CN118059878A - Reaction vanadium-based catalyst for synthesizing vanillin by catalytic oxidation of 4-methyl phenol, preparation method and manufacturing method of vanillin - Google Patents
Reaction vanadium-based catalyst for synthesizing vanillin by catalytic oxidation of 4-methyl phenol, preparation method and manufacturing method of vanillin Download PDFInfo
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- CN118059878A CN118059878A CN202211426084.6A CN202211426084A CN118059878A CN 118059878 A CN118059878 A CN 118059878A CN 202211426084 A CN202211426084 A CN 202211426084A CN 118059878 A CN118059878 A CN 118059878A
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- Prior art keywords
- vanadium
- vanillin
- catalyst
- carrier
- nitrate
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 74
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 239000011246 composite particle Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 26
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- RIVXQHNOKLXDBP-UHFFFAOYSA-K aluminum;hydrogen carbonate Chemical compound [Al+3].OC([O-])=O.OC([O-])=O.OC([O-])=O RIVXQHNOKLXDBP-UHFFFAOYSA-K 0.000 claims description 2
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
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- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
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Landscapes
- Catalysts (AREA)
Abstract
The invention provides a reaction vanadium-based catalyst for synthesizing vanillin by catalytic oxidation of 4-methyl phenol, a preparation method and a manufacturing method of vanillin, and a vanadium-based carrier, wherein the carrier contains composite particles formed by vanadium in an oxidation state and X (X represents at least 1 element selected from the group consisting of cobalt, iron, nickel and cerium) and a carrier for loading the composite nano particles, the surface of a shell layer does not contain the composite particles, and the composite particles are distributed in a local area below the outer surface of the composite nano particle carrier. The catalyst is used for catalyzing and oxidizing 4-methyl phenol to synthesize vanillin. Compared with the existing catalyst, the catalyst has good water resistance and acid and alkali resistance, can keep higher mechanical strength and chemical stability in the long-time reaction process, and has the advantages of simple preparation method, lower cost and the like.
Description
Technical Field
The present invention relates to a composite particle carrier comprising vanadium in an oxidized state and X (X represents at least 1 element selected from the group consisting of cobalt, iron, nickel, and cerium) supported on a carrier, and a method for producing a vanillin catalyst by catalytic oxidation of 4-methylphenols using the composite particle carrier.
Background
Vanillin, also known as vanillin chemical name 3-methoxy-4-hydroxybenzaldehyde, is an organic compound extracted from the plant Vanilla fabacea of the family Rutaceae. The vanillin has rich milk fragrance and vanilla bean fragrance, plays roles in fixing fragrance and enhancing fragrance, is widely applied to industries such as cosmetics, tobacco, cakes, candies, baked foods and the like, is one of the synthetic spice varieties with the largest global yield, and has the history of industrialized production of the vanillin for over 100 years.
The main processes for the industrial production of vanillin at present are lignin method, guaiacol method, safrole method and eugenol method. The traditional synthesis process has the problems of long reaction route, low yield, more side reactions and more three wastes in different degrees. In 2005, domestic enterprises continue to adopt the glyoxylate method to produce vanillin by using the production process, but the glyoxylate price of domestic production is relatively high, and some key technical problems such as oxidation stability, wastewater reuse (about 20 tons of wastewater is produced by 1 ton of vanillin), low product yield and the like are not solved well.
There are patent reports on the direct oxidation of vanillin with heterogeneous catalysts to give vanillin. As in the patent with publication number CN102527389A, cobalt iron is used as an active component to prepare a heterogeneous catalyst; as another example, in the patent publication CN101234351a, a supported solid metal oxide catalyst is disclosed, in which a transition metal oxide is used as an active component, at least one of alumina, silica, titania and activated carbon is used as a carrier, and a rare earth element is used as a promoter; further, as disclosed in the patent publication No. CN104607182A, a supported catalyst using nano palladium as an active component is used for the direct oxidation of vanillyl alcohol. However, the raw material vanillyl alcohol is expensive, the synthesis process is still immature, and the wide process application cannot be obtained temporarily.
