CN111545202A - Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof - Google Patents
Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof Download PDFInfo
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- CN111545202A CN111545202A CN202010347034.3A CN202010347034A CN111545202A CN 111545202 A CN111545202 A CN 111545202A CN 202010347034 A CN202010347034 A CN 202010347034A CN 111545202 A CN111545202 A CN 111545202A
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- lignin
- metal catalyst
- cheap metal
- depolymerization
- lignin oligomer
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- 229920005610 lignin Polymers 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000001360 synchronised effect Effects 0.000 title abstract description 11
- 230000006872 improvement Effects 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000002161 passivation Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000007791 liquid phase Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- 239000001307 helium Substances 0.000 claims description 20
- 229910052734 helium Inorganic materials 0.000 claims description 20
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 20
- 239000005457 ice water Substances 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 239000000852 hydrogen donor Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000005815 base catalysis Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 18
- 239000000539 dimer Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 17
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/75—Cobalt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a cheap metal catalyst for synchronously upgrading lignin oligomer hydrogenation depolymerization and a preparation method and application thereof. Belonging to the field of lignin conversion; the cheap metal catalyst can efficiently break carbon-carbon connecting bonds in the lignin oligomers, effectively catalyze the removal of oxygen-containing functional groups, and realize the catalytic depolymerization and synchronous quality improvement of the lignin oligomers to prepare high-grade liquid fuel; the preparation method is simple, easy to operate and suitable for industrial production, and the passivation process can eliminate too active reaction sites and avoid the problems of agglomeration, inactivation and the like caused by the storage and use of cheap metal catalysts; the solvent in-situ hydrogen supply avoids the use of high-pressure hydrogen, and provides a reliable method for the safe catalytic conversion of lignin oligomers; can efficiently convert the lignin oligomer into liquid fuel, has the characteristics of high product yield, good quality and the like, realizes the conversion and the reutilization of the lignin oligomer, and has good application prospect.
Description
Technical Field
The invention belongs to the field of lignin conversion, relates to a catalyst for reconversion of lignin oligomers and preparation and application methods thereof, and particularly relates to a cheap metal catalyst for preparing high-grade liquid fuel by performing depolymerization and simultaneous upgrading on lignin oligomers, and a preparation method and application thereof.
Background
In the prior art, renewable energy is an important component of an energy supply system, the cost of the renewable energy is rapidly reduced along with the continuous expansion of the development and utilization scale of the renewable energy in the global scope, and the renewable energy becomes the core content of energy transformation promotion and an important way for coping with climate change in many countries. Compared with new energy sources such as solar energy, wind energy, tidal energy and the like, the biomass is the only renewable organic carbon source in nature, and the unique advantage of preparing products with high added values is given to the biomass. The lignocellulosic biomass is mainly composed of cellulose, hemicellulose and lignin, the conversion and utilization of the cellulose and the hemicellulose are widely researched and developed, and although the conversion and utilization of the lignin are also widely researched, the industrial application of the lignin is rarely reported, and the lignin is difficult to be effectively converted mainly due to the special structure of the lignin. The lignin is formed by connecting aromatic rings through high-energy carbon-carbon bonds and aryl ether bonds, only part of ether bonds (mainly beta-O-4 ether bonds) can be broken in the depolymerization process, the generated high-value single benzene ring products are limited, and most of the products are lignin oligomers mainly connected by carbon-carbon bonds. The effective re-degradation of the lignin oligomers is the key for realizing the conversion and utilization of the lignin, and has important significance for converting the lignin into liquid fuel with high yield, high energy density and high grade.
CN105753654A, CN103524283A, CN101892080A and the like relate to separation and extraction of pyrolytic lignin (one of oligomers obtained by lignin degradation), mainly comprise methods such as water washing, organic solvent classification, molecular distillation and the like, and Sep PurifTechnol 152(2015)123-132, Chinese J Chem Eng 25(2017)324-329, Green Chem 18(2016)271281 and the like report structural characteristics of the pyrolytic lignin. The lignin oligomer obtained by other conversion methods has a structure similar to that of pyrolytic lignin, mainly adopts carbon-carbon connection, can be prepared by the separation and extraction method, and can also be subjected to structure determination by the characterization method. At present, there are few reports on the degradation and reconversion of lignin oligomers, and some reports such as Green Chem 18(2016)271281 adopt Ru/TiO2The catalytic pyrolysis lignin is subjected to hydrogenation upgrading, the content of unsaturated aromatic ring carbon is effectively reduced, but the pyrolysis lignin is not broken into small molecules; CN101892080A discloses a method for refining pyrolytic lignin in bio-oil catalyzed by supported metal catalyst, which achieves higher liquid yield, but also does not evaluate the capability of the system to depolymerize pyrolytic lignin into monomers and dimers.
