CN108970604B - Molybdenum vanadium niobium-based composite oxide and synthesis method and application thereof - Google Patents
Molybdenum vanadium niobium-based composite oxide and synthesis method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- SXZJFAXGFNHJEM-UHFFFAOYSA-N [V].[Nb].[Mo] Chemical compound [V].[Nb].[Mo] SXZJFAXGFNHJEM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 229920005610 lignin Polymers 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000010955 niobium Substances 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 21
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 150000002576 ketones Chemical class 0.000 claims description 10
- 239000011949 solid catalyst Substances 0.000 claims description 10
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 63
- -1 ketone compound Chemical class 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 239000000539 dimer Substances 0.000 description 18
- 238000004090 dissolution Methods 0.000 description 16
- 229910021642 ultra pure water Inorganic materials 0.000 description 16
- 239000012498 ultrapure water Substances 0.000 description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 11
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 9
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003333 secondary alcohols Chemical group 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229930014251 monolignol Natural products 0.000 description 1
- 125000002293 monolignol group Chemical group 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229930015704 phenylpropanoid Natural products 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- B01J35/23—
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- B01J35/393—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a method for synthesizing a lignin C alpha ketone compound, in particular to a molybdenum vanadium niobium-based composite oxide and a synthesis method and application thereof. The general formula of the molybdenum vanadium niobium composite oxide is MoVxNbyAzOm, wherein A is doped metal ions, and x, y, z and m are the atomic ratios of V, Nb, A and O relative to Mo respectively; the doped metal ions are one of antimony, bismuth and nickel. The catalyst can selectively catalyze and oxidize the lignin C alpha alcohol dimer compound into C alpha ketone compounds, and the reaction temperature is controlled to be lower than 140 ℃. The catalyst used in the method is prepared by a solvothermal method, the process is simple, the synthesis cost is low, and the proportion of the composite oxide is adjusted, so that C alpha-OH alcoholic hydroxyl in more than 50% of polymerization bond beta-O-4 bonds in the lignin can be oxidized into C alpha-O ketone with high selectivity, and a lignin oxidation raw material is provided for the next catalytic depolymerization of the lignin.
Description
Technical Field
The invention relates to a method for synthesizing lignin C alpha ketone compounds, in particular to a molybdenum vanadium niobium based composite oxide and a synthesis method thereof, and application of the molybdenum vanadium niobium based composite oxide as a catalyst in selectively oxidizing C alpha alcohol in lignin into C alpha ketone under a certain condition to obtain a C alpha ketone semi-oxidation product of lignin.
Background
Lignin, one of the major components of plants (cellulose, hemicellulose, lignin), accounts for 30% of non-fossil organic carbon worldwide, is the most abundant natural aromatic polymer, can provide more energy than cellulose, and is an important renewable resource. At present, lignin is refined by biomass to obtain alternative energy and high value-added products, and the technical development of the lignin has important strategic significance on energy.
Compared with cellulose and hemicellulose, the chemical stability of lignin is high, the lignin is not easy to decompose, and the technical bottleneck is that C-O-C bonds connecting lignin monomers are selectively depolymerized. The lignin is polymerized by phenylpropanoid compounds, p-hydroxyphenol, guaiacyl and syringyl (H, guaiacyl (G) and syringyl (S)) are main structural monomers of the lignin (shown in figure 1), the connection mode among the three monomers is mainly ether bond, and the decomposed bottleneck chemical bond is beta-O-4 bond (shown in figure 2).
The C alpha secondary alcohol unit on the phenylpropyl makes the chemical energy barrier of beta-O-4 larger, so that the dissociation of the dimer ether bond is more difficult. After C alpha alcohol is oxidized into ketone, the C alpha alcohol is changed into oxidized lignin, the adjacent beta-O-4 bond is easily decomposed, and the C alpha alcohol shows higher efficiency in the ether bond decomposition process.
The traditional selective oxidation catalyst, such as Mn and Cr homogeneous cationic catalysts, produces waste liquid after reaction, which pollutes the environment and has higher recovery cost; TEMPO homogeneous catalysts are relatively expensive and not easily separable.
