au-containing compound into distilled water, then adding the SAPO-11 molecular sieve and triazole prepared in the step 1), then adding a stabilizer, stirring, standing, adding sodium borohydride, drying, cooling to room temperature, grinding, roasting, cooling, and grinding to prepare an Au/SAPO-11 molecular sieve;
dissolving a Mg-containing compound in distilled water, then weighing the prepared Au/SAPO-11 molecular sieve, stirring, standing, adding sodium borohydride for reaction, drying, cooling to normal temperature, grinding and roasting to obtain the Au-Mg/SAPO-11 molecular sieve catalyst.
Further, the aluminum source is selected from at least one of pseudo-boehmite and aluminum oxide; the phosphorus source is selected from phosphoric acid; the silicon source is at least one of tetraethoxysilane and silicon dioxide; the template machine is selected from at least one of di-n-propylamine and hexadecyl phosphate.
Further, in the step 2), the stabilizer is isopropanol.
Further, the Au-containing compound is KAuCl4Or AuCl3Is (CH) and the Mg-containing compound is3COO)2Mg or Mg (OTf)2At least one of (1).
Further, adding an Au-containing compound into distilled water in the step 2), then adding the SAPO-11 molecular sieve and triazole prepared in the step 1), then adding isopropanol serving as a stabilizer, stirring for 4-12h, then standing for 12-48h, then adding sodium borohydride for reduction reaction for 2-24h, drying for 2-18h in a vacuum drying box at the temperature of 100-120 ℃, cooling to normal temperature, grinding, roasting for 2-48h at the temperature of 400-500 ℃, cooling to room temperature, and then grinding to obtain the Au/SAPO-11 molecular sieve.
Further, in the step 2), dissolving a compound containing Mg in distilled water, then weighing the prepared Au/SAPO-11 molecular sieve, stirring for 2-12h, standing for 2-24h, adding sodium borohydride for reacting for 2-24h, drying for 2-24h in an environment with the temperature of 100-.
Further, the step 1) of synthesizing the SAPO-11 molecular sieve comprises the following steps of:
(a) adding an aluminum source into deionized water, then adding the phosphorus source according to the molar ratio of the phosphorus source to the aluminum source of 1.2-1.5, and stirring to obtain a solution 1;
(b) adding a silicon source with the molar ratio of a silicon source to an aluminum source of 0.1-0.3 into the solution 1, and stirring to obtain a solution 2;
(c) adding a template agent with the molar ratio of the template agent to the aluminum source of 0.4-1 into the solution 2, and stirring to obtain a solution 3;
(d) placing the solution 3 in a high-pressure kettle, and reacting for 2-3 days at the temperature of 120-250 ℃; cooling the high-pressure kettle to normal temperature, filtering, washing, drying and roasting to obtain the SAPO-11 molecular sieve;
further, the molar ratio of the phosphorus source to the aluminum source is 1.2-1.5:1, the molar ratio of the silicon source to the aluminum source is 0.1-0.2:1, preferably, the molar ratio of the silicon source to the aluminum source is 0.15-0.2:1, the molar ratio of the template agent to the aluminum source is 0.6-1:1, and the molar ratio of the template agent to the aluminum source is 0.7-0.9: 1.
The application of the Au-Mg/SAPO-11 molecular sieve catalyst prepared by the Au-Mg/SAPO-11 molecular sieve catalyst or the Au-Mg/SAPO-11 molecular sieve catalyst preparation method, wherein the Au-Mg/SAPO-11 molecular sieve catalyst is used for synthesizing bisphenol F, and comprises the following steps: under the condition of 30-100 ℃, in a reaction kettle, taking phenol as a raw material and toluene as a solvent, adding the Au-Mg/SAPO-11 catalyst, adding a formaldehyde solution, reacting for 6-12h, standing and cooling after the reaction is finished, performing suction filtration after solid is separated out, and washing twice by using a hot solvent; recrystallizing the solid again to obtain bisphenol F, wherein the mass ratio of phenol to formaldehyde to the Au-Mg/SAPO-11 molecular sieve catalyst is (3-47): 1:(0.001-0.7).
Further, in the application of the Au-Mg/SAPO-11 molecular sieve catalyst for synthesizing bisphenol F, after reactants are added, phosphoric acid is added into a reaction kettle to provide an acidic environment, wherein the mass ratio of the phosphoric acid to the formaldehyde is 1: (0.3-1.6).