The p-cresol method technology for preparing vanillin by one-step oxidation of 4-methyl guaiacol is valued by people, and the method has the advantages of wide sources of raw materials, simple process route, low price, simple process, safe reaction process and convenient post-treatment; and the three wastes are less discharged, and the product quality is good and is equivalent to the natural product of the same class. Therefore, the oxidation of p-cresol has more development potential and process development advantage. However, in the process, the one-step oxidation of 4-methyl guaiacol to prepare vanillin is a difficult point of the process, so that the yield of the process is low, and the preparation of a proper catalyst is a key problem of the process route.
In recent years, many patents report that the conversion rate of vanillin can reach 90% by using salts of transition metals (such as Co, cr, mn, cu, ni, zn and the like) as catalysts and performing homogeneous reaction in strong alkali and alcohol solutions (more cobalt salt catalysts are commonly used, and the yield of vanillin can reach more than 70%). The homogeneous phase reaction uses homogeneous phase catalyst, which can lead to low yield of vanillin, difficult separation and secondary pollution. Therefore, the preparation of an excellent heterogeneous catalyst is a path for solving the technical problem by performing a heterogeneous process. The patent of CN 106986756A introduces a multiphase reaction system to prepare a heterogeneous supported catalyst which takes nano cobalt as an active component and takes a porous nitrogen-doped carbon material as a carrier, wherein the layered catalyst carries out heterogeneous catalytic oxidation on 4-methyl guaiacol, the conversion rate of reactants is 100 percent, and the highest selectivity is 90 percent. CN104162444 a discloses a layered catalyst with cobalt as an active component. The layered catalyst carries out heterogeneous catalytic oxidation on 4-methyl guaiacol, the conversion rate is 100%, and the selectivity is 66% at most. The monopoly of the technology can not meet the market demand of China, so the development of more excellent novel heterogeneous catalysts is very necessary.
Disclosure of Invention
In order to fill the technical blank of China, the subject group provides a vanadic composite particle catalyst for synthesizing vanillin by catalytic oxidation of 2-methoxy-4-methylphenol. Compared with the existing catalyst, the catalyst provided by the invention has the advantages of no noble metal, good water resistance and acid and alkali resistance, high mechanical strength and chemical stability in the long-time reaction process, simple preparation method, low cost and the like. The method is used for catalytic synthesis of vanillin, the conversion rate of 4-methyl phenol is up to 98%, the selectivity is up to 93%, other byproducts are reduced, and the post-treatment cost is reduced.
The multi-component water-resistant catalyst provided by the patent is in a 'core-shell' structure, wherein VmXn composite particles are not contained on the surface of a shell, and the composite particles are distributed in a local area below the outer surface of a composite particle load, so that the multi-component water-resistant catalyst has the advantages of simple preparation method, low cost, good long-time reaction stability and the like. VmXn composite particles are not uniformly loaded into the carrier, so that the diffusion resistance of the carrier to reaction raw materials and reaction products is reduced; the shell layer does not contain composite particles, so that the problem that active points are covered and deactivated caused by the adsorption of byproducts is solved; at the same time, the catalyst shell can reduce the loss of active components caused by mechanical abrasion.
When the composite particle load is used for the preparation reaction of vanillin, the conversion rate of 2-methoxy-4-methylphenol is up to 98%, the conversion rate of 2-methoxy-4-methylphenol is up to 93%, the activity of the catalyst is basically unchanged after 9 times of reaction, and only trace vanadium is stripped and dissolved in ICP detection before and after the reaction, so that the problems are better solved.
The implementation method of the invention is as follows:
1. A reaction vanadium-based catalyst for catalytic oxidation of 4-methylphenol to vanillin, characterized in that the catalyst contains vanadium in oxidation state and X in a V/X atomic ratio ranging from 0.01 to 6 (preferably from 0.3 to 0.8, more preferably from 0.5 to 0.8) supported on a carrier,
Wherein the valence state of vanadium is five, and X represents at least 1 element selected from the group consisting of cobalt, iron, nickel and cerium.
2. The vanadium-based catalyst for catalytic synthesis of vanillin according to claim 1, wherein the catalyst is composed of composite nanoparticles of oxides of vanadium and X in oxidation state, with particle size Here, X represents an iron element. From the observation result of a Transmission Electron Microscope (TEM), approximately spherical nanoparticles of 2 to 5nn were uniformly dispersed and supported on a carrier. From elemental analysis of nanoparticles using energy dispersive X-ray analysis (EDS), it was observed that vanadium and iron were co-present in either particle, and that the surface of the vanadium nanoparticle was coated with iron.