The lignin oligomer is difficult to depolymerize and convert and is mainly characterized by a special carbon-carbon connecting structure, the recycling of the lignin oligomer can be realized by realizing the effective breaking of a high-energy carbon-carbon connecting bond, and the overall utilization rate of the lignin is greatly improved. Catalytic hydrogenolysis is a potential method for depolymerizing and upgrading lignin oligomers into high quality liquid fuels in a number of conversion modes, however most current hydrogenolysis studies employ H2As a hydrogen source, the safety and the economical efficiency are poor, and the solvent in-situ hydrogen supply can provide a durable hydrogen source and can effectively inhibit coking. In addition, noble metal elementary catalysts including Pd, Pt, Re, Ru and the like and multi-metal composite catalysts have good catalytic effects and strong product selectivity on the synchronous upgrading of lignin hydrogenation depolymerization, but the noble metal catalysts are high in cost, so that the application of the catalytic system is greatly limited. Thus, an inexpensive and efficient catalytic system was developed for cleavageThe carbon-carbon connecting bond in the lignin oligomer has very important significance for the oriented catalytic hydrogenation depolymerization and synchronous quality improvement of the lignin oligomer.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a cheap metal catalyst for synchronously upgrading lignin oligomer hydrogenation depolymerization and application thereof in synchronously upgrading lignin oligomer hydrogenation depolymerization;
the invention aims to provide a cheap metal catalyst for synchronously upgrading lignin oligomer hydrogenation depolymerization.
Another object of the present invention is to provide a method for preparing the above-mentioned cheap metal catalyst for the simultaneous upgrading of lignin oligomer depolymerization by hydrogenation.
The invention further aims to provide an application method for preparing high-quality liquid fuel by synchronously upgrading lignin oligomer hydrogenation depolymerization based on the cheap metal catalyst.
The technical scheme of the invention is as follows: a cheap metal catalyst for synchronously upgrading lignin oligomer by means of hydro-depolymerization is characterized in that magnesium-aluminum hydrotalcite is used as a main body of the catalyst, one or more of cheap metals are used as active components, the content of the active components is 3-30 mol% in terms of metal elements, and the ratio of divalent metal to trivalent metal in the catalyst is 2-4.
Further, the cheap metal is one or more of copper, nickel and cobalt.
Further, a preparation method of a cheap metal catalyst for synchronously upgrading lignin oligomer hydrogenation depolymerization comprises the following specific steps:
(1) under stirring, adding M2+、Mg2+、Al3+The mixed solution and NaOH solution are respectively dripped with Na2CO3In the solution, controlling the temperature and pH of the mixed solution to precipitate the mixed solution;
(2) after the dropwise addition is finished, aging the mixed solution under a stirring state, and then filtering, washing and drying the mixed solution;
(3) and calcining the ground catalyst powder, and then reducing and passivating to obtain the cheap metal catalyst.
Further, a preparation method of the cheap metal catalyst for synchronously upgrading the lignin oligomer by the depolymerization by the hydrogenation, wherein the temperature of the mixed solution in the step (3.1) is controlled to be 50-70 ℃, and the pH value is 9-11.
Further, the cheap metal catalyst in the step (3.3) needs to be in H2Reduction in the atmosphere with 1% O2And carrying out passivation treatment.
Further, an application of the cheap metal catalyst for lignin oligomer depolymerization synchronous upgrading in the lignin oligomer depolymerization synchronous upgrading comprises the following specific steps:
(1) putting lignin oligomer, hydrogen-donating solvent and cheap metal catalyst into a reactor;
(2) washing with inert gas, pressurizing, sealing the reactor, heating to a specified temperature, and carrying out heat preservation reaction;
(3) and after the reaction is finished, rapidly cooling the reactor by adopting an ice water bath to stop the reaction, filtering a liquid-phase product, and removing a hydrogen donor solvent to obtain the high-grade liquid fuel.