The application of the Au-Mg/SAPO-11 molecular sieve catalyst comprises the following steps: and (2) placing the benzyl alcohol derivative in an acetonitrile solvent, wherein the mass ratio of the benzyl alcohol derivative to the Au-Mg/SAPO-11 molecular sieve catalyst is 1: (0.01-0.8) adding the Au-Mg/SAPO-11 molecular sieve catalyst for catalysis to obtain the corresponding aldehyde.
The invention has the beneficial effects that:
(1) compared with the catalyst in the prior art, the Au-Mg/SAPO-11 molecular sieve catalyst synthesized by the invention has stronger catalytic efficiency and catalytic performance and high recycling rate, and simultaneously reduces the use of strong acid, thereby reducing the corrosion to equipment, reducing the energy consumption and having good application prospect.
(2) In the process of synthesizing bisphenol F, compared with the prior art, the catalyst is used to mainly obtain 4, 4-dihydroxy diphenylmethane, and the content of other two isomers is reduced, so that the performance of bisphenol F epoxy resin is improved.
(3) The catalyst prepared by the invention is used for alcohol oxidation reaction, replaces highly toxic oxidant such as dichromate and the like and strong oxidizing oxidant such as permanganate and the like, realizes high-efficiency selectivity of alcohol under mild conditions, has strong catalytic activity and good catalytic effect, and has the conversion rate of 100 percent and the chemical selectivity of the product of 99 percent.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 is an SEM image of an Au-Mg/SAPO-11 molecular sieve catalyst prepared by example 1 of the invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and examples, but the embodiments of the invention are not limited thereto. In addition, the calculation formula of the yield in the invention is as follows: yield-the actual mass of the target product obtained/theoretically 100% of the target product obtained.
Example 1
The Au-Mg/SAPO-11 molecular sieve catalyst of the example was prepared by the following steps:
1) synthesis of SAPO-11 molecular sieve
(a) Adding 3.0g of pseudo-boehmite into 60ml of deionized water, then adding 5.0g of phosphoric acid according to the molar ratio of a phosphorus source to an aluminum source of 1.2, and stirring for 2 hours to obtain a solution 1;
(b) adding 1.4g of tetraethoxysilane with the molar ratio of tetraethoxysilane to pseudo-boehmite of 0.16 into the solution 1, and stirring for 2 hours to obtain a solution 2;
(c) adding 2.5g of di-n-propylamine into the solution 2, wherein the molar ratio of the di-n-propylamine template to the pseudo-boehmite is 0.6, and stirring for 2 hours to obtain a solution 3;
(d) placing the solution 3 in a high-pressure autoclave, and reacting for 3 days at 120 ℃; cooling the autoclave to normal temperature, filtering, washing to obtain a white solid, placing the white solid in an oven at 110 ℃ for drying for 12h, placing a sample in a crucible, heating to 250 ℃ in a muffle furnace for roasting for 2h, and heating to 650 ℃ for roasting for 5h to obtain the SAPO-11 molecular sieve;
2) preparation of Au-Mg/SAPO-11 molecular sieve catalyst
(e) 0.257g of KAuCl4Adding 3ml of distilled water, then adding the SAPO-11 molecular sieve prepared in the step 1) and 0.386g of triazole, then adding isopropanol serving as a stabilizer, stirring for 4h, standing for 12h, adding 0.257g of sodium borohydride, reacting for 2h, putting the sample into a vacuum drying oven at 110 ℃ for drying for 12h, cooling to room temperature, grinding into powder by using a mortar, putting the powder into a crucible, putting the crucible into a muffle furnace, and roasting for 6h at 400 ℃ to prepare the Au/SAPO-11 molecular sieve;
(f) 0.072g of Mg (OTf)2Dissolving the Au/SAPO-11 molecular sieve in 3ml of distilled water, weighing 0.100g of the Au/SAPO-11 molecular sieve prepared in the step (e), stirring for 4h, standing for 12h, adding 0.083g of sodium borohydride for reaction for 2h, then putting the sample into a vacuum drying oven at 110 ℃ for drying for 12h, cooling to normal temperature, grinding the sample into powder by using a mortar, putting the powder into a crucible, putting the crucible into a muffle furnace, and roasting for 6h at 400 ℃ to obtain the Au-Mg/SAPO-11 molecular sieve catalyst. FIG. 1 is an SEM image of an Au-Mg/SAPO-11 molecular sieve catalyst prepared by example 1 of the invention.
