CN114588910A - Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization - Google Patents
Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization Download PDFInfo
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- CN114588910A CN114588910A CN202210249077.7A CN202210249077A CN114588910A CN 114588910 A CN114588910 A CN 114588910A CN 202210249077 A CN202210249077 A CN 202210249077A CN 114588910 A CN114588910 A CN 114588910A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229920005610 lignin Polymers 0.000 title claims abstract description 75
- 229910018605 Ni—Zn Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012263 liquid product Substances 0.000 claims abstract description 19
- -1 ester compound Chemical class 0.000 claims abstract description 4
- 239000002023 wood Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 57
- 239000011701 zinc Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052725 zinc Inorganic materials 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910000856 hastalloy Inorganic materials 0.000 claims description 8
- 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 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000012691 depolymerization reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 34
- 239000000126 substance Substances 0.000 abstract description 14
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- KPSSHRNLEXOPHK-UHFFFAOYSA-N 2-(4-hydroxy-3,5-dimethoxyphenyl)acetaldehyde Chemical compound COC1=CC(CC=O)=CC(OC)=C1O KPSSHRNLEXOPHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 abstract description 2
- 241000209504 Poaceae Species 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 240000008042 Zea mays Species 0.000 description 13
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 13
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 13
- 235000005822 corn Nutrition 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 239000010902 straw Substances 0.000 description 13
- 229910003962 NiZn Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
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- 230000008569 process Effects 0.000 description 6
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- 238000011049 filling Methods 0.000 description 5
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- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CHWNEIVBYREQRF-UHFFFAOYSA-N 4-Ethyl-2-methoxyphenol Chemical compound CCC1=CC=C(O)C(OC)=C1 CHWNEIVBYREQRF-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 1
- XUQXZROVMZNKPO-UHFFFAOYSA-N 3-(4-Hydroxy-3-methoxyphenyl)-2-methylpropionic acid Chemical compound COC1=CC(CC(C)C(O)=O)=CC=C1O XUQXZROVMZNKPO-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000878006 Miscanthus sinensis Species 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000006324 decarbonylation Effects 0.000 description 1
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- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000001785 ferulic acid Nutrition 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 1
- 229940114124 ferulic acid Drugs 0.000 description 1
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
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- 229930005346 hydroxycinnamic acid Natural products 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- QOHGMEYPUKSMST-UHFFFAOYSA-N methyl 2-(4-hydroxyphenyl)propanoate Chemical compound COC(=O)C(C)C1=CC=C(O)C=C1 QOHGMEYPUKSMST-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- B01J35/399—
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- B01J35/617—
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- B01J35/618—
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- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/06—Alkylated phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method and application of a Ni-Zn supported catalyst for lignin depolymerization. The catalyst is applied to the hydrogenolysis production of high value-added chemicals by the gramineae lignin suspended bed, has higher hydrogenolysis reaction activity and liquid product yield, and when the catalyst/lignin =20%, the total monomer yield can reach 18.25 wt%; when the catalyst/lignin =40%, the selectivity of the ester compound and the 4-hydroxy-3, 5-dimethoxyphenylacetaldehyde can reach about 36.43% and 16.75% respectively. Provides a new way for expanding the industrialization of wood biomass chemicals.
Description
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to preparation of a Ni-Zn supported catalyst and application of the Ni-Zn supported catalyst in producing fine chemicals by adding hydrogenolysis polymerization in a lignin suspension bed.
Background
In recent years, biomass as renewable organic carbon has attracted a wide attention under a large background of carbon neutralization and dual standards of international regulations for reducing carbon emissions, in the hope of being able to partially replace fossil fuels that are being depleted in the future. Lignin is the only renewable organic carbon source containing aromatic compounds in the nature and has great potential for conversion into liquid fuels and high value-added chemicals. The challenge of utilizing lignin to produce high value-added chemicals is to develop a catalyst that is efficient, highly stable, and highly selective.