3. The vanadium-based catalyst for catalytic synthesis of vanillin according to claim 2, wherein said composite nanoparticle is a particle comprising a carrier prepared first and then vanadium in oxidation state and X in oxidation state supported on the carrier. From the comparison of example 5 and examples 6, 7, 8, 9, it can be assumed that vanadium and X are complex coactive supported on the support, and that vanadium and X may form a similar alloy, altering the electron cloud state itself. Wherein vanadium in an oxidation state and X in an oxidation state are active ingredients, the surface of the carrier contains few active ingredients, and the active ingredients are mainly distributed in a local area below the outer surface of the composite particle carrier. Example 7 the very low vanadium content of the support surface can be seen by the electronic image of EDX, thus suggesting that the active ingredient composite particles should be distributed predominantly below the support surface.
4. The vanadium-based catalyst for catalytic synthesis of vanillin according to claim 1, wherein the carrier is a composite oxide containing silica, alumina, and oxides of other metal elements, and wherein the molar ratio of the other elements except oxygen is as follows: it comprisesSilicon in the mole% range,/>The proportion of elements other than aluminum, silicon and aluminum in the molar% range is/>Molar ratio;
The other elements are one or more of magnesium, iron, erbium, lanthanum and cerium (for example, silica-alumina-magnesia-titania, silica-alumina-lanthanum oxide, silica-alumina-magnesia-ceria, etc.).
5. The vanadium-based catalyst for catalytic synthesis of vanillin according to claim 4, wherein the specific surface area of the carrier isPore diameter is/>Pore volume is/> Particle size is
6. According to the aboveThe vanadium-based catalyst for catalytic synthesis of vanillin has the composition ratio of manganese to silicon oxide calculated by Mn/Si atomic ratio of/>(Preferably 0.01-0.2, more preferably 0.01-0.1).
7. According to the aboveThe vanadium-based catalyst for catalytic synthesis of vanillin, which is characterized in that the catalyst is prepared by firstly preparing a carrier, and then loading vanadium in an oxidation state and X in an oxidation state on the carrier;
preparation of composite oxide carrier:
The precursor of two or three oxides in Al 2O3、MgO、Ti2O3、La2O3、CeO2 and the aqueous solution of SiO 2 precursor are mixed with concentrated nitric acid (concentration range of 60% -85% and weight of 30% silica sol) at 0-100deg.C (preferred range of 30-50deg.C) Multiple weight) are evenly mixed, stirred and cured for 10-48 hours at 50-80 ℃, and a spray drying forming technology is adopted to obtain the composite oxide carrier (the grain diameter is 20-450 mu m, the specific surface area is/>)Pore diameter is/>Pore volume of )。
The precursor of SiO 2 is selected fromSilica sol;
the precursor of MgO is one or more than two of magnesium salts such as magnesium oxalate, magnesium acetate, magnesium nitrate, magnesium chloride, magnesium hydroxide, magnesium carbonate or magnesium oxide;
The precursor of Al 2O3 is one or more than two of aluminum salts such as aluminum hydroxide, aluminum ammonium carbonate, aluminum ammonium sulfate, aluminum bicarbonate, aluminum nitrate or aluminum trichloride;
The precursor of La 2O3 is selected from one or more than two of lanthanum salts such as lanthanum nitrate, lanthanum acetate and the like;
The precursor of TiO 2 is one or more than two of titanium salts such as titanium nitrate, titanium acetate and the like;
the precursor of CeO 2 is selected from one or two of cerium nitrate and ammonium cerium nitrate.