Example 2
The Au-Mg/SAPO-11 molecular sieve catalyst of the example was prepared by the following steps:
1) synthesis of SAPO-11 molecular sieve
(a) 4.0gAl2O3Adding the mixture into 80ml of deionized water, then adding 4.614g of phosphoric acid according to the molar ratio of 1.2 of a phosphorus source to an aluminum source, and stirring for 2 hours to obtain a solution 1;
(b) adding SiO to solution 12And Al2O30.375g of silicon dioxide with the molar ratio of 0.16, and stirring for 2 hours to obtain a solution 2;
(c) adding hexadecyl phosphate template and Al into the solution 22O3In a molar ratio of7.545g of 0.6 g of hexadecyl phosphate, and stirring for 2 hours to obtain a solution 3;
(d) placing the solution 3 in a high-pressure autoclave, and reacting for 3 days at 120 ℃; cooling the autoclave to normal temperature, filtering, washing to obtain a white solid, placing the white solid in an oven at 110 ℃ for drying for 12h, placing a sample in a crucible, heating to 250 ℃ in a muffle furnace for roasting for 2h, and heating to 650 ℃ for roasting for 5h to obtain the SAPO-11 molecular sieve;
2) preparation of Au-Mg/SAPO-11 molecular sieve catalyst
(e) 0.206g of AuCl3Adding 3ml of distilled water, then adding the SAPO-11 molecular sieve prepared in the step 1) and 0.309g of triazole, then adding isopropanol serving as a stabilizer, stirring for 4h, standing for 12h, adding 0.257g of sodium borohydride, putting the sample into a vacuum drying oven at 110 ℃ for drying for 12h, cooling to room temperature, grinding into powder by using a mortar, putting the powder into a crucible, putting the crucible into a muffle furnace, and roasting for 6h at 400 ℃ to prepare the Au/SAPO-11 molecular sieve;
(f) 0.031g of (CH)3COO)2Dissolving Mg in 2mL of distilled water, weighing 0.100g of the Au/SAPO-11 molecular sieve prepared in the step (e), stirring for 4h, standing for 12h, adding 0.083g of sodium borohydride for reacting for 2h, putting the sample into a vacuum drying oven at 110 ℃ for drying for 12h, cooling to normal temperature, grinding into powder by using a mortar, putting the powder into a crucible, putting the crucible into a muffle furnace, and roasting for 6h at 400 ℃ to obtain the Au-Mg/SAPO-11 molecular sieve catalyst.
Example 3
The Au-Mg/SAPO-11 molecular sieve catalyst of the example was prepared by the following steps:
1) synthesis of SAPO-11 molecular sieve
(a) Adding 5.5g of pseudo-boehmite into 90ml of deionized water, then adding 9.089g of phosphoric acid according to the molar ratio of a phosphorus source to an aluminum source of 1.2, and stirring for 2 hours to obtain a solution 1;
(b) adding SiO to solution 120.740g of silicon dioxide with the molar ratio of the silicon dioxide to the pseudo-boehmite of 0.16 is stirred for 2 hours to obtain a solution 2;
(c) 4.675g of template di-n-propylamine with the molar ratio of 0.6 between the template and the aluminum source is added into the solution 2, and the solution is stirred for 2 hours to obtain a solution 3;
(d) placing the solution 3 in a high-pressure autoclave, and reacting for 3 days at 120 ℃; cooling the autoclave to normal temperature, filtering, washing to obtain a white solid, placing the white solid in an oven at 110 ℃ for drying for 12h, placing a sample in a crucible, heating to 250 ℃ in a muffle furnace for roasting for 2h, and heating to 650 ℃ for roasting for 5h to obtain the SAPO-11 molecular sieve;
2) preparation of Au-Mg/SAPO-11 molecular sieve catalyst
(e) 0.514g of KAuCl4Adding 4mL of distilled water, then adding the SAPO-11 molecular sieve prepared in the step 1) and 0.71g of triazole, then adding isopropanol serving as a stabilizer, stirring for 4h, standing for 12h, adding 0.386g of sodium borohydride, putting the sample into a vacuum drying oven at 110 ℃ for drying for 12h, cooling to room temperature, grinding into powder by using a mortar, putting the powder into a crucible, putting the crucible into a muffle furnace, and roasting for 6h at 400 ℃ to prepare the Au/SAPO-11 molecular sieve;
(f) 0.142g of Mg (OTf)2Dissolving the Au/SAPO-11 molecular sieve in 2mL of distilled water, weighing 0.100g of the Au/SAPO-11 molecular sieve prepared in the step (e), stirring for 4h, standing for 12h, adding 0.133g of sodium borohydride for reaction for 2h, drying the sample in a vacuum drying oven at 110 ℃ for 12h, cooling to normal temperature, grinding the sample into powder by using a mortar, placing the powder in a crucible, placing the crucible in a muffle furnace, and roasting at 400 ℃ for 6h to obtain the Au-Mg/SAPO-11 molecular sieve catalyst.
