CN115007157A - Lignin-derived carbon-nickel-based multi-metal catalyst and preparation method and application thereof - Google Patents
Lignin-derived carbon-nickel-based multi-metal catalyst and preparation method and application thereof Download PDFInfo
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- CN115007157A CN115007157A CN202210688914.6A CN202210688914A CN115007157A CN 115007157 A CN115007157 A CN 115007157A CN 202210688914 A CN202210688914 A CN 202210688914A CN 115007157 A CN115007157 A CN 115007157A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 151
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 79
- 239000002184 metal Substances 0.000 title claims abstract description 78
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 108
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000005859 coupling reaction Methods 0.000 claims abstract description 26
- 230000008878 coupling Effects 0.000 claims abstract description 23
- 238000010168 coupling process Methods 0.000 claims abstract description 23
- 150000001298 alcohols Chemical class 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 78
- 239000002243 precursor Substances 0.000 claims description 61
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 30
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 28
- 229940106681 chloroacetic acid Drugs 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 12
- 239000004246 zinc acetate Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 2
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- -1 polyoxymethylene Polymers 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000011701 zinc Substances 0.000 description 21
- 238000002474 experimental method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910003962 NiZn Inorganic materials 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WNDLTOTUHMHNOC-UHFFFAOYSA-N 3-ethylhexan-3-ol Chemical compound CCCC(O)(CC)CC WNDLTOTUHMHNOC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000002194 amorphous carbon material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a lignin-derived carbon nickel-based multi-metal catalyst. According to the invention, the electronic environment of Ni is changed by a multi-metal doping method, so that the Ni is in an electron-rich state, the defect structure of the nickel-based catalyst is increased, and the hydrogenolysis and methanation of carbon-carbon bonds in the reaction process are effectively inhibited, thereby improving the catalytic activity of the catalyst and the selectivity of the product. The catalyst obtained by the preparation method has the advantages that the ethanol conversion rate can reach 75.2%, the yield of higher alcohols can reach 41.7%, the catalytic effect is good, and the problems of low ethanol conversion rate, complex synthesis process, poor stability and the like of the conventional ethanol Guerbet coupling catalyst can be effectively solved.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a lignin-derived carbon nickel-based multi-metal catalyst, and a preparation method and application thereof.
Background
With the increasing consumption of fossil fuels, the search for sustainable, low-cost, green alternative fossil fuels is a topic of great concern. When used as fuel, the bioethanol has the advantages of low price, easy obtainment, environmental protection and the like, and can replace non-renewable fossil fuel. Meanwhile, ethanol obtained by fermentation of renewable biomass is utilized to further realize conversion of the ethanol into higher alcohols (butanol, n-hexanol, diethylbutanol and the like), so that the cost can be effectively reduced. However, the disadvantages of easy water absorption, low energy value and the like of ethanol greatly limit the application of biomass ethanol as fuel. Therefore, converting ethanol to higher alcohols with higher heating values can effectively solve this problem. Higher alcohols have the advantages of high energy, density close to gasoline, etc., making them a candidate fuel additive of great interest.
At present, the high-efficiency catalyst used in the ethanol coupling reaction mainly comprises heterogeneous catalysts such as homogeneous ruthenium, iridium complex catalyst, Mg-Al composite oxide and zeolite catalyst, Hydroxyapatite (HAP), metal load and the like. The high production costs and organic solvent contamination during the reaction process limit the large-scale application of homogeneous catalysts to some extent. The supported metal catalyst has the advantages of low cost, excellent chemical stability, controllable microstructure and the like, and is preferably a catalytic material for converting ethanol into higher alcohol.
Lignin is a natural aromatic polymer that exhibits a random network structure of monomeric phenylpropane, and contains about 60% organic carbon. A large number of monomer structures contain abundant functional groups (phenyl-OH, -OH and the like), and are beneficial to the functionalized modification of lignin, so that metal is effectively complexed and dispersed, a carbon-based metal-coated structure is formed by in-situ reduction and carbonization, and the catalytic performance is improved by utilizing the synergistic effect of the metal and a carbon substrate. In addition, nitrogen sites are introduced after lignin amination, which helps nucleation and dispersion of the catalyst, and nitrogen doping can result in high pyridine-N and graphite-N contents and rich edge defect structures.