8. The method for preparing a catalyst according to claim 7, wherein the step of supporting vanadium in an oxidized state and X in an oxidized state on a carrier comprises the steps of:
step 1, preparing an aqueous solution containing soluble metal salts of vanadium and X, adding a precipitant and a composite oxide carrier, and reacting at 50-100deg.C Cooling the mixture to room temperature, and filtering to obtain a solid;
The concentration of vanadium in the aqueous solution is (Preferably 0.01-0.05, more preferably 0.01-0.04);
the precipitant is one or two of urea and hexamethylenetetramine, and its concentration in water solution is (Preferably 0.1 to 0.6, more preferably 0.2 to 0.5);
the soluble metal salt of vanadium is one or two of sodium metavanadate and potassium metavanadate;
the soluble metal salt of X is one or more than two of cobalt nitrate, cobalt acetate, cerium nitrate hexahydrate, ammonium cerium nitrate, ferric nitrate nonahydrate, ferric acetate, nickel acetate and nickel nitrate;
and 2, drying the obtained catalyst precursor by heat treatment at 30-100 ℃, and then roasting at high temperature to enable vanadium to be in an oxide state.
Calcining by using a muffle furnace; the roasting temperature is 300-900 ℃, preferably 400-600 ℃, and the roasting time is 2-20h, preferably 2-8h.
A method for producing vanillin is characterized by comprising the steps of: oxidizing 4-methyl phenol in one step in the presence of the vanadium-based catalyst and oxygen and/or air to generate vanillin;
The reaction condition is that 4-methyl phenol, proton solvent, inorganic base and the catalyst prepared in the step 1-11 are placed in a reaction kettle, oxygen sources such as oxygen, air or mixed gas containing oxygen are added, and the reaction is carried out for 8-15 hours at 70-100 ℃ in the kettle, and the control of the reaction gas phase is completed. The treatment mode of the reaction liquid is as follows: filtering the reaction solution, and neutralizing the filtrate with concentrated hydrochloric acid until the pH value is 3-6; quantitative analysis of the treated liquid was performed qualitatively and quantitatively by high performance gas chromatography, and the yield of vanillin as a reaction product was determined by internal standard method based on the standard curve.
The reaction kettle is 250ml and matches the flow rate of oxygen source gas
The 4-methylphenol is 4-methylphenol, 2-methoxy-4-methylphenol.
The proton solvent is glycol, glycol monomethyl ether, isopropanol, glycol dimethyl ether, and water, and the mass ratio of the 4-methyl phenol to the proton solvent is
The inorganic alkali is sodium hydroxide, lithium hydroxide and potassium hydroxide, and the mol ratio of the 4-methyl phenol to the inorganic alkali is
The specific embodiment is as follows:
The present invention is not limited to the following embodiments, and may be implemented by various modifications within the scope of the gist thereof.
Carrier preparation examples
Example 1
Mixing 30% silica sol (pH=4.5) (20 g,10 mmol), aluminum nitrate nonahydrate (3 g,8 mmol), magnesium hydroxide (0.116 g,2 mmol) and 6g of 65% concentrated nitric acid, deionized water 120mL uniformly at 25 ℃, stirring and curing the mixture at 50 ℃ for 24 hours to obtain a uniform solid solution suspension, and adopting a spray drying molding technology to obtain SiO 2-Al2O3 -MgO composite oxide (the molar ratio of the elements of the carrier silicon aluminum magnesium is 50:40:10, the particle size is 50-100 mu m, the specific surface area is 280m 2/g, and the pore diameter is 280m 2/g)Pore volume was 0.7 mL/g).
Example 2
30% Silica sol (pH=4.5) (20 g,10 mmol), aluminum nitrate nonahydrate (2.25 g,6 mmol), magnesium hydroxide (0.058 g,1 mmol), titanium nitrate (0.3 g,1 mmol), 4g of concentrated nitric acid with concentration of 80%, 120mL of deionized water are uniformly mixed at 25 ℃, the mixture is kept at 50 ℃ and stirred and cured for 24 hours to obtain uniform solid solution suspension, and a spray drying molding technology is adopted to obtain a composite oxide carrier SiO 2-Al2O3-MgO-TiO2 (the molar ratio of the elements of the carrier silicon aluminum magnesium titanium is 55.6:33.3:5.6:5.5.5, the particle size is 63-105 mu m, the specific surface area is 302m2/g, and the pore diameter is 302 mu m 2/g)Pore volume was 0.7 mL/g).