Disclosure of Invention
The invention aims to provide a catalytic oxidative dehydrogenation method for synthesizing a lignin C alpha ketone compound by catalyzing gas-liquid reaction by using a solid catalyst.
In order to achieve the purpose, the invention adopts the technical scheme that:
a molybdenum vanadium niobium based composite oxide has a general formula of MoVxNbyAzOm, wherein A is doped metal ions, and x, y, z and m are atomic ratios of V, Nb, A and O relative to Mo respectively; the doped metal ions are one of antimony, bismuth and nickel.
X is 0.51, y is 0.13, z is 0.1-0.55, and m is determined by the valence of other elements present in the composite metal oxide of the formula. The doping metal ion is preferably antimony or bismuth.
The application of the molybdenum vanadium niobium-based composite oxide as a solid catalyst in selective oxidative dehydrogenation of lignin is disclosed.
A solid catalyst is a molybdenum vanadium niobium composite oxide with a general formula of MoVxNbyAzOm, wherein A is doped metal ions, and x, y, z and m are the atomic ratios of V, Nb, A and O relative to Mo respectively; the doped metal ions are one of antimony, bismuth and nickel; x is 0.51, y is 0.13, z is 0.1-0.55, and m is determined by the valence of other elements present in the composite metal oxide of the formula.
The doping metal ion is preferably antimony or bismuth.
The selective oxidative dehydrogenation method of lignin adopts the molybdenum vanadium niobium-based composite oxide as a solid catalyst, and oxidizes C alpha-OH alcoholic hydroxyl in a lignin structure unit into C alpha-O ketone through selective oxidative dehydrogenation reaction so as to obtain a C alpha ketone semi-oxidation product of lignin.
Further, the molybdenum vanadium niobium-based composite oxide is used as a solid catalyst, lignin or a model compound thereof is used as a substrate, the substrate is dissolved in a solvent, the solid catalyst is utilized to carry out solid-liquid-gas three-phase reaction in the presence of an oxidant, and the reaction temperature is controlled to be 65-140 ℃.
The solvent is acetonitrile, N-dimethylacetamide or acetophenone.
The model compound is 2- (2 '-methoxyphenoxy) -1-phenethyl alcohol and 2- (2' -phenoxy) -1-phenethyl alcohol.
The dosage ratio of the substrate to the catalyst is 6:1-8: 1.
The reaction is carried out in a closed system or under stirring in a flowing system.
The reaction takes oxygen or air as an oxidant in a closed system, and the oxidant is injected into the closed system at room temperature at the pressure of 14.5-21.8 psi;
the reaction uses oxygen or air as oxidant in the flowing system, and the oxygen or air is introduced into the reaction solution at an excessive flow rate.
The C alpha alcohol in the lignin is selectively oxidized into C alpha ketone under the condition of being lower than 140 ℃ by adopting the molybdenum vanadium niobium composite oxide as the catalyst, wherein M ═ O active oxidation center is provided for oxidation reaction by utilizing molybdenum and vanadium in the catalyst, A represents antimony, bismuth and nickel, the function of adjusting oxidation capacity is achieved, peroxidation is prevented, the yield of semi-oxidation products is improved, and the C alpha ketone semi-oxidation products of the lignin are obtained; meanwhile, the catalyst is roasted at high temperature by nitrogen to form a four-component composite oxide crystal with oxygen defects (an X-ray diffraction pattern is shown in figure 3), the average grain size is about 100nm, the niobium in the catalyst plays a role in grain refinement, the nano-scale catalyst can be obtained, and the refined grains provide sufficient reaction interfaces for selective oxidation catalytic reaction.
The invention has the advantages that:
the molybdenum-vanadium-niobium composite oxide heterogeneous catalyst is suitable for high-selectivity oxidation of organic secondary alcohol into ketone, and is particularly suitable for selective oxidation reaction of C alpha-alcohol in a lignin structure. The low-temperature catalytic conversion of the secondary alcohol in the lignin dimer into the ketone compound through oxidative dehydrogenation is realized, the catalyst and a reaction product are easy to separate, and the catalyst is low in synthesis cost and can be repeatedly used; the catalyst obtained by the invention is suitable for the production of C alpha-ketone compounds synthesized by C alpha-alcohol through pharmaceutical intermediates, agricultural chemicals and food additives.