Of the various reported strategies for lignin chemical decomposition, catalytic lignin hydrogenolysis using supported noble metal catalysts is one of the most popular methods. The noble metal for lignin degradation is Pd, Pt and Ru loaded on various carriers. Dou et al, in water as solvent, at 180 deg.C, with Pd-PdO/TiO2As a catalyst, the monomer yield of lignin can reach 40 wt% [ Applied Catalysis B: Environmental, 2022, 301: 120767 ]. Although the catalytic activity of the noble metal is high and the reaction conditions are mild, the scarcity of the noble metal and excessive hydrogenation to the depolymerization product result in failure to put into production.
The catalyst carriers widely used at present are oxide carriers, particularly Al2O3. However, for the lignin degradation reaction, firstly, due to γ -Al2O3And secondly, water is a byproduct of HDO and gamma-Al is formed under hydrothermal conditions2O3Is metastable and can be converted into beta-Al2O3And is not beneficial to the effective degradation of lignin. Carbon carriers have been increasingly studied because of their advantages of developed pores, large specific surface area, small density, good heat resistance, acid and alkali resistance, and the like. The patent CN 111659400 a discloses a bimetallic catalyst composed of Ni and Cu, which uses rGO as a carrier to prepare a highly dispersed hydrogenation catalyst using Ni-Cu as an active component. It is reported that the NiCu/C is used as catalyst to depolymerize poplar lignin which is organic solvent, ethanol and isopropanol are used as mixed solvent, and the obtained phenolic monomer can reach 63.4 wt% [ ACS Sustainable Chemistry ]& Engineering, 2020, 8(43): 16217-16228.】。
In conclusion, the development of a suspension bed hydrogenation catalyst with high activity, good selectivity, low cost and good stability is very necessary in the aspect of producing high value-added chemicals. The key point is how to select a material with high hydrogenation activity and low price as an active component and prepare the catalyst with high dispersity, high stability and high selectivity. In order to achieve the effect, the invention promotes the depolymerization degree of lignin by adjusting the proper synergistic effect between the acid sites and the metal sites of the catalyst, invents a Ni-Zn supported catalyst material for preparing ester high-added-value chemicals by the hydrogenation depolymerization of lignin, has green and simple preparation process and cheap raw materials, and has very important guiding significance and practical value for the production of the chemicals.
Disclosure of Invention
The invention aims to apply Ni-Zn supported catalyst material to the aspect of producing high value-added chemicals by lignin suspension bed hydrogenation depolymerization. Active carbon with high specific surface area is used as a carrier, active sites are highly dispersed by ultrasound, and the proportion of a nickel source and a zinc source is adjusted to prepare a series of active carbon supported Ni-Zn bimetallic catalysts for catalytic hydrogenolysis of organic solvent corn straw lignin in a methanol solvent. In the catalytic hydrogenolysis process, under the synergistic effect between the metal active sites and the acid sites, the liquid product yield is high, and the total monomer yield and the target product selectivity are also high. The prepared activated carbon supported Ni-Zn bimetallic catalyst material has good application prospect in the production of high value-added chemicals by the hydro-depolymerization of the lignin suspension bed.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Ni-Zn supported catalyst material is prepared from a nickel source and a zinc source through immersing, ultrasonic dispersing on the surface of active carbon, high-temp calcining in nitrogen atmosphere, and carbon reduction.
In the invention, the molar ratio of the nickel source to the zinc source is 10: 1-5: 4, preferably 2.2: 1.
In the invention, the nickel source is soluble nickel salt of nickel, such as nickel nitrate, nickel acetate, nickel sulfate and the like.
In the invention, the zinc source is soluble zinc salt of zinc, such as zinc nitrate, zinc acetate, zinc sulfate and the like.
In the invention, the impregnation is carried out by a conventional impregnation method process, such as constant volume impregnation and over volume impregnation reaction at normal temperature.
In the invention, the reduction and activation are carried out for 3-6 h under the carbon reduction condition in a nitrogen atmosphere at 350-600 ℃.
In the invention, the activated carbon is one or more of wood activated carbon, shell activated carbon, coconut activated carbon and coal activated carbon.