Further, the lignin oligomers include oligomers produced by degradation of lignin in 5 processes of pyrolysis, hydrogenolysis, oxidation, base catalysis, and acid catalysis.
Further, the hydrogen donor solvent is one or more of water, methanol, ethanol, propanol, isopropanol, tetralin and decalin;
further, the inert gas is one of nitrogen, helium, neon and argon; the number of times of gas washing is 3-5.
Further, the reaction temperature is more than or equal to 250 ℃, and the reaction time is 0.25-8 h.
The invention has the beneficial effects that: (1) the cheap metal catalyst has high activity, can efficiently break carbon-carbon connecting bonds in the lignin oligomers, simultaneously effectively catalyze the removal of oxygen-containing functional groups, and can realize the catalytic depolymerization and synchronous quality improvement of the lignin oligomers to prepare high-grade liquid fuel; (2) the preparation method of the cheap metal catalyst is simple, easy to operate, low in cost and suitable for industrial production, and the passivation process can eliminate too active reaction sites, so that the problems of agglomeration, inactivation and the like caused by extreme oxidation in the storage and use processes of the cheap metal catalyst are avoided; (3) the solvent in-situ hydrogen supply avoids the use of high-pressure hydrogen, and provides a reliable method for the safe catalytic conversion of lignin oligomers; (4) the lignin oligomer hydrogenation and depolymerization synchronous upgrading system based on the cheap metal catalyst can efficiently convert lignin oligomers into liquid fuels, has the characteristics of high product yield, good quality and the like, realizes the conversion and reutilization of the lignin oligomers, and has good application prospect.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the present invention will be further described below; obviously, the following description is only a part of the embodiments, and it is obvious for a person skilled in the art to apply the technical solutions of the present invention to other similar situations without creative efforts; in order to more clearly illustrate the technical solution of the present invention, the following further detailed description is made on the technical solution of the present invention:
a cheap metal catalyst for synchronously upgrading lignin oligomer by means of hydro-depolymerization is characterized in that magnesium-aluminum hydrotalcite is used as a main body of the catalyst, one or more of cheap metals are used as active components, the content of the active components is 3-30 mol% in terms of metal elements, and the ratio of divalent metal to trivalent metal in the catalyst is 2-4.
Further, the cheap metal is one or more of copper, nickel and cobalt.
Further, a preparation method of a cheap metal catalyst for synchronously upgrading lignin oligomer hydrogenation depolymerization comprises the following specific steps:
(1) under stirring, adding M2+、Mg2+、Al3+The mixed solution and NaOH solution are respectively dripped with Na2CO3In the solution, controlling the temperature and pH of the mixed solution to precipitate the mixed solution;
(2) after the dropwise addition is finished, aging the mixed solution under a stirring state, and then filtering, washing and drying the mixed solution;
(3) and calcining the ground catalyst powder, and then reducing and passivating to obtain the cheap metal catalyst.
Further, a preparation method of the cheap metal catalyst for synchronously upgrading the lignin oligomer by the depolymerization by the hydrogenation, wherein the temperature of the mixed solution in the step (3.1) is controlled to be 50-70 ℃, and the pH value is 9-11.
Further, the cheap metal catalyst in the step (3.3) needs to be in H2Reduction in the atmosphere with 1% O2And carrying out passivation treatment.
Further, an application of the cheap metal catalyst for lignin oligomer depolymerization synchronous upgrading in the lignin oligomer depolymerization synchronous upgrading comprises the following specific steps:
(1) putting lignin oligomer, hydrogen-donating solvent and cheap metal catalyst into a reactor;
(2) washing with inert gas, pressurizing, sealing the reactor, heating to a specified temperature, and carrying out heat preservation reaction;
(3) and after the reaction is finished, rapidly cooling the reactor by adopting an ice water bath to stop the reaction, filtering a liquid-phase product, and removing a hydrogen donor solvent to obtain the high-grade liquid fuel.