Experimental example 1
Preparation of bisphenol F25 g of phenol were placed in a four-necked flask with electric stirring, thermometer, constant pressure dropping funnel and reflux condenser and heated in an oil bath. 100mL of toluene was added, heated until the raw material was completely dissolved, 3.0g of 85% phosphoric acid solution by mass was added to provide an acidic environment, the reaction mixture was stirred rapidly to mix well, and 130Mg of the Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1 was added. Then adding 3.24g of formaldehyde solution with the mass fraction of 37% into a constant-pressure dropping funnel, slowly dropwise adding, controlling the temperature at 42 ℃, reacting for 2 hours, then heating to 60 ℃, reacting for 4 hours, after the reaction is finished, transferring the reaction liquid into a separating funnel, separating out inorganic phosphoric acid solution, adjusting the pH of an organic phase to about 6 by using sodium bicarbonate solution, separating the organic phase from a water phase by using the separating funnel, distilling out redundant phenol and water by organic phase vacuum distillation, and carrying out suction filtration by a vacuum pump to obtain a crude product. Dissolving the crude product with saturated NaOH solution, standing for 2 hr, filtering to remove insoluble substances, adjusting pH of the filtrate to 4 with dilute hydrochloric acid, precipitating solid, and filtering. And recrystallizing by using ethanol to obtain the bisphenol F with higher purity, wherein the yield is 80%. Wherein the chemical selectivity of 4, 4' -dihydroxydiphenylmethane is 63%.
Experimental example 2
Preparing bisphenol F: adding 25g of phenol into a four-mouth bottle with an electric stirring device, a thermometer, a constant-pressure dropping funnel and a reflux condenser tube, adding 100mL of toluene, heating until the raw materials are completely dissolved, adding 3g of phosphoric acid solution with the mass fraction of 85% and strongly stirring to provide an acidic environment, fully mixing, adding 150Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, slowly dropping 3.24g of formaldehyde solution (with the mass fraction of 37%), stopping the reaction after 6 hours of reaction, adding 20mL of water and 20mL of ethanol, standing to separate out a solid, performing suction filtration, washing twice with 25mL of hot toluene solution, dissolving the solid in ethanol, recrystallizing, separating out the solid, performing suction filtration, and washing twice with 25mL of hot toluene solution to obtain a pure bisphenol F. The yield was 82% and the chemoselectivity of 4, 4' -dihydroxydiphenylmethane was 61%.
Experimental example 3
Preparing bisphenol F: adding 25g of phenol into a four-mouth bottle with an electric stirring device, a thermometer, a constant-pressure dropping funnel and a reflux condenser tube, adding 100mL of toluene, heating until the raw materials are completely dissolved, adding 3g of phosphoric acid solution with the mass fraction of 85% to provide an acidic environment, simultaneously stirring strongly to mix the raw materials sufficiently, adding 160Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, slowly dropping 3.24g of formaldehyde solution (mass fraction of 37%), stopping the reaction after 8 hours of reaction, adding 20mL of water and 20mL of ethanol, standing to precipitate a solid, performing suction filtration, washing the 25mL of hot toluene solution twice, dissolving the solid in ethanol, recrystallizing, precipitating the solid, performing suction filtration, and washing the solution twice with 25mL of hot toluene solution to obtain a pure bisphenol F. The yield was 85% and the chemoselectivity of 4, 4' -dihydroxydiphenylmethane was 65%.