The catalyst is prepared by a solvothermal method, the process is simple, and the synthesis cost is low. And by adopting the three-component oxide catalyst, the proportion of the composite oxide can be adjusted, so that C alpha-OH alcoholic hydroxyl in more than 50% of polymerization bond beta-O-4 bonds in the lignin can be oxidized into C alpha ═ O ketone with high selectivity, and a raw material is provided for the next catalytic depolymerization of the lignin.
The molybdenum-vanadium-niobium three-component oxide heterogeneous catalyst replaces the traditional TEMPO homogeneous catalyst, Cr ion catalyst and Cu ion catalyst, and the reaction is easy to operate. The method has the advantages of less pollution, low energy consumption, easy separation of products and a catalyst system and suitability for large-scale production.
The method can directly use clean and green air or oxygen as an oxidant, avoids using hydrogen peroxide or ozone or potassium permanganate as the oxidant, has certain environmental protection and safe production values, and shows industrial application values with certain prospects.
Drawings
FIG. 1 shows three monomer chemical formulas of natural macromolecular lignin.
FIG. 2 is a schematic view of a monolignol linkage β -O-4 bond.
FIG. 3 shows Mo1V0.51Nb0.13Sb0.11OxX-ray diffraction pattern of the complex metal oxide.
FIG. 4 is a microstructure of a typical Mo-V-Nb oxide catalyst from example 7 provided by the present invention, wherein the average grain size of the synthesized composite oxide catalyst is about 100nm and the refined grains provide a sufficient reaction interface for selective oxidation catalysis.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following specific examples.
Preparation of composite oxide catalyst: ammonium molybdate tetrahydrate (NH) is used4)6Mo7O24·4H2O as molybdenum source for complex oxides, ammonium metavanadate NH4VO3Ammonium niobate oxalate hydrate C as vanadium source4O8NbOH·NH3Antimony trioxide Sb as a niobium source2O3As antimony source, nickel nitrate hexahydrate, Ni (NO)3)2·6H2O as a nickel source, bismuth nitrate pentahydrate Bi (NO)3)3·5H2O as bismuth source. The general formula of the synthesized composite oxide catalyst is a composite metal oxide shown by MoVxNbyAzOm; wherein A is doped metal ion, one element of antimony, bismuth and nickel.
Lignin C alpha-alcohol oxidation reaction: in the specific embodiment, the oxidation reactor used is a pressure-resistant glass reactor, but the reaction method of the present invention is not limited to this type of reactor, and a tank reactor or a fixed bed reactor may be used. The temperature of the selective oxidation reaction is controlled within 140 ℃, and the catalyst is required to be continuously stirred in order to ensure that the catalyst is contacted with a reactant in the reaction process. If the reactor is closed, oxygen or air is injected into the closed system at room temperature at a pressure of 14.5-21.8 psi; if the reactor is open, oxygen or air is introduced into the reaction solution at an excess flow rate.
The catalyst can selectively catalyze and oxidize a lignin C alpha alcohol dimer compound into a C alpha ketone compound, and the reaction temperature is controlled to be lower than 140 ℃. The catalyst used in the method is prepared by a solvothermal method, the process is simple, the synthesis cost is low, and the proportion of the composite oxide is adjusted, so that C alpha-OH alcoholic hydroxyl in more than 50% of polymerization bond beta-O-4 bonds in the lignin can be oxidized into C alpha-O ketone with high selectivity, and a lignin oxidation raw material is provided for the next catalytic depolymerization of the lignin.