In the invention, the activated carbon is mesoporous activated carbon, and the specific surface area of the activated carbon can reach 1632 m2/g。
In the invention, the ultrasonic frequency is 30-60 KHz, and the ultrasonic temperature is 45-55 ℃.
The invention discloses a preparation method of a Ni-Zn supported catalyst for lignin depolymerization, which comprises the following steps:
(1) mixing a metal nickel source and a zinc source according to a certain molar ratio, adding a certain amount of deionized water, and performing ultrasonic treatment until the metal nickel source and the zinc source are completely dissolved to form a mixed solution;
(2) dropwise adding the mixed solution into a certain amount of activated carbon carriers, and carrying out ultrasonic treatment, standing and drying to obtain a compound;
(3) and heating the composite to 300-600 ℃ at a heating rate of 3-6 ℃/min, and carrying out reduction activation for 3-6 h in a nitrogen atmosphere to obtain the Ni-Zn supported catalyst for lignin depolymerization.
In the step (1), the concentration of the zinc source in deionized water is preferably 0.4-1.2 mol/L; carrying out ultrasonic treatment at the temperature of 20-40 ℃ for 2-8 min;
in the step (1), 3-5 mL of deionized water is used;
in the step (2), the dripping time is 15-30 min, the ultrasonic temperature is kept unchanged at 40-55 ℃, and the ultrasonic time is 10-14 min;
in the step (2), the standing time is kept for 6-8 h; the drying temperature was maintained at 80 ℃ for 2 h.
In the step (3), the temperature of the compound is increased to 300-550 ℃ at the heating rate of 4-5 ℃/min, and the compound is reduced and activated for 3-5 h in the atmosphere of nitrogen atmosphere, so that the Ni-Zn supported catalyst for lignin depolymerization is obtained.
The application of a Ni-Zn supported catalyst for lignin depolymerization: mixing lignin, Ni-Zn supported catalyst and reaction solvent, adding the mixture into a reaction kettle, sealing the reaction kettle, introducing air in a nitrogen displacement device, heating the reaction kettle to a reaction temperature, cooling and depressurizing the reaction kettle after the reaction is finished, filtering out solids in the reaction kettle to obtain a liquid product, extracting and evaporating the liquid product in a rotary manner, and weighing the weight of the liquid product to calculate the yield of the liquid product. And then, adding 20 mg of internal standard substance, and carrying out GC-MS instrument qualitative and quantitative analysis to obtain the monomer yield and selectivity.
In the invention, the lignin comprises organic dissolved corn straw lignin, organic dissolved bagasse lignin and organic dissolved Chinese silvergrass lignin.
In the invention, the reaction solvent is one of methanol, ethanol, isopropanol, 1, 4-dioxane and formic acid, or the mixture of the above solvents in any proportion, and the liquid product is a phenol, ester or oligomer compound.
In the invention, the mass ratio of the catalyst to the lignin is (1: 1) - (1: 8), and the mass ratio of the lignin to the reaction solvent is (1: 50) - (1: 100).
The specific operating conditions in the application process are as follows: introducing nitrogen at the temperature of 20-30 ℃ at the pressure of 0-6 MPa, heating to the target reaction temperature (220-300 ℃) after 30-100 min, stirring at the stirring speed of 400-800 rpm/min during the reaction process for 1-6h, naturally cooling to the room temperature after the reaction is finished, and reducing the pressure to the normal pressure.
The liquid product yield, monomer yield and monomer selectivity were calculated according to the following formulas:
Yresidue of riceRepresenting the residue rate after the reaction; y isLiquid productRepresents the yield of the liquid product; m isLiquid productRepresents the mass of the liquid product; m isLigninRepresents the mass of lignin; y isMonomerRepresents the yield of the monomer; m isInternal standard substanceRepresents the mass of the internal standard; deltaMonomerRepresents an influencing factor of the monomer; sMonomer peak areaRepresents the relative peak area of the monomer detected in GC-MS; sPeak area of internal standardRepresents the relative peak area of the internal standard detected in GC-MS. L is a radical of an alcoholMonomerRepresenting the selectivity of the monomer.