Experimental example 4
Preparing bisphenol F: adding 25g of phenol into a four-mouth bottle with an electric stirring device, a thermometer, a constant-pressure dropping funnel and a reflux condenser tube, adding 100mL of toluene, heating to 80 ℃ in an oil bath, heating until the raw materials are completely dissolved, adding 3g of phosphoric acid solution with the mass fraction of 85% to provide an acid environment, simultaneously stirring strongly to mix the raw materials sufficiently, adding 170Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, slowly dropping 3.24g of formaldehyde solution (mass fraction of 37%), stopping the reaction after 10 hours of reaction, adding 20mL of water and 20mL of ethanol, standing to separate out a solid, performing suction filtration, washing twice with 25mL of hot toluene solution, dissolving the solid in ethanol, recrystallizing, separating out the solid, performing suction filtration, and washing twice with 25mL of hot toluene solution to obtain the pure bisphenol F. The yield was 86% and the chemoselectivity for 4, 4' -dihydroxydiphenylmethane was 66%.
Experimental example 5
Preparing bisphenol F: adding 25g of phenol into a four-mouth bottle with an electric stirring device, a thermometer, a constant-pressure dropping funnel and a reflux condenser tube, adding 100mL of toluene, heating the mixture to 90 ℃ in an oil bath, heating the mixture until the raw materials are completely dissolved, adding 3g of phosphoric acid solution with the mass fraction of 85% to provide an acid environment, simultaneously stirring the mixture strongly to mix the mixture fully, adding 180Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, slowly dropping 3.24g of formaldehyde solution (mass fraction of 37%), stopping the reaction after reacting for 12 hours, adding 20mL of water and 20mL of ethanol, standing the mixture to separate out a solid, performing suction filtration, washing the mixture twice with 25mL of hot toluene solution, dissolving the solid in ethanol, recrystallizing the mixture to separate out the solid, performing suction filtration, and washing the mixture twice with 25mL of hot toluene solution to obtain the pure bisphenol F finally. The yield was 88% and the chemoselectivity of 4, 4' -dihydroxydiphenylmethane was 61%.
Experimental example 6
Preparing bisphenol F: 25g of phenol were charged into a four-necked flask equipped with an electric stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, and heated in an oil bath. Adding 100mL of toluene, adding 3g of solid oxalic acid to provide an acidic environment, heating in an oil bath at 70 ℃, heating until the raw materials are completely dissolved, adding 150Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, slowly dripping 3.24g of formaldehyde solution (mass fraction of 37%), stopping the reaction after 8 hours of reaction, distilling under reduced pressure to recover excessive phenol, adding 20mL of water and 20mL of ethanol, standing to separate out a solid, performing suction filtration, washing twice with 25mL of hot toluene solution, dissolving the solid in ethanol, recrystallizing, separating out the solid, performing suction filtration, and washing twice with 25mL of hot toluene solution to finally obtain a pure product of bisphenol F. The yield was 94% and the chemoselectivity for 4, 4' -dihydroxydiphenylmethane was 62%.
Experimental example 7
Preparing bisphenol F: 60g of phenol was charged into a four-necked flask equipped with an electric stirrer, a thermometer, a constant pressure dropping funnel and a reflux condenser, and heated in an oil bath. Adding 180mL of toluene, heating until the raw materials are completely dissolved, adding 7.27g of phosphoric acid solution with the mass fraction of 85% to provide an acid environment, rapidly stirring to uniformly mix the reaction solution, and adding 260Mg of the Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1. Then adding 7.78g of formaldehyde solution with the mass fraction of 37% into a constant-pressure dropping funnel, slowly dropwise adding, controlling the temperature at 42 ℃, reacting for 2 hours, then heating to 60 ℃, reacting for 4 hours, after the reaction is finished, transferring the reaction liquid into a separating funnel, separating out inorganic phosphoric acid solution, adjusting the pH of an organic phase to about 6 by using sodium bicarbonate solution, separating the organic phase from a water phase by using the separating funnel, distilling out redundant phenol and water by organic phase differential pressure distillation, and performing suction filtration by a vacuum pump to obtain a crude product. Dissolving the crude product with saturated NaOH solution, standing for 2 hr, filtering to remove insoluble substances, adjusting pH of the filtrate to 4 with dilute hydrochloric acid, precipitating solid, and filtering. And recrystallizing by using ethanol to obtain the bisphenol F with higher purity, wherein the yield is 81 percent, and the chemical selectivity of the 4, 4' -dihydroxy diphenylmethane is 60 percent.