Example 3
30% Silica sol (pH=4.5) (20 g,10 mmol), aluminum nitrate nonahydrate (2.25 g,6 mmol), lanthanum nitrate hexahydrate (0.433 g,1 mmol) and 60% concentrated nitric acid with a mass concentration of 6g, 120mL deionized water are stirred and cured for 24 hours at 50 ℃ to obtain a uniform solid solution suspension, and a spray drying molding technology is adopted to obtain a composite oxide carrier SiO 2-Al2O3-La2O3 (the molar ratio of elements of the carrier silicon-aluminum-lanthanum is 58.8:35.3:5.9, the particle size is 55-105 mu m, the specific surface area is 310m 2/g, and the pore diameter is 310m 2/g)Pore volume was 0.8 mL/g).
Example 4
30% Silica sol (pH=4.5) (20 g,10 mmol), aluminum nitrate nonahydrate (1.13 g,3 mmol), magnesium hydroxide (0.058 g,1 mmol), cerium nitrate hexahydrate (0.433 g,1 mmol), 75% concentrated nitric acid with mass concentration of 6g and 120mL deionized water are uniformly mixed at 25 ℃, the mixture is stirred and cured for 24 hours at 50 ℃ to obtain uniform solid solution suspension, and a spray drying molding technology is adopted to obtain a composite oxide carrier SiO 2-Al2O3-MgO-CeO2 (the molar ratio of the elements of the carrier silicon aluminum magnesium cerium is 66.7:20:6.7:6.6. The particle size is 58-100 mu.m, the specific surface area is 320m 2/g and the pore diameter is 320 m) Pore volume was 0.9 mL/g).
Catalyst preparation examples
Example 5
6G of SiO 2-Al2O3 -MgO carrier A, 1.5g of urea, sodium metavanadate (0.244 g,2 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. And cooling to obtain a catalyst A1, and determining the vanadium content to be 1.32% and a V/Si atomic ratio meter 0.0290. The electron image of EDX shows that the vanadium content of the support surface is 0. And the particle size of the active vanadium particles is 2-3nm by SEM measurement.
Example 6
6G of SiO 2-Al2O3 -MgO carrier A, 1.5g of urea, sodium metavanadate (0.244 g,2 mmol), cerium nitrate hexahydrate (1.74 g,4 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. And cooling to obtain a catalyst A2, wherein the content of vanadium is 1.23%, the content of cerium is 5.91%, the V/Ce atomic ratio meter is 0.571, and the V/Si atomic ratio meter is 0.0286. The electron image of EDX shows that the vanadium content of the support surface is 0.001 of all elements (i.e. the support surface contains little active component, which is mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium-cerium active composite particles is 2-3nm as determined by SEM.
Example 7
6G of SiO 2-Al2O3 -MgO carrier A, 1.5g of urea, sodium metavanadate (0.244 g,2 mmol), ferric nitrate nonahydrate (1.21 g,3 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, the mixture is cooled to room temperature and filtered, the obtained solid is dried in vacuum at 80 ℃ for 1h, and the obtained solid is placed in a muffle furnace for calcination at 600 ℃ for 3h. And cooling to obtain a catalyst A3, wherein the content of vanadium is 1.29%, the content of iron is 1.86%, and the V/Fe atomic ratio is 0.762. And the particle size of the active manganese-cerium composite particles is 2-5nm as determined by SEM. V/Si atomic ratio meter 0.0285. The electron image of EDX shows that the vanadium content of the support surface is 0 (i.e. the support surface contains little active components, which are mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active ferrovanadium composite particles is 2-3nm as determined by SEM.
Example 8
6G of SiO 2-Al2O3 -MgO carrier A, 1.5g of urea, sodium metavanadate (0.244 g,2 mmol), cobalt nitrate hexahydrate (0.873 g,3 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. And cooling to obtain a catalyst A4, wherein the content of vanadium is 1.29%, the content of cobalt is 1.96%, the V/Co atomic ratio is 0.761, and the V/Si atomic ratio is 0.0288. The electron image of EDX shows that the vanadium content of the support surface is 0 (i.e. the support surface contains little active components, which are mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium cobalt composite particles is 2-3nm as determined by SEM.