The method of the invention uses an immersion method to load Ni and Zn on the carrier simultaneously, and can promote the mixed solution to be rapidly dispersed on the surface of the carrier and better enter the inside of the pore channel through ultrasound; the reduction capability of the active carbon is utilized to carry out metal reduction at high temperature, so that the reduction temperature of the simple substance Ni can be reduced, and the interaction between the metal and the carrier is facilitated; meanwhile, the existence of Zn can not only provide Lewis acid sites, but also promoteHigh dispersion of Ni component and increase of Ni in catalyst0The catalytic activity is improved; meanwhile, the active carbon with the advantages of large specific surface area, porous structure and the like is used as a carrier to further improve the dispersibility of active metal and active catalytic sites, thereby improving the catalytic efficiency.
The invention also provides the Ni-Zn supported catalyst for lignin depolymerization prepared by the method, which is applied to lignin depolymerization by hydrogenation, wherein when the mass of the catalyst/the mass of lignin is =20% (corresponding to example 1), the yield of liquid products after lignin hydrogenolysis can reach 73.1 wt%, the total monomer yield can reach 18.25 wt%, and when the mass of the catalyst/the mass of lignin is =40% (corresponding to example 5), the monomer compound selectivities of esters (compounds f and h) and aldehydes (compound g) are 36.43 wt% and 16.75 wt%, respectively.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention uses low-price soluble nickel salt (such as nickel nitrate) and zinc salt (such as zinc nitrate) as precursor materials, the preparation process is simple, safe, easy to control and low in manufacturing cost, and the Ni-Zn supported catalyst prepared by the method has the following advantages: (1) the ultrasonic action can quickly promote the dispersion degree of the metal on the carrier and enter the inside of the pore channel as much as possible, thereby being beneficial to carrying out the secondary reaction of the small molecular compound; (2) phase contrast H2The reduction of atmosphere, the carbon reduction not only can reduce the reduction temperature of the metal, but also can promote the interaction between the metal and the carrier and prevent the loss of the metal; (3) the metal nickel and zinc are uniformly dispersed on the active carbon carrier to form NiZn alloy, and the metal, the metal and the Ni are mixed0The synergistic effect between the metal sites and the Lewis acid sites improves the catalytic activity of the catalyst; (4) the yield of the liquid product of the lignin is high, and the ester compound and the 4-hydroxy-3, 5-dimethoxyphenylacetaldehyde in the product are main products, so that the selectivity is high. (5) A new way is developed for the utilization of lignin, the dependence on petroleum and other stone resources can be reduced, the additional value of chemicals can be considered, and the economy is improved.
Drawings
FIG. 1 is a GC-MS spectrum of the liquid product of examples 1, 5.
FIG. 2 is XRD patterns of Ni-Zn supported catalysts of examples 1 to 3 and Ni supported catalyst of comparative example 1.
FIG. 3 is N of Ni-Zn supported catalysts of examples 1 to 3 and Ni supported catalyst of comparative example 12Adsorption and desorption isotherm diagrams.
FIG. 4 is a Py-IR chart of the Ni-Zn supported catalyst of example 1 and the Ni supported catalyst of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
Example 1
First, 0.99g of nickel nitrate and 0.46g of zinc nitrate (molar ratio of nickel to zinc is 2.2: 1) were added to 3.8 mL of deionized water, sonicated at 30 ℃ for 4 min, mixed well to form a mixed solution, the solution was added dropwise onto 2.0 g of activated carbon, sonicated at 45 ℃ for 10 min, then allowed to stand at 30 ℃ for 7 h, dried at 80 ℃ for 2 h to obtain a black solid complex. And then transferring the catalyst to a tubular furnace, and heating to 450 ℃ at the heating rate of 4 ℃/min for reduction activation for 4 h under the atmosphere of 80 mL/min nitrogen to obtain the Ni-Zn supported catalyst, wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 5 wt%. The mass ratio of Zn/Ni was 50%, and the catalyst was designated as NiZn/AC-50. The BET specific surface area of the catalyst is 1080 m2g-1Average pore volume of 0.911 cm3g-1The average pore diameter was 4.73 nm.