Experimental example 8
Catalyzing 4-methyl benzyl alcohol oxidation reaction: adding 1mmol of 4-methylbenzyl alcohol into a 25mL reaction tube, adding 50Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, adding 2mL of acetonitrile serving as a solvent, reacting at 100 ℃ for 24 hours, cooling to room temperature after the reaction is finished, adding distilled water, extracting for 4 times by using ethyl acetate, collecting an organic phase, removing water by using anhydrous magnesium sulfate, evaporating a mixture of the organic phase and silica gel powder by using a rotary evaporator, and separating by using column chromatography to obtain 4-methylbenzaldehyde, wherein the yield is 100%, and the chemoselectivity of a product is 99%.
Experimental example 9
Catalyzing 4-bromobenzyl oxidation reaction: adding 1mmol of 4-bromobenzaldehyde into a 25mL reaction tube, adding 40Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, adding 2mL of acetonitrile serving as a solvent, reacting at 80 ℃ for 36h, cooling to room temperature after the reaction is finished, adding distilled water, extracting for 4 times by using ethyl acetate, collecting an organic phase, removing water by using anhydrous magnesium sulfate, evaporating a mixture of the organic phase and silica gel powder by using a rotary evaporator, and separating by using column chromatography to obtain 4-bromobenzaldehyde, wherein the yield is 96%, and the chemical selectivity of the product is 96%.
Experimental example 10
Catalyzing 2-naphthalic alcohol oxidation reaction: adding 1mmol of 2-naphthylmethanol into a 25mL reaction tube, adding 50Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, adding 2mL of acetonitrile as a solvent, reacting at 60 ℃ for 18h, cooling to room temperature after the reaction is finished, adding distilled water, extracting for 4 times by using ethyl acetate, collecting an organic phase, removing water by using anhydrous magnesium sulfate, evaporating the organic phase, silica gel powder and a mixture by using a rotary evaporator, and separating by using column chromatography to obtain the 2-naphthylformaldehyde, wherein the yield is 97%, and the chemical selectivity of the product is 97%.
Experimental example 11
Catalyzing 2-naphthalic alcohol oxidation reaction: adding 1mmol of 2-naphthylmethanol into a 25mL reaction tube, adding 80Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, adding 2mL of acetonitrile as a solvent, reacting at 40 ℃ for 24h, cooling to room temperature after the reaction is finished, adding distilled water, extracting for 4 times by using ethyl acetate, collecting an organic phase, removing water by using anhydrous magnesium sulfate, evaporating the organic phase, silica gel powder and a mixture by using a rotary evaporator, and separating by using column chromatography to obtain the 2-naphthylformaldehyde, wherein the yield is 98%, and the chemical selectivity of a product is 95%.
Experimental example 12
Repeated use experiment of Au-Mg/SAPO-11 molecular sieve catalyst:
adding 10mmol of 4-methylbenzyl alcohol into a 100mL reaction tube, adding 300Mg of Au-Mg/SAPO-11 molecular sieve catalyst prepared in example 1, adding 20mL of acetonitrile serving as a solvent, reacting at 60 ℃ for 6h, cooling to room temperature after the reaction is finished, filtering out the Au-Mg/SAPO-11 molecular sieve solid catalyst, washing with ethanol and distilled water for three times respectively, drying in an oven at 75 ℃ for 2h, continuously adding the recovered catalyst into the reaction for use, and circulating for 5 times, wherein the reaction yield is shown in the following table 1.