Example 1:
Mo1V0.51Nb0.13Sb0.38Oxsynthesis of composite oxide catalyst: 10.77g of ammonium molybdate tetrahydrate was dissolved in 150ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 3.63g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 7.26g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 3.35g of antimony trioxide and 4g of nitric acid are added, the temperature is increased to 80 ℃, the mixture is heated and stirred for 1.5 hours, the solution gradually becomes yellow green liquid, and finally the color is dark greenish black. 2.42g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, and heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ to evaporate the water and dried at 120 ℃ for 12 hours. Drying, grinding, roasting the ground powder in a tubular furnace at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -methoxyphenoxy) -1-phenethyl alcohol as a reaction substrate and Mo1V0.51Nb0.13Sb0.38OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of the reaction substrate to the catalyst is 7:1, 200ml of acetonitrile is used as a solvent, the reaction temperature is controlled at 85 ℃, reflux reaction is carried out for 14 hours, and the yield of the reaction product 2- (2' -methoxyphenoxy) -1-acetophenone obtained by separating a sample through column chromatography is 53%.
Example 2:
Mo1V0.51Nb0.13Ni0.38Oxsynthesis of composite oxide catalyst: 5.74g of ammonium molybdate tetrahydrate was dissolved in 75ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 1.25g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 3.40g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 2.19g nitric acid hexahydrateNickel, heating to 80 deg.C, stirring for 1.5 hr, and making the solution become light green liquid and dark greenish black. 1.23g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 12 hours. And placing the ground powder into a tubular furnace for roasting, and roasting at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -phenoxy) -1-phenethyl alcohol as a reaction substrate, Mo1V0.51Nb0.13Ni0.38OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of the reaction substrate to the catalyst is 7:1, 200ml of acetonitrile is used as a solvent, the reaction temperature is controlled at 85 ℃, the reflux reaction is carried out for 10 hours, and the yield of the reaction product 2- (2' -phenoxy) -1-acetophenone obtained by separating a sample through column chromatography is 32%.
Example 3:
Mo1V0.51Nb0.13Bi0.38Oxsynthesis of composite oxide catalyst: 5.38g of ammonium molybdate tetrahydrate was dissolved in 150ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 1.81g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 3.63g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. Heating 5.58g of bismuth nitrate pentahydrate to 80 ℃, stirring for 1.5 hours, and gradually changing the solution into brownish black liquid, and finally turning into brick red. 1.22g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 8 hours. And placing the ground powder into a tubular furnace for roasting, and roasting at 600 ℃ for 4 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -methoxyphenoxy) -1-phenethyl alcohol as a reaction substrate and Mo1V0.51Nb0.13Bi0.38OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of the reaction substrate to the catalyst is 6:1, 200ml of acetonitrile is used as a solvent, the reaction temperature is controlled at 85 ℃, reflux reaction is carried out for 14 hours, and the yield of the reaction product 2- (2' -methoxyphenoxy) -1-acetophenone obtained by separating a sample through column chromatography is 67%.
Example 4:
Mo1V0.51Nb0.13Sb0.11Oxsynthesis of composite oxide catalyst: 10.77g of ammonium molybdate tetrahydrate was dissolved in 150ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 3.63g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 7.26g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 1.02g of antimony trioxide and 4g of nitric acid are added, the temperature is increased to 80 ℃, the mixture is heated and stirred for 1.5 hours, the solution gradually becomes yellow green liquid, and finally the color is dark greenish black. 2.42g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 12 hours. And placing the ground powder into a tubular furnace for roasting, and roasting at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -phenoxy) -1-phenethyl alcohol as a reaction substrate, Mo1V0.51Nb0.13Sb0.11OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of the reaction substrate to the catalyst is 8:1, 200ml of acetonitrile is used as a solvent, the reaction temperature is controlled at 75 ℃, air is used as an oxidant, the reaction system is a flow open system, the air flow rate is 30ml/min, and the yield of the reaction product 2- (2' -phenoxy) -1-acetophenone obtained by separating a sample through column chromatography is 43%.