Taking 0.5 g of organic soluble corn straw lignin and 0.1 g of Ni-Zn supported catalyst material, loading the organic soluble corn straw lignin and the Ni-Zn supported catalyst material into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
Example 2
First, 0.99g of nickel nitrate and 0.68 g of zinc nitrate (molar ratio of nickel to zinc is 1.5: 1) were added to 3.8 mL of deionized water, sonicated at 30 ℃ for 4 min, mixed well to form a mixed solution, this solution was added dropwise to 2.0 g of activated carbon, sonicated at 45 ℃ for 10 min, allowed to stand at 30 ℃ for 7 h, dried at 80 ℃ for 2 h to give a black solid composite. And then transferring the catalyst to a tubular furnace, and heating to 450 ℃ at the heating rate of 4 ℃/min for reduction activation for 4 h under the atmosphere of 80 mL/min nitrogen to obtain the Ni-Zn supported catalyst, wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 7.5 wt%. The mass ratio of Zn/Ni was 75%, and the catalyst was designated as NiZn/AC-75. The BET specific surface area of the catalyst was 931 m2g-1Average pore volume of 0.81 cm3g-1The average pore diameter was 5.17 nm.
Taking 0.5 g of organic soluble corn straw lignin and 0.1 g of Ni-Zn supported catalyst material, loading the organic soluble corn straw lignin and the Ni-Zn supported catalyst material into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
Example 3
First, 0.99g of nickel nitrate and 0.23 g of zinc nitrate (molar ratio of nickel to zinc is 4.5: 1) were added to 3.8 mL of deionized water, sonicated at 30 ℃ for 4 min, mixed well to form a mixed solution, this solution was added dropwise to 2 g of activated carbon, sonicated at 45 ℃ for 10 min, allowed to stand at 30 ℃ for 7 h, and dried at 80 ℃ for 2 h to give a black solid composite. And then transferring the catalyst to a tubular furnace, and heating to 450 ℃ at the heating rate of 4 ℃/min for reduction activation for 4 h under the atmosphere of 80 mL/min nitrogen to obtain the Ni-Zn supported catalyst, wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 2.5 wt%. Theoretically, the mass of Zn/NiThe ratio was 25%, and the catalyst was designated as NiZn/AC-25. The BET specific surface area of the catalyst was 1122m2g-1Average pore volume of 0.96 cm3g-1The average pore diameter was 5.1 nm.
Taking 0.5 g of organic soluble corn straw lignin and 0.1 gNi-Zn supported catalyst material, loading the organic soluble corn straw lignin and the 0.1 gNi-Zn supported catalyst material into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
Figure 2 is an XRD spectrum of the catalyst. As can be seen from the figure, the characteristic diffraction peaks of the synthesized series of catalysts, in which elemental Ni appears at 2 θ =44.3 °, 51.7 °, 76.6 °, are consistent with Ni standard cards (PDF #65-2865), corresponding to the (111), (200), (220) crystal faces thereof, respectively. No diffraction characteristic peak of oxidation state NiO was found in the spectrum, probably because the concentration of NiO was low and was not detected or was in an amorphous state. As the content of Zn increases, characteristic diffraction peaks related to Zn element do not appear at Zn/Ni =25% and Zn/Ni =50%, which may indicate that Zn element is highly dispersed in the structure of Ni or characteristic diffraction peaks of its oxide are observed due to low Zn content, and as the content of Zn continues to increase, characteristic diffraction peaks of ZnO (31.8 °, 34.4 °, 36.3 °, 47.5 °, 56.6 °, 62.9 °, 68.0 ° and 69.1 °) appear in NiZn/AC-75 catalyst, indicating that Zn species are aggregated. And with the addition of Zn, the characteristic diffraction peak of Ni starts to shift slightly to the left, indicating that there may be NiZn alloy formation.