The nickel-based catalyst shows excellent dehydrogenation and hydrogenation capabilities, and the synergistic effect of the nickel-based catalyst and a carbon material can increase the stability of the catalyst and effectively inhibit the agglomeration of metals, so that the nickel-based catalyst becomes one of the research hotspots of the ethanol coupling high-efficiency catalyst. However, because of the strong metallic property of nickel, Ni has excellent dehydrogenation activity and capability of breaking C-C bond/C-O bond, so that the Ni is easy to cause serious methanation to generate gas byproducts such as methane, carbon monoxide, carbon dioxide and the like in the process of ethanol coupling dehydrogenation, thereby influencing the yield of higher alcohols. The problems of low inherent activity and less active site exposure of the nickel-based single metal catalyst also make the nickel-based single metal catalyst uncompetitive in the application of ethanol coupling to prepare higher alcohol.
Disclosure of Invention
The invention aims to overcome the defects and defects in the background technology, so that the lignin-derived carbon-nickel-based multi-metal catalyst is provided, carbon deposition can be effectively reduced by a multi-metal doping method, the electronic environment of Ni is changed to enable the nickel to be in an electron-rich state, the defect structure of the nickel-based catalyst is increased, the hydrogenolysis and methanation of carbon-carbon bonds in the reaction process are effectively inhibited, and the catalytic activity of the catalyst and the selectivity of products are improved.
In order to achieve the above purpose, the present invention is realized by the following means:
a preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) synthesizing a functionalized lignin precursor by using a carbon source, a carboxylation reagent, an amination reagent and an additive under an alkaline condition, wherein the carbon source is selected from lignin;
(2) complexing the functional lignin precursor obtained in the step (1) with nickel nitrate and a metal salt solution by a coprecipitation method, and drying after complete reaction to prepare a lignin-metal composite material;
(3) and (3) calcining the lignin-metal composite material obtained in the step (2) in a protective gas atmosphere to obtain powdery particles, and fully grinding to obtain the lignin-derived carbon-nickel-based multi-metal catalyst.
Preferably, the lignin in step (1) is selected from one or more of alkali lignin, Longli enzymatic hydrolysis lignin, kraft paper lignin and Russian sodium.
Preferably, the carboxylation reagent in the step (1) is one or more selected from chloroacetic acid, bromoacetic acid and iodoacetic acid.
Preferably, the amination reagent in step (1) is selected from one or more of diethylenetriamine, ethylenediamine, lysine, polyethyleneimine and histidine.
Preferably, the additive in step (1) is selected from one or more of formaldehyde, acetaldehyde, glutaraldehyde, polyoxymethylene, and urea.
Preferably, the carbon source, the carboxylation reagent, the amination reagent and the additive in the step (1) are respectively used in the amounts of 10-45wt%, 2-40wt%, 4-20wt% and 15-70 wt%; most preferably, the carbon source, the carboxylation agent, the amination agent and the additive are used in amounts of 24wt%, 15wt%, 12wt% and 49wt%, respectively.
Preferably, the alkaline conditions in step (1) are specifically: pH = 8-13.
Preferably, the conditions for synthesizing the functionalized lignin precursor in step (1) are as follows: the synthesis temperature is 30-90 ℃, and the synthesis time is 4-10 h.
Preferably, the metal salt solution in step (2) is selected from one or more of zinc acetate solution, manganese chloride solution, copper acetate solution, cobalt nitrate solution, ferric nitrate solution and chromium chloride solution; most preferably, the metal salt solution is selected from a zinc acetate solution.
Preferably, the molar mass ratio of the nickel in the step (2) to the metal element in the metal salt solution is 10-30: 1; most preferably, the molar mass ratio of nickel to metal elements in the metal salt solution is 20: 1.