Example 5:
Mo1V0.51Nb0.13Sb0.51Oxsynthesis of composite oxide catalyst: dissolving 10.77g ammonium molybdate tetrahydrate in 150ml ultrapure water, heating at 40 deg.C, stirringThe solution was dissolved and colorless and transparent. After dissolution, 3.63g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 7.26g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 4.52g of antimony trioxide and 4g of nitric acid are added, the temperature is raised to 80 ℃, the mixture is heated and stirred for 1.5 hours, the solution gradually becomes yellow green liquid, and finally the color is dark greenish black. 2.42g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 12 hours. And placing the ground powder into a tubular furnace for roasting, and roasting at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -methoxyphenoxy) -1-phenethyl alcohol as a reaction substrate and Mo1V0.51Nb0.13Sb0.51OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of the reaction substrate to the catalyst is 7:1, 200ml of acetonitrile is used as a solvent, the reaction temperature is controlled at 85 ℃, the reflux reaction is carried out for 10 hours, and the yield of the reaction product 2- (2' -methoxyphenoxy) -1-acetophenone obtained by separating a sample by column chromatography is 61%.
Example 6:
Mo1V0.51Nb0.13Sb0.38Oxsynthesis of composite oxide catalyst: 10.77g of ammonium molybdate tetrahydrate was dissolved in 150ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 3.63g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 7.26g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 3.35g of antimony trioxide and 4g of nitric acid are added, the temperature is increased to 80 ℃, the mixture is heated and stirred for 1.5 hours, the solution gradually becomes yellow green liquid, and finally the color is dark greenish black. 2.42g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 12 hours. Roasting the ground powder in a tubular furnace with nitrogen gasRoasting at 600 deg.c for 2 hr to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -phenoxy) -1-phenethyl alcohol as a reaction substrate, Mo1V0.51Nb0.13Sb0.38OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of the reaction substrate to the catalyst is 7:1, 200ml of acetonitrile is used as a solvent, the reaction temperature is controlled at 85 ℃, the reflux reaction is carried out for 14 hours, and the yield of the reaction product 2- (2' -phenoxy) -1-acetophenone obtained by separating a sample through column chromatography is 60%.
Example 7:
Mo1V0.51Nb0.13Sb0.11Oxsynthesis of composite oxide catalyst: 10.77g of ammonium molybdate tetrahydrate was dissolved in 150ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 3.63g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 7.26g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 1.02g of antimony trioxide and 4g of nitric acid are added, the temperature is increased to 80 ℃, the mixture is heated and stirred for 1.5 hours, the solution gradually becomes yellow green liquid, and finally the color is dark greenish black. 2.42g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 12 hours. And placing the ground powder into a tubular furnace for roasting, and roasting at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The obtained catalyst is roasted at high temperature by nitrogen to form four-component composite oxide crystals with oxygen defects (an X-ray diffraction pattern is shown in figure 3), the average grain size is about 100nm (shown in figure 4), the niobium in the catalyst plays a role in grain refinement, the nano-scale catalyst can be obtained, and the refined grains provide sufficient reaction interfaces for selective oxidation catalytic reactions.
The selective oxidation reaction process of the lignin dimer: adopts lignin dimer model compound 2- (2' -methoxyphenoxy) -1-phenethyl alcohol as a reaction substrate，Mo1V0.51Nb0.13Sb0.11OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of a reaction substrate to the catalyst is 7:1, 200ml of acetophenone is used as a solvent, the reaction temperature is controlled at 105 ℃, reflux reaction is carried out for 10 hours, and the yield of the reaction product 2- (2' -methoxyphenoxy) -1-acetophenone obtained by separating a sample by column chromatography is 45%.
Example 8:
Mo1V0.51Nb0.13Sb0.38Oxsynthesis of composite oxide catalyst: 10.77g of ammonium molybdate tetrahydrate was dissolved in 150ml of ultrapure water, and the solution was dissolved by heating and stirring at 40 ℃ to give a colorless transparent solution. After dissolution, 3.63g of ammonium metavanadate was added to the above solution, the solution became orange-yellow turbid, then 7.26g of oxalic acid was added to aid dissolution, the solution was brown-yellow transparent, and stirred for 20 minutes. 3.35g of antimony trioxide and 4g of nitric acid are added, the temperature is increased to 80 ℃, the mixture is heated and stirred for 1.5 hours, the solution gradually becomes yellow green liquid, and finally the color is dark greenish black. 2.42g of ammonium niobate oxalate hydrate was dissolved in 25mL of ultrapure water, added to the above solution, heated and stirred at 80 ℃ for 1 hour, then the temperature was raised to 85 ℃ and the water was evaporated to dryness, and dried at 120 ℃ for 12 hours. And placing the ground powder into a tubular furnace for roasting, and roasting at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the composite oxide catalyst.