Example 4 (different reaction temperature during depolymerization of lignin compared to example 1)
0.5 g of organic soluble corn straw lignin and 0.1 g of NiZn/AC-50 catalyst material in example 1 are loaded into a Hastelloy reactor of a simulated suspension bed reactor, air in the reactor and a pipeline is purged by nitrogen, and then 2 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the reaction conditions that: the temperature is 220 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
Example 5 (example 1 compared to different amounts of catalyst used in the depolymerization of lignin)
0.5 g of organic soluble corn straw lignin and 0.2 g of NiZn/AC-50 catalyst material in example 1 are loaded into a Hastelloy reactor of a simulated suspension bed reactor, air in the reactor and a pipeline is purged by nitrogen, and then 2 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the reaction conditions that: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
Example 6 (catalyst preparation compared with example 5, reduction activation temperature)
First, 0.99g of nickel nitrate and 0.46g of zinc nitrate (molar ratio of nickel to zinc is 2.2: 1) were added to 3.8 mL of deionized water, sonicated at 30 ℃ for 4 min, mixed thoroughly to form a mixed solution, this solution was added dropwise onto 2 g of activated carbon, sonicated at 45 ℃ for 10 min, allowed to stand at 30 ℃ for 7 h, and dried at 80 ℃ for 2 h to give a black solid composite. And then transferring the catalyst to a tubular furnace, and heating to 525 ℃ at the heating rate of 4 ℃/min for reduction activation for 4 h under the atmosphere of 80 mL/min nitrogen atmosphere to obtain the Ni-Zn supported catalyst. Wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 5 wt%. The mass ratio of Zn/Ni was 50%, and the catalyst was designated as NiZn/AC-50-525. The BET specific surface area of the catalyst was 1126m2g-1Average pore volume of 0.94 cm3g-1The average pore diameter was 4.7 nm.
Taking 0.5 g of organic soluble corn straw lignin and 0.2 g of Ni-Zn supported catalyst material, loading the organic soluble corn straw lignin and the Ni-Zn supported catalyst material into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
Comparative example 1
Firstly, 0.99g of nickel nitrate is added into 3.8 mL of deionized water, ultrasonic treatment is carried out for 4 min at the temperature of 30 ℃, the mixture is fully mixed to form a solution, the solution is dropwise added to 2 g of activated carbon as a carrier, ultrasonic treatment is carried out for 10 min at the temperature of 45 ℃, then standing is carried out for 7 h at the temperature of 30 ℃, and drying is carried out for 2 h at the temperature of 80 ℃ to obtain a black solid compound. Then transferring the mixture to a tubular furnace, heating to 525 ℃ at the heating rate of 4 ℃/min for reduction activation for 4 h under the atmosphere of 80 mL/min nitrogen, and obtaining the Ni-supported catalyst, wherein the mass percentage of Ni is 10 wt%, and the BET specific surface area of the catalyst is 1165m2g-1Average pore volume of 0.96 cm3g-1The average pore diameter was 4.66 nm.
Taking 0.5 g of organic soluble corn straw lignin and 0.1 g of Ni supported catalyst material, loading the materials into a Hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline by using nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction, wherein the reaction conditions are as follows: the temperature is 220 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, the products after the hydrogenation depolymerization are filtered and extracted, and the physical properties of the liquid phase products are analyzed.
The yields of the reaction products obtained in the above examples and comparative examples are shown in Table 1.
TABLE 1 comparison of yields of phenolic monomers for the examples and comparative examples
The yields of the objective products obtained in the above examples and comparative examples are shown in Table 2.