Preferably, the conditions of the coprecipitation method in step (2) are: the reaction temperature is 10-50 ℃, and the treatment time is 2 h.
Preferably, the conditions of the drying treatment in step (2) are: the reaction temperature is 70-120 ℃, and the treatment time is 1-4 h.
Preferably, the protective gas in step (3) is selected from one or more of ammonia, nitrogen, argon and air; most preferably, the shielding gas is selected from nitrogen.
Preferably, the conditions of the calcination treatment in step (3) are: the calcining temperature is 300-800 ℃, and the calcining time is 3-8 h.
The invention provides a lignin-derived carbon nickel-based multi-metal catalyst prepared according to the preparation method.
The third aspect of the invention provides an application of the lignin-derived carbon nickel-based multi-metal catalyst in preparation of higher alcohol through ethanol coupling.
According to the invention, when the element-doped lignin resin precursor is prepared, carboxymethylation treatment is carried out on lignin by adopting a carboxylation reagent, formaldehyde is selected as an additive, and simultaneously, grafting reaction is carried out by taking diethylenetriamine and the like as an amination reagent so as to uniformly distribute N elements in a carbon material, and then condensation reaction is carried out on a carboxymethylated lignin solution and the amination reagent so as to obtain the N element-doped lignin resin precursor. The catalytic performance of the lignin-derived carbon nickel-based multi-metal catalyst is in certain relation with the content of the doping elements, and the selectivity of the n-butyl alcohol is increased along with the increase of alkaline sites. In the invention, the lignin-metal composite material is prepared by a coprecipitation method by doping the element with lignin resin precursor and using multi-metal solution such as NiZn and the like, and the lignin-metal composite material is dried after complete reaction so as to complex metal ions such as Ni, Zn, Cr, Co, Mn, Fe and the like with the lignin-based carrier; and then calcining the prepared lignin-metal porous carbon material in a tube furnace in the atmosphere of protective gas to obtain the lignin-derived carbon nickel-based multi-metal catalyst (NiX @ NC catalyst, wherein X is one or more of Zn, Cr, Co, Mn and Fe), and the average particle size of the catalyst can reach 11.2 nm. The lignin derived carbon nickel-based multi-metal catalyst prepared by the invention is used for ethanol coupling reaction, the ethanol conversion rate of the catalyst can reach 75.2%, the yield of higher alcohol can reach 41.7%, and the catalytic effect is good.
Compared with the prior art, the invention has the following beneficial effects:
(1) when the functionalized lignin precursor is prepared, the N, O elements of the carbon material are greatly enriched by carboxymethylation, amination and other treatments of lignin, the nucleation and dispersion of the catalyst are facilitated, the N doping can cause high pyridine-N and graphite-N contents and rich edge defect structures, the accurate coordination of lignin and ions such as Ni, Zn, Cr, Co, Mn and the like is improved, and the applicability of the functionalized lignin-based metal catalyst as an ethanol-to-higher alcohol material is improved.
(2) According to the invention, lignin with abundant reserves is used as a carbon source, diethylenetriamine and the like are used as a nitrogen source, the raw material source is abundant, the prepared catalyst is green and environment-friendly, carbon deposition can be effectively reduced by a multi-metal doping method, the electronic environment of Ni is changed to enable the nickel to be in an electron-rich state, the defect structure of the nickel-based catalyst is increased, and hydrogenolysis and methanation of carbon-carbon bonds in the reaction process are effectively inhibited, so that the catalytic activity of the catalyst and the selectivity of a product are improved.
Drawings
Fig. 1 is a scanning electron micrograph of the lignin-based multimetallic catalyst prepared in example 3 of the present invention.
Fig. 2 is a transmission electron micrograph of the lignin-based multimetallic catalyst prepared in example 3 of the present invention.
Fig. 3 is a high-resolution transmission electron microscope image of the lignin-based multimetallic catalyst prepared in example 3 of the present invention.