The selective oxidation reaction process of the lignin dimer: adopts a lignin dimer model compound 2- (2' -methoxyphenoxy) -1-phenethyl alcohol as a reaction substrate and Mo1V0.51Nb0.13Sb0.38OxThe dosage of the composite oxide catalyst is 0.5g, the mass ratio of a reaction substrate to the catalyst is 7:1, 200ml of N, N-dimethylacetamide is used as a solvent, the reaction temperature is controlled at 135 ℃, reflux reaction is carried out for 8 hours, and the yield of the reaction product 2- (2' -methoxyphenoxy) -1-acetophenone obtained by separating a sample through column chromatography is 69%.
The catalyst is centrifugally precipitated, the rotating speed is controlled at 4000rpm, the catalyst is taken out after being kept at 200 ℃ in a drying oven for 8 hours, the selective oxidation reaction is carried out again under the same conditions, the yield of the obtained reaction product 2- (2' -methoxyphenoxy) -1-acetophenone is 68 percent, the reaction is repeatedly carried out for 5 times, and the yield of the reaction product is almost unchanged.
Claims (6)
1. The application of the molybdenum vanadium niobium-based composite oxide is characterized in that: the general formula of the molybdenum vanadium niobium composite oxide is MoVxNbyAzOm, wherein A is doped metal ions, and x, y, z and m are the atomic ratios of V, Nb, A and O relative to Mo respectively; the doped metal ions are one of antimony, bismuth and nickel;
x is 0.51, y is 0.13, z is 0.1-0.55, m is determined by the valence of other elements existing in the composite metal oxide of the general formula;
the molybdenum vanadium niobium-based composite oxide is used as a solid catalyst and is applied to selective oxidative dehydrogenation of lignin at the temperature of below 140 ℃.
2. A selective oxidative dehydrogenation method for lignin is characterized in that: the molybdenum vanadium niobium-based composite oxide as claimed in claim 1 is used as a solid catalyst, C alpha-OH alcoholic hydroxyl in a lignin structure unit is subjected to selective oxidative dehydrogenation reaction to be oxidized into C alpha = O ketone, and then a C alpha ketone semi-oxidation product of lignin is obtained;
the general formula of the molybdenum vanadium niobium-based composite oxide is MoVxNbyAzOm, wherein A is doped metal ions, and x, y, z and m are the atomic ratios of V, Nb, A and O relative to Mo respectively; the doped metal ions are one of antimony, bismuth and nickel;
x is 0.51, y is 0.13, z is 0.1-0.55, and m is determined by the valence of other elements present in the composite metal oxide of the formula.
3. The selective oxidative dehydrogenation process of lignin according to claim 2, wherein: the molybdenum vanadium niobium-based composite oxide is used as a solid catalyst, lignin or a model compound thereof is used as a substrate, the substrate is dissolved in a solvent, the solid catalyst is utilized to carry out solid-liquid-gas three-phase reaction in the presence of an oxidant, and the reaction temperature is controlled between 65 ℃ and 140 ℃.
4. A process for selective oxidative dehydrogenation of lignin according to claim 3, characterized in that: the solvent is acetonitrile, N-dimethylacetamide or acetophenone.
5. The selective oxidative dehydrogenation process of lignin according to claim 4, wherein: the reaction is carried out in a closed system or under stirring in a flowing system.
6. The selective oxidative dehydrogenation process of lignin according to claim 5, wherein: the reaction takes oxygen or air as an oxidant in a closed system, and the oxidant is injected into the closed system at room temperature at the pressure of 14.5-21.8 psi;
the reaction uses oxygen or air as oxidant in the flowing system, and the oxygen or air is introduced into the reaction solution at an excessive flow rate.
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