TABLE 2 comparison of yield and selectivity of target monomers for examples and comparative examples
From the reaction data (examples 1-3), on the basis of the fixed Ni loading, the liquid yield is reduced and the residue rate is increased along with the increase of the Zn loading, which shows that the acidic sites provided by ZnO promote the re-polymerization of the product intermediate; while the monomer ratio shows a tendency of increasing first and then decreasing with increasing Zn loading, when the molar ratio of nickel and zinc is 2.2:1, the best results are achieved, probably because the hydrogenolysis reaction and the repolymerization reaction in the lignin depolymerization process are in competition, and the molar ratio of nickel and zinc is 2.2: before 1, hydrogenolysis reaction is dominant, and along with the increase of Lewis acid sites provided by ZnO, the depolymerization depth of lignin is promoted, and meanwhile, the side reaction, namely the re-polymerization reaction, is also aggravated; in a molar ratio of nickel to zinc of 2.2:1, the Ni metal site and the Lewis acid site provided by ZnO achieve proper synergistic effect, and the monomer yield obtained under the condition is maximum and the maximum benefit is achieved; the molar ratio of nickel to zinc is 2.2: after 1, it may be the predominant position for the repolymerization, resulting in a decrease in the monomer yield and an increase in the residue rate.
From the reaction data (examples 1 and 4), the reaction temperature has a great influence on depolymerization of lignin, and the reason why the monomer yield is low in the depolymerization reaction at 220 ℃ is probably because the depolymerization reaction is not sufficiently performed, compared to the supercritical reaction system at 260 ℃. Under subcritical conditions, the energy condition required for breaking the C-O or C-C bond linkage in the lignin macromolecular structure monomer is not achieved, and the macromolecular structure can not be broken and fall off in the form of small molecular monomers, so that the phenomenon of low yield of monomers generated by lignin depolymerization is caused. Relatively speaking, 260 ℃ is a suitable reaction temperature.
From the reaction data (examples 1 and 5), as the amount of the catalyst is increased, the residue rate is increased, the yield of the liquid product and the total monomer yield are reduced, but the monomer yield of the 4-ethylphenol and the 4-ethylguaiacol is reduced, the monomer yield of the methyl p-hydroxyphenylpropionate and the methyl dihydroferulic acid is increased, which is probably a hydroxy cinnamic acid and ferulic acid monomer intermediate produced by depolymerization of the gramineous lignin, and two main reaction paths exist: one is esterification with methanol and one is free radical decarbonylation, and these two pathways are in competition. The catalyst amount is increased, so that the substrate can be more fully contacted with the active sites of the catalyst, and the process of the lignin reduction degradation is deeper. Meanwhile, the degree of reductive depolymerization is deepened, and a side reaction, namely a heavy polymerization reaction, is obviously aggravated, so that the liquid yield is reduced, and the residue rate is increased. The effect of example 1 is therefore best in terms of overall monomer yield; whereas example 5 works best with respect to the selection of the target monomer.
From the reaction data (examples 5, 6), as the reduction activation temperature of the catalyst was increased, the yield and residue rate of the liquid product were not greatly changed, but the total monomer yield and the target monomer yield were increased, which is likely that the increase in the reduction temperature promoted the metal activity Ni0The content is increased, thereby promoting the depolymerization process of the lignin. But the selectivity of esters and aldehydes decreases, which indicates that Ni0An increase in the content of (a) tends to promote the progress of other reactions, decreasing the selectivity of esters and aldehydes.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a Ni-Zn supported catalyst for lignin depolymerization is characterized in that: the preparation method comprises the steps of taking a nickel source and a zinc source as raw materials, dispersing the raw materials on the surface of a carbon carrier through impregnation and ultrasonic treatment, and calcining the raw materials at high temperature and reducing carbon in a nitrogen atmosphere.
2. The preparation method of Ni-Zn supported catalyst for lignin depolymerization according to claim 1, wherein: the molar ratio of the nickel source to the zinc source is in the range of 10: 1-5: 4.
3. the preparation method of Ni-Zn supported catalyst for lignin depolymerization according to claim 1, wherein: the nickel source comprises at least one of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride; the zinc salt comprises at least one of zinc nitrate, zinc acetate, zinc sulfate and zinc chloride.
4. The preparation method of the Ni-Zn supported catalyst for lignin depolymerization according to claim 1, wherein: and the high-temperature calcination is carried out for 2-8 h at the temperature of 300-700 ℃.