Example 9
6G of SiO 2-Al2O3 -MgO carrier A, 1.5g of urea, sodium metavanadate (0.244 g,2 mmol), hexahydrate and nickel nitrate (0.872 g,3 mmol) are sequentially added into a reactor, uniformly mixed with 60mL of deionized water, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. And cooling to obtain a catalyst A5, wherein the content of vanadium is 1.29%, the content of nickel is 1.95%, the V/Ni atomic ratio meter is 0.760, and the V/Si atomic ratio meter 0.0286. The electron image of EDX shows that the vanadium content of the support surface is 0.001 of all elements (i.e. the support surface contains little active component, which is mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium-nickel composite particles is 2-3nm as determined by SEM.
Example 10
6G of SiO 2-Al2O3-MgO-TiO2 carrier B, 0.8g of hexamethyltetramine, sodium metavanadate (0.244 g,2 mmol), ferric nitrate nonahydrate (1.21 g,3 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. Naturally cooling to obtain a catalyst B, wherein the content of vanadium is 1.29%, the content of iron is 2.74%, the V/Fe atomic ratio meter is 0.761, and the V/Si atomic ratio meter is 0.0286. The electron image of EDX shows that the vanadium content of the support surface is 0.001 of all elements (i.e. the support surface contains little active component, which is mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active ferrovanadium composite particles is 2-3nm as determined by SEM.
Example 11
6G of SiO 2-Al2O3-La2O3 carrier C, 0.8g of hexamethylenetetramine, sodium metavanadate (0.244 g,2 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. Naturally cooling to obtain a catalyst C1, and determining the vanadium content to be 1.32% and the V/Si atomic ratio to be 0.0285. The electron image of EDX shows that the vanadium content of the support surface is 0 (i.e. the support surface contains little active components, which are mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium particles is 2-3nm by SEM measurement.
Example 12
6G of SiO 2-Al2O3-La2O3 carrier C, 0.8g of hexamethyltetramine, sodium metavanadate (0.244 g,2 mmol), ferric nitrate nonahydrate (1.21 g,3 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. And naturally cooling to obtain a catalyst C2, wherein the content of vanadium is 1.29%, the content of iron is 1.85%, the V/Fe atomic ratio meter is 0.763, and the V/Si atomic ratio meter is 0.0284. The electron image of EDX shows that the vanadium content of the support surface is 0.001 of all elements (i.e. the support surface contains little active component, which is mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active ferrovanadium composite particles is 2-3nm as determined by SEM.
Example 13
6G of SiO 2-Al2O3-La2O3 carrier C, 0.8g of hexamethyltetramine, sodium metavanadate (0.244 g,2 mmol), hexahydrate and nickel nitrate (0.872 g,3 mmol) are sequentially added into a reactor, uniformly mixed with 60mL of deionized water, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 600 ℃ for 3h. And naturally cooling to obtain the catalyst C3, wherein the content of vanadium is 1.293%, the content of nickel is 1.96%, the V/Ni atomic ratio meter is 0.760, and the V/Si atomic ratio meter is 0.0285. The electron image of EDX shows that the vanadium content of the support surface is 0.001 of all elements (i.e. the support surface contains little active component, which is mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium-nickel composite particles is 2-3nm as determined by SEM.
Example 14
6G of SiO 2-MgO-Al2O3-CeO2 carrier D, 0.8g of hexamethylenetetramine, sodium metavanadate (0.244 g,2 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 500 ℃ for 3h. And cooling to obtain a catalyst D1, and determining the vanadium content to be 1.325% and a V/Si atomic ratio meter 0.0257. The electron image of EDX shows that the vanadium content of the support surface is 0 (i.e. the support surface contains little active components, which are mainly distributed in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium particles is 2-3nm by SEM measurement.
Example 15
6G of SiO 2-MgO-Al2O3-CeO2 carrier D, 0.8g of hexamethylenetetramine, sodium metavanadate (0.244 g,2 mmol), cerium nitrate hexahydrate (1.31 g,3 mmol) and 60mL of deionized water are sequentially added into a reactor, uniformly mixed, reacted for 0.5h at 80 ℃, cooled to room temperature, filtered, and the obtained solid is dried in vacuum at 80 ℃ for 1h, and is placed in a muffle furnace for calcination at 500 ℃ for 3h. After cooling, catalyst D2 was obtained, which was found to have a vanadium content of 1.252%, a cerium content of 6.67%, a V/Ce atomic ratio of 0.516 and a V/Si atomic ratio of 0.0256. The electron image of EDX can see that the vanadium content of the support surface is 0.001. Electron images of the active vanadium cerium EDX were examined by SEM and it was seen that the vanadium content of the support surface was 0.001 of all elements (i.e. the support surface contained little active component, which was distributed mainly in the localized area below the outer surface of the composite particle support). And the particle size of the active vanadium-nickel composite particles is 2-3nm as determined by SEM. The particle size of the active composite particles is 2-3nm.