TABLE 1 reaction yields at different catalyst cycle times
| Number of cycles | 0 | 1 | 2 | 3 | 4 | 5 |
| Conversion rate/% | 100 | 98 | 96 | 96 | 96 | 95 |
| Selectivity/%) | 99 | 97 | 94 | 94 | 94 | 93 |
Comparative example 1
Adding 25g of phenol into a four-mouth bottle with an electric stirrer, a thermometer, a constant-pressure dropping funnel and a reflux condenser tube, adding 100mL of toluene, heating until the raw materials are completely dissolved, adding 3g of phosphoric acid solution with the mass fraction of 85% and stirring strongly to fully mix the raw materials, wherein the phosphoric acid not only provides an acidic environment for the reaction, but also has a catalytic action. And then slowly dripping 3.24g of formaldehyde solution (mass fraction of 37%), reacting for 6 hours, stopping the reaction, adding 20mL of water and 20mL of ethanol, standing to separate out a solid, performing suction filtration, washing twice with 25mL of hot toluene solution, dissolving the solid in ethanol, recrystallizing, separating out the solid, performing suction filtration, and washing twice with 25mL of hot toluene solution to finally obtain the pure bisphenol F. The yield of bisphenol F is 60%; the chemical selectivity of 4, 4' -dihydroxydiphenylmethane was 45%.
Comparative example 2
Catalyzing 4-methyl benzyl alcohol oxidation reaction: adding 1mmol of 4-methylbenzyl alcohol into a 25mL reaction tube, adding 1mL of sodium hypochlorite solution as an oxidant, adding 20mg of 2,2,6, 6-tetramethylpiperidine-1-oxygen free radical as a catalyst, adding 2mL of acetonitrile as a solvent, reacting at 60 ℃ for 18h, cooling to room temperature after the reaction is finished, adding distilled water, extracting for 4 times by using ethyl acetate, collecting an organic phase, removing water by using anhydrous magnesium sulfate, evaporating the organic phase, silica gel powder and a mixture by using a rotary evaporator, and separating by using column chromatography to obtain 4-methylbenzaldehyde, wherein the yield is 70%, and the chemoselectivity of a product is 60%.
Comparative example 3
Catalyzing 4-methyl benzyl alcohol oxidation reaction: adding 1mmol of 4-methylbenzyl alcohol into a 25mL reaction tube, adding 2mL of 1.6% acidic potassium permanganate solution, reacting for 6 hours at 35 ℃, cooling to room temperature after the reaction is finished, adding distilled water, extracting for 4 times by using ethyl acetate, collecting an organic phase, removing water by using anhydrous magnesium sulfate, evaporating the organic phase, silica gel powder and a mixture by using a rotary evaporator, and separating by using column chromatography to obtain 4-methylbenzaldehyde, wherein the yield is 73%, and the chemical selectivity of a product is 61%.
Compared with the catalyst in the prior art, the Au-Mg/SAPO-11 molecular sieve catalyst has stronger catalytic efficiency and catalytic performance and high repeated utilization rate, and simultaneously reduces the use of strong acid, thereby reducing the corrosion to equipment, reducing the energy consumption and having good application prospect. The catalyst prepared by the invention is used for alcohol oxidation reaction, replaces strong oxidizing oxidants such as permanganate and the like, realizes high-efficiency selectivity of alcohol under mild conditions, and has strong catalytic activity and good catalytic effect.
In light of the foregoing description of preferred embodiments in accordance with the invention, it is to be understood that numerous changes and modifications may be made by those skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An Au-Mg/SAPO-11 molecular sieve catalyst is characterized in that: the Au-Mg/SAPO-11 molecular sieve catalyst is prepared from an SAPO-11 molecular sieve and a composite nano metal Au-Mg.
2. The method for preparing an Au-Mg/SAPO-11 molecular sieve catalyst according to claim 1, comprising the steps of:
1) synthesis of SAPO-11 molecular sieve
Mixing an aluminum source, a phosphorus source and a silicon source to form an aqueous solution, adding a template agent into the aqueous solution to perform reaction, and separating and purifying to obtain the SAPO-11 molecular sieve, wherein the molar ratio of the aluminum source to the phosphorus source to the silicon source is as follows: an aluminum source: a phosphorus source: silicon source 1: (1.2-1.5): (0.1-0.3);
2) preparation of Au-Mg/SAPO-11 molecular sieve catalyst
Adding an Au-containing compound into distilled water, then adding the SAPO-11 molecular sieve and triazole prepared in the step 1), then adding a stabilizer, stirring, standing, adding sodium borohydride for reduction, drying, cooling to room temperature, grinding, and roasting to prepare an Au/SAPO-11 molecular sieve;
dissolving a Mg-containing compound in distilled water, then weighing the prepared Au/SAPO-11 molecular sieve, stirring, standing, adding sodium borohydride for reaction, drying, cooling to normal temperature, grinding and roasting to obtain the Au-Mg/SAPO-11 molecular sieve catalyst.