5. The preparation method of the Ni-Zn supported catalyst for lignin depolymerization according to claim 1, wherein: the carbon carrier is one or more of wood activated carbon, shell activated carbon, coconut activated carbon and coal activated carbon.
6. The preparation method of Ni-Zn supported catalyst for lignin depolymerization according to claim 1, wherein: the ultrasonic frequency is 30-60 KHz.
7. The preparation method of Ni-Zn supported catalyst for lignin depolymerization according to claim 1, wherein: the method specifically comprises the following steps:
(1) mixing a metal nickel source and a zinc source according to a certain molar ratio, adding a certain amount of deionized water, and performing ultrasonic treatment until the metal nickel source and the zinc source are completely dissolved to form a mixed solution;
(2) dropwise adding the mixed solution into a certain amount of activated carbon carriers, and carrying out ultrasonic treatment, standing and drying at a certain temperature to obtain a compound;
(3) heating the composite to 300-600 ℃ at a heating rate of 2-6 ℃/min, and carrying out reduction activation for 3-6 h in a nitrogen atmosphere to obtain the Ni-Zn supported catalyst for lignin depolymerization.
8. The preparation method of Ni-Zn supported catalyst for lignin depolymerization according to claim 7, characterized by:
in the step (1), the concentration of a zinc source in deionized water is 0.2-1.2 mol/L, the ultrasonic temperature is 20-40 ℃, and the ultrasonic time is 2-8 min;
in the step (2), the dripping time is 15-30 min, the ultrasonic temperature is 40-55 ℃, and the ultrasonic time is 8-20 min; standing for 5-15 h, drying at 80 ℃, and drying for 2 h.
9. The application of the Ni-Zn supported catalyst for lignin depolymerization, which is prepared by the preparation method according to any one of claims 1 to 8, is characterized in that lignin, the Ni-Zn supported catalyst and a reaction solvent are placed in a Hastelloy reaction kettle of a suspension bed reactor, the air atmosphere in a reaction device is purged by nitrogen, then high-purity hydrogen is filled in the suspension bed reactor to carry out a lignin depolymerization reaction under the following reaction conditions: the temperature is 150-350 ℃, the hydrogen pressure is 0-6 MPa, the stirring speed is 300-1000 rpm/min, and the liquid product is obtained by filtering, extracting and rotary evaporating the reaction product after the depolymerization.
10. Use according to claim 9, characterized in that: the reaction solvent is one of methanol, ethanol, isopropanol, 1, 4-dioxane and formic acid or a mixture of the solvents in any proportion, and the liquid product is a phenol compound, an ester compound or an oligomer compound; the mass ratio of the catalyst to the lignin is (1: 1) - (1: 15), and the mass ratio of the lignin to the reaction solvent is (1: 30) - (1: 200).
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| CN115286478A (en) * | 2022-07-17 | 2022-11-04 | 曲阜师范大学 | Method for preparing lignin-derived phenolic monomer by catalyzing Ni-Cu alloy through selective hydrogenation and aromatic ring protection mechanism |
| CN115286478B (en) * | 2022-07-17 | 2023-11-24 | 曲阜师范大学 | Ni-Cu alloy is catalyzed and prepared into lignin-derived phenolic monomer through selective hydrogenation and aromatic ring protection mechanism |
| CN115364862A (en) * | 2022-09-20 | 2022-11-22 | 南京师范大学 | Nickel-based catalyst, preparation method and application in lignin depolymerization process |
| CN115672332A (en) * | 2022-10-12 | 2023-02-03 | 中国石油大学(华东) | Papermaking black liquor lignin conversion catalyst and preparation method and application thereof |
| CN117383999A (en) * | 2023-12-12 | 2024-01-12 | 北京林业大学 | Method for preparing styrene by using lignin |
| CN117383999B (en) * | 2023-12-12 | 2024-04-05 | 北京林业大学 | Method for preparing styrene by using lignin |
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