Experimental results of catalyst for vanillin preparation (1):
13.8g of 2-methoxy-4-methylphenol, 82.8g of ethylene glycol monomethyl ether, 8g of sodium hydroxide and 1.38g of the catalyst prepared in each of examples 5-15 are placed in a 250ml reaction kettle, oxygen is added at the speed of 10ml/min, and the reaction is carried out for 12 hours at the temperature of 80 ℃ in the kettle, so that the reaction is finished.
The treatment mode of the reaction liquid is as follows: the reaction solution was filtered, the filtrate was neutralized to a pH of 3 to 6 (herein, 5) with concentrated hydrochloric acid, and 5g of the treated solution was measured. The body was analyzed qualitatively and quantitatively using high performance gas chromatography, 150mg of an internal standard was added according to the standard curve, and the yield of vanillin as a product after the reaction was determined using an internal standard method.
The standard curve of gas chromatography is prepared by using biphenyl as an internal standard, 150mg of the internal standard, and standard solutions with mass contents of 7%, 18%, 29%, 40%, 51%, 62%, 73%, 84% and 95% of 2-methoxy-4-methylphenol and 2-methoxy-4-aldehyde phenol are respectively prepared to prepare the standard curve.
The reaction was carried out 1 time and 9 times (the catalyst was filtered out after the reaction and the above reaction was repeated, and the experimental results are shown in Table 1.
TABLE 1
The results show that: when the composite particle load is used for the preparation reaction of vanillin, the conversion rate of 2-methoxy-4-methylphenol is up to 98%, the selectivity of 2-methoxy-4-aldehyde phenol is up to 93%, and the activity of the catalyst is basically unchanged after 9 times of reaction.
Claims (10)
1. A reaction vanadium-based catalyst for catalytic oxidation of 4-methylphenol to vanillin, characterized in that the catalyst contains vanadium in oxidation state and X in a V/X atomic ratio ranging from 0.01 to 6 (preferably from 0.3 to 0.8, more preferably from 0.5 to 0.8) supported on a carrier,
Wherein the valence state of vanadium is five, and X represents at least 1 element or more than two elements selected from the group consisting of cobalt, iron, nickel and cerium.
2. The vanadium-based catalyst for catalytic synthesis of vanillin according to claim 1, wherein the catalyst consists of composite nanoparticles of vanadium in oxidation state and X, with particle size ranging from 2 to 100 μm (preferably ranging from 2 to 10, more preferably ranging from 2 to 5), X representing at least 1 element selected from the group consisting of cobalt, iron, nickel and cerium or more, where X preferably represents an iron element.
3. The vanadium-based catalyst according to claim 1, wherein the support surface contains little active component, the active component being distributed predominantly in a localized area below the outer surface of the composite particle support.
4. A vanadium-based catalyst for the catalytic synthesis of vanillin according to any of claims 1-3, wherein the support is a composite oxide containing silica, alumina, and oxides of other metal elements, in which the molar ratio of the other elements than oxygen: it comprisesSilicon in the mole% range,/> The proportion of elements other than aluminum, silicon and aluminum in the molar% range is/>Molar ratio;
The other elements are one or more of magnesium, iron, erbium, lanthanum and cerium (for example, silica-alumina-magnesia-titania, silica-alumina-lanthanum oxide, silica-alumina-magnesia-ceria, etc.).
5. The vanadium-based catalyst for catalytic synthesis of vanillin according to claim 4, wherein the specific surface area of the carrier isPore diameter is/>Pore volume is/> Particle size is
6. According to the aboveThe vanadium-based catalyst for catalytic synthesis of vanillin has the composition ratio of manganese to silicon oxide calculated by Mn/Si atomic ratio of/>(Preferably 0.01-0.2, more preferably 0.01-0.1).