3. The method for preparing the Au-Mg/SAPO-11 molecular sieve catalyst according to claim 2, wherein the aluminum source is at least one selected from the group consisting of pseudoboehmite and alumina; the phosphorus source is selected from phosphoric acid; the silicon source is at least one of tetraethoxysilane and silicon dioxide; the template agent is selected from at least one of di-n-propylamine and hexadecyl phosphate.
4. The method for preparing the Au-Mg/SAPO-11 molecular sieve catalyst according to claim 2, wherein in step 2), the stabilizer is isopropanol.
5. The method of preparing an Au-Mg/SAPO-11 molecular sieve catalyst according to claim 2, wherein the Au containing compound is KAuCl4Or AuCl3Is (CH) and the Mg-containing compound is3COO)2Mg or Mg (OTf)2At least one of (1).
6. The method for preparing Au-Mg/SAPO-11 molecular sieve catalyst as claimed in claim 2, wherein the Au-containing compound in step 2) is added into distilled water, then the SAPO-11 molecular sieve prepared in step 1) and triazole are added, then stabilizer isopropanol is added, stirring is carried out for 4-12h, then standing is carried out for 12-48h, sodium borohydride is added for reduction reaction for 2-24h, the obtained product is placed into a vacuum drying box with the temperature of 100 ℃ and 120 ℃ for drying for 2-18h, cooling is carried out to normal temperature, grinding is carried out, roasting is carried out for 2-48h under the condition of 500 ℃ of 400 ℃ and cooling to room temperature, and grinding is carried out to obtain the Au/SAPO-11 molecular sieve.
7. The method for preparing Au-Mg/SAPO-11 molecular sieve catalyst as claimed in claim 2, wherein in the step 2), the Mg-containing compound is dissolved in distilled water, then the prepared Au/SAPO-11 molecular sieve is weighed, stirred for 2-12h, kept stand for 2-24h, added with sodium borohydride for reaction for 2-24h, dried for 2-24h in an environment with temperature of 100-120 ℃, cooled to normal temperature, ground, and roasted for 2-24h at 800 ℃ of 300-.
8. Use of the Au-Mg/SAPO-11 molecular sieve catalyst according to claim 1 or the Au-Mg/SAPO-11 molecular sieve catalyst prepared by the method of preparation of the Au-Mg/SAPO-11 molecular sieve catalyst according to any one of claims 2 to 7, wherein: the Au-Mg/SAPO-11 molecular sieve catalyst is used for synthesizing bisphenol F.
9. The use of an Au-Mg/SAPO-11 molecular sieve catalyst according to claim 8, wherein: the method comprises the following steps: under the condition of 30-100 ℃, in a reaction kettle, taking phenol as a raw material and toluene as a solvent, adding the Au-Mg/SAPO-11 catalyst, adding a formaldehyde solution, reacting for 6-12h, standing and cooling after the reaction is finished, leaching after solid is separated out, and washing with a hot solvent; recrystallizing the solid again to obtain bisphenol F, wherein the mass ratio of phenol to formaldehyde to the Au-Mg/SAPO-11 molecular sieve catalyst is (3-47): 1:(0.001-0.7).
10. Use of the Au-Mg/SAPO-11 molecular sieve catalyst according to claim 1 or the Au-Mg/SAPO-11 molecular sieve catalyst prepared by the method of preparation of the Au-Mg/SAPO-11 molecular sieve catalyst according to any one of claims 2 to 7, wherein: the Au-Mg/SAPO-11 molecular sieve catalyst is used for alcohol oxidation reaction and comprises the following steps: and (2) placing the benzyl alcohol derivative in an acetonitrile solvent, wherein the mass ratio of the benzyl alcohol derivative to the Au-Mg/SAPO-11 molecular sieve catalyst is 1: (0.01-0.8) adding the Au-Mg/SAPO-11 molecular sieve catalyst for catalysis to obtain the corresponding aldehyde.
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| CN202110504195.3A Active CN113198530B (en) | 2021-05-10 | 2021-05-10 | Au-Mg/SAPO-11 molecular sieve catalyst, and preparation method and application thereof |
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