Figure 4 is a pore size distribution plot for the lignin-based multimetallic catalyst prepared in example 3.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods. The lignin used in the examples and comparative examples of the present invention is alkali lignin as an example, and it should be understood that the lignin is used only as a raw material for providing a carbon source, and the specific type of the lignin has no significant influence on the properties of the finished catalyst, and when the catalyst preparation is performed by using other lignin types such as Longli enzymatic hydrolysis lignin, kraft paper lignin, Russian wood sodium and the like, the obtained catalyst performance is not significantly different from that of the alkali lignin, and thus, the alkali lignin is not listed any more.
Example 1
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding monochloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.15, 0.09, 0.15 and 0.61.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into the functionalized lignin precursor solution at room temperature, reacting for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni/Zn is 20: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 69.4% and the yield of higher alcohols of 30.2%.
Example 2
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding monochloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.19, 0.11, 0.14 and 0.56.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into the functionalized lignin precursor solution at room temperature, reacting for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni/Zn is 20: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has an ethanol conversion rate of 72.7% and a higher alcohol yield of 34.8%.
Example 3
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into the functionalized lignin precursor solution at room temperature, reacting for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni/Zn is 20: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
As can be seen from fig. 1 and 2, the scanning electron microscope images and the transmission electron microscope images of the lignin-derived carbon nickel-based catalyst prepared in this example are shown, and it is known that the lignin-derived carbon nickel-based multi-metal catalyst prepared in this example has a lamellar thin-layer structure and has a rich pore structure.
As shown in fig. 3 and 4, it can be seen that Ni of the lignin-derived carbon-nickel-based multi-metal catalyst prepared in this embodiment is wrapped in an amorphous carbon material, and lattice fringes with a lattice spacing of 0.197nm are exposed, corresponding to a Ni (111) crystal plane in an XRD spectrum, although a diffraction peak of Zn is not detected in the XRD spectrum, the metal particles also have lattice fringes with a lattice spacing of 0.258nm, which are attributed to a (002) crystal plane of Zn, indicating that Zn is successfully doped and loaded on Ni nano-particles, and an average particle size of the metal particles formed by NiZn is 11.2 nm. In addition, it can be clearly observed in fig. 3 that there is an atomic defect structure in the metal cluster, since the doping of Zn favors the formation of a defect structure in the Ni metal cluster.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 75.2% and the yield of higher alcohols of 41.7%.
Example 4
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.35, 0.21, 0.09 and 0.35.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into the functionalized lignin precursor solution at room temperature, reacting for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni/Zn is 20: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has an ethanol conversion rate of 71.3% and a higher alcohol yield of 31.4%.
Example 5
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and a manganese chloride solution into a functionalized lignin precursor solution at room temperature to react for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-manganese compound precursor; wherein the molar ratio of Ni to Mn is 20: 1.
(3) Calcining the lignin-nickel-manganese compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 68.0% and the yield of higher alcohols of 34.5%.
Example 6
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and a cobalt nitrate solution into a functionalized lignin precursor solution at room temperature for reaction for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel cobalt composite precursor; wherein the molar ratio of Ni/Co is 20: 1.
(3) Calcining the lignin-nickel cobalt compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 66.5% and the yield of higher alcohols of 32.8%.
Example 7
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and an iron nitrate solution into a functionalized lignin precursor solution at room temperature to react for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel iron compound precursor; wherein the molar ratio of Ni to Fe is 20: 1.
(3) Calcining the lignin-nickel-iron composite precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 63.5% and the yield of higher alcohols of 36.0%.
Example 8
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and a chromium chloride solution into a functionalized lignin precursor solution at room temperature to react for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel chromium compound precursor; wherein the molar ratio of Ni to Cr is 20: 1.
(3) Calcining the lignin-nickel-chromium compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 50.3% and the yield of higher alcohols of 32.2%.
Example 9
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into a functionalized lignin precursor solution at room temperature to react for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni/Zn is 30: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 85.5% and the yield of higher alcohols of 36.6%.