7. A claimThe vanadium-based catalyst for catalytic synthesis of vanillin, which is characterized in that the catalyst is prepared by firstly preparing a carrier, and then loading vanadium in an oxidation state and X in an oxidation state on the carrier;
preparation of composite oxide carrier:
The Al 2O3 precursor, the MgO, the Ti 2O3、La2O3、CeO2 precursor of two or three oxides and the SiO 2 precursor aqueous solution are mixed with concentrated nitric acid (concentration range is 60-85% and weight is 30% of silica sol weight) at 0-100 ℃ (preferably range is 30-50 ℃) Multiple weight) are evenly mixed, stirred and cured for 10-48 hours at 50-80 ℃, and a spray drying forming technology is adopted to obtain the composite oxide carrier (the grain diameter is 20-450 mu m, the specific surface area is/>)Pore diameter is/>Pore volume of
The precursor of SiO 2 is selected fromSilica sol;
the precursor of MgO is one or more than two of magnesium salts such as magnesium oxalate, magnesium acetate, magnesium nitrate, magnesium chloride, magnesium hydroxide, magnesium carbonate or magnesium oxide;
The precursor of Al 2O3 is one or more than two of aluminum salts such as aluminum hydroxide, aluminum ammonium carbonate, aluminum ammonium sulfate, aluminum bicarbonate, aluminum nitrate or aluminum trichloride;
The precursor of La 2O3 is selected from one or more than two of lanthanum salts such as lanthanum nitrate, lanthanum acetate and the like;
The precursor of TiO 2 is one or more than two of titanium salts such as titanium nitrate, titanium acetate and the like;
the precursor of CeO 2 is selected from one or two of cerium nitrate and ammonium cerium nitrate.
8. The method for preparing a catalyst according to claim 7, wherein the step of supporting vanadium in an oxidized state and X in an oxidized state on a carrier comprises the steps of:
step 1, preparing an aqueous solution containing soluble metal salts of vanadium and X, adding a precipitant and a composite oxide carrier, and reacting at 50-100deg.C Cooling the mixture to room temperature, and filtering to obtain a solid;
The concentration of vanadium in the aqueous solution is (Preferably 0.01-0.05, more preferably 0.01-0.04);
the precipitant is one or two of urea and hexamethylenetetramine, and its concentration in water solution is (Preferably 0.1 to 0.6, more preferably 0.2 to 0.5);
the soluble metal salt of vanadium is one or two of sodium metavanadate and potassium metavanadate;
the soluble metal salt of X is one or more than two of cobalt nitrate, cobalt acetate, cerium nitrate hexahydrate, ammonium cerium nitrate, ferric nitrate nonahydrate, ferric acetate, nickel acetate and nickel nitrate;
and 2, drying the obtained catalyst precursor by heat treatment at 30-100 ℃, and then roasting at high temperature to enable vanadium to be in an oxide state.
Calcining by using a muffle furnace; the roasting temperature is 300-900 ℃, preferably 400-600 ℃, and the roasting time is 2-20h, preferably 2-8h.
9. A method for producing vanillin is characterized by comprising the steps of: in the claimsOxidizing 4-methylphenol in one step in the presence of any one of the vanadium-based catalysts, and oxygen and/or air to form vanillin;
The reaction condition is that 4-methyl phenol, proton solvent, inorganic base and the catalyst in the above 1-6 are placed in a reaction kettle, one or more than two oxygen sources of oxygen, air or mixed gas containing oxygen are added, and the reaction is completed in the kettle at 70-100 ℃ for 8-15 hours.
10. The manufacturing method according to claim 9, characterized in that: the reaction kettle is 250ml and matches the flow rate of oxygen source gas
The 4-methylphenol is 4-methylphenol and/or 2-methoxy-4-methylphenol;
The proton solvent is one or more than two of ethylene glycol, ethylene glycol monomethyl ether, isopropanol, ethylene glycol dimethyl ether and water, and the mass ratio of the 4-methyl phenol to the proton solvent is
The inorganic alkali is one or more than two of sodium hydroxide, lithium hydroxide and potassium hydroxide, and the mol ratio of the 4-methyl phenol to the inorganic alkali is
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