Example 10
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into a functionalized lignin precursor solution at room temperature to react for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni to Zn is 10: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the conversion rate of the lignin-derived carbon-nickel-based multi-metal catalyst prepared in the embodiment can reach 84.6%, and the yield of higher alcohols can reach 37.6%.
Comparative example 1
A preparation method of a lignin-derived carbon nickel-based multi-metal catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, adding chloroacetic acid at 70 ℃ for reacting for 90 minutes to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin and the chloroacetic acid are 0.62 and 0.38 respectively.
(2) Sequentially adding a nickel nitrate solution and a zinc acetate solution into a functionalized lignin precursor solution at room temperature for reaction for 2 hours, and drying at 100 ℃ to obtain a lignin-nickel-zinc compound precursor; wherein the molar ratio of Ni/Zn is 20: 1.
(3) Calcining the lignin-nickel-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based multi-metal catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based multi-metal catalyst prepared in the embodiment has the ethanol conversion rate of 70.8% and the yield of higher alcohols of 19.2%.
Comparative example 2
A method of making a lignin-derived zinc-based catalyst, comprising the steps of:
(1) dissolving lignin in 20% sodium hydroxide solution, and adding chloroacetic acid to react for 90 minutes at 70 ℃; adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the chloroacetic acid, the diethylenetriamine and the formaldehyde are respectively 0.24, 0.15, 0.12 and 0.49.
(2) Adding the zinc acetate solution into the functionalized lignin precursor solution at room temperature for reaction for 2 hours, and drying at 100 ℃ to obtain the lignin-zinc compound precursor.
(3) Calcining the lignin-zinc compound precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived zinc-based catalyst.
In an ethanol coupling experiment, the lignin-derived zinc-based catalyst prepared in the embodiment has the ethanol conversion rate of 26.5% and the yield of higher alcohols of 8.0%.
Comparative example 3
A preparation method of a lignin-derived carbon nickel-based catalyst comprises the following steps:
(1) dissolving lignin in 20% sodium hydroxide solution, adjusting the pH value of the solution to 11, sequentially adding formaldehyde and diethylenetriamine at 70 ℃, and reacting for 4 hours to obtain a dark brown functionalized lignin precursor; wherein the mass fractions of the lignin, the diethylenetriamine and the formaldehyde are respectively 0.28, 0.14 and 0.57.
(2) Adding the nickel nitrate solution into the functionalized lignin precursor solution at room temperature for reaction for 2 hours, and drying at 100 ℃ to obtain the lignin-nickel composite precursor.
(3) Calcining the lignin-nickel composite precursor for 2 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to obtain a powdery mixture, namely the lignin-derived carbon-nickel-based catalyst.
In an ethanol coupling experiment, the lignin-derived carbon nickel-based catalyst prepared in the embodiment has an ethanol conversion rate of 62.6% and a higher alcohol yield of 21.2%.
Verification example 1
The NiX @ NC catalysts prepared according to different raw material proportions can catalyze ethanol coupling to be converted into higher alcohols, water phase products and oil phase products generated in ethanol coupling experiments are analyzed through GC, gas products generated in the ethanol coupling experiments are analyzed through TCD and FID, and data in Table 1 are obtained. From the results in table 1, it is known that when chloroacetic acid is used as carboxymethylation reagent, diethylenetriamine is used as amination reagent, formaldehyde is used as additive, zinc acetate is used as metal salt, the mass fractions of lignin, chloroacetic acid, diethylenetriamine and formaldehyde are 0.24, 0.15, 0.12 and 0.49 respectively, and the molar ratio of Ni/Zn is 20:1, the catalyst has the best catalytic synthesis effect on higher alcohols, the ethanol conversion rate can reach 75.2%, and the yield of higher alcohols can reach 41.7%. The doping of Zn/N can effectively disperse Ni crystal grains and improve the catalytic activity, meanwhile, the doping of Zn can enable Ni to be in an electron-rich state, thereby being beneficial to the generation of a defect structure, and when the Zn/N is applied to the ethanol coupling reaction, the C-C bond fracture can be effectively inhibited, and the selectivity of a target product is improved. The doping content of N is adjusted by changing the amination degree of alkali lignin, and the defect structure of the catalyst and the dispersion degree of metal clusters are improved, so that high ethanol conversion rate and high yield of C4+ higher alcohol of the lignin derived carbon material catalyst for coupling and converting ethanol into higher alcohol are realized.
TABLE 1 analytical results of examples 1 to 10 and comparative examples 1 to 3
The above detailed description section specifically describes the analysis method according to the present invention. It should be noted that the above description is only for the purpose of helping those skilled in the art better understand the method and idea of the present invention, and not for the purpose of limiting the relevant contents. The present invention may be appropriately adjusted or modified by those skilled in the art without departing from the principle of the present invention, and the adjustment and modification also fall within the scope of the present invention.
Claims (10)
1. The preparation method of the lignin-derived carbon nickel-based multi-metal catalyst is characterized by comprising the following steps of:
(1) synthesizing a functionalized lignin precursor by using a carbon source, a carboxylation reagent, an amination reagent and an additive under an alkaline condition, wherein the carbon source is selected from lignin;
(2) complexing the functionalized lignin precursor obtained in the step (1) with nickel nitrate and a metal salt solution by a coprecipitation method, and drying after complete reaction to prepare a lignin-metal composite material;
(3) and (3) calcining the lignin-metal composite material obtained in the step (2) in a protective gas atmosphere to obtain powdery particles, and fully grinding to obtain the lignin-derived carbon-nickel-based multi-metal catalyst.
2. The method according to claim 1, wherein the carboxylation reagent in the step (1) is one or more selected from chloroacetic acid, bromoacetic acid and iodoacetic acid.
3. The method according to claim 1, wherein the amination reagent in the step (1) is one or more selected from the group consisting of diethylenetriamine, ethylenediamine, lysine, polyethyleneimine and histidine.
4. The method according to claim 1, wherein the additive in step (1) is one or more selected from the group consisting of formaldehyde, acetaldehyde, glutaraldehyde, polyoxymethylene, and urea.
5. The process according to claim 1, wherein the basic conditions in step (1) are in particular: pH = 8-13.
6. The method according to claim 1, wherein the metal salt solution in step (2) is one or more selected from a group consisting of a zinc acetate solution, a manganese chloride solution, a copper acetate solution, a cobalt nitrate solution, an iron nitrate solution, and a chromium chloride solution.
7. The production method according to claim 1, wherein the molar mass ratio of nickel to the metal element in the metal salt solution in step (2) is 10-30: 1.
8. The preparation method according to claim 1, wherein the protective gas in step (3) is selected from one or more of ammonia, nitrogen, argon, and air; most preferably, the shielding gas is selected from nitrogen.
9. The lignin-derived carbon nickel-based multi-metal catalyst prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the lignin-derived carbon nickel-based multimetallic catalyst of claim 9 in the preparation of higher alcohols by ethanol coupling.
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| CN115722198A (en) * | 2022-10-18 | 2023-03-03 | 北京林业大学 | Preparation and application of metal ion doped aminated lignin-based dye adsorbent |
| CN117160435A (en) * | 2023-08-09 | 2023-12-05 | 广东工业大学 | Lignin carbon/zinc oxide nanocomposite and preparation and application thereof |
| CN117548148A (en) * | 2023-11-15 | 2024-02-13 | 南京工业大学 | Application of MOF catalyst in ethanol coupling higher alcohol |
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| CN117548148A (en) * | 2023-11-15 | 2024-02-13 | 南京工业大学 | Application of MOF catalyst in ethanol coupling higher alcohol |
| CN117548148B (en) * | 2023-11-15 | 2024-05-10 | 南京工业大学 | Application of MOF catalyst in ethanol coupling higher alcohol |
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