Further, the lignin oligomers include oligomers produced by degradation of lignin in 5 processes of pyrolysis, hydrogenolysis, oxidation, base catalysis, and acid catalysis.
Further, the hydrogen donor solvent is one or more of water, methanol, ethanol, propanol, isopropanol, tetralin and decalin;
further, the inert gas is one of nitrogen, helium, neon and argon; the number of times of gas washing is 3-5.
Further, the reaction temperature is more than or equal to 250 ℃, and the reaction time is 0.25-8 h.
In the embodiment of the cheap metal catalyst and the preparation method thereof, the volume of deionized water used for preparing the solution is not greatly influenced, and the metal salt can be completely dissolved; the metal salt is not limited to nitrate, and other metal chlorides and metal sulfates can be contained.
Example 1:
mixing 0.072molMg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.003mol Cu(NO3)2·3H2O in 150mL deionized water, 0.25mol NaOH in 250mL deionized water, 0.025mol Na2CO3Dissolved in 187.5mL deionized water; mixing Na2CO3Transferring the solution into a 1L beaker, heating to 50-70 ℃ through a water bath under a stirring state, then slowly dripping the metal ion mixed solution and the NaOH solution into the beaker respectively through a peristaltic pump, and keeping the temperature of the mixed solution at 50-70 ℃ and the pH value at 9-11; after titration, transferring the mixed solution into a 1L sealed glass bottle, and carrying out aging treatment at 50-70 ℃ under a stirring state; after the aging was completed, the mixture was filtered using a Buchner funnel (the following filtration step is the same as above), and the filtered solid was redispersed in 150mL of a solution containing 15gNa2CO3Pouring the mixed solution into a glass bottle, and stirring for 1h at 50-70 ℃; filtering the mixed solution again, re-dispersing the filtered solid in 300mL of 50-70 ℃ deionized water, adding 500mL of 50-70 ℃ deionized water for filtering, repeating the steps for more than 3-5 times, and then putting the obtained solid in a 110 ℃ oven for drying overnight; grinding the dried catalyst precursor into powder, then putting the powder into a muffle furnace, heating to 460 ℃ at the speed of 5 ℃/min, and carrying out heat preservation and calcination for 12 h; placing the calcined powder in flowing H2Heating to 350 ℃ at the speed of 1 ℃/min in the atmosphere, and preserving heat and reducing for 4 h; when the temperature is reduced to room temperature, the mixture is switched to flowing 1% O2Passivating the catalyst to obtain a cheap metal catalyst; the catalyst is labeled a.
Example 2:
the metal salts are used in the following amounts: 0.0675molMg (NO)3)2·6H2O、0.025mol Al(NO3)3·9H2O、0.0075molCu(NO3)2·3H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled B.
Example 3:
the metal salts are used in the following amounts: 0.06mol Mg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.015molCu(NO3)2·3H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled C.
Example 4:
the metal salts are used in the following amounts: 0.045molMg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.03molCu(NO3)2·3H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled D.
Example 5:
the metal salts are used in the following amounts: 0.03875molMg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.01125molCu(NO3)2·3H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled E.
Example 6:
the metal salts are used in the following amounts: 0.08125molMg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.01875molCu(NO3)2·3H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled F.
Example 7:
the metal salts are used in the following amounts: 0.06mol Mg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.015molNi(NO3)2·6H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled G.
Example 8:
the metal salts are used in the following amounts: 0.06mol Mg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.015molCo(NO3)2·6H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled H.
Example 9:
the metal salts are used in the following amounts: 0.06mol Mg (NO)3)2·6H2O、0.025molAl(NO3)3·9H2O、0.0075molCu(NO3)2·3H2O、0.0/075molNi(NO3)2·6H2O, the amounts and the steps of other reagents are the same as those in example 1; the catalyst is labeled I.
The following examples are application examples of lignin oligomer depolymerization and simultaneous upgrading of lignin oligomer based on the cheap metal catalyst to prepare high-quality liquid fuel.
Example 10:
placing 0.1g lignin oligomer, 0.1g catalyst A and 2.4g ethanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 25.25C% and the dimer yield was 28.31C%.
Example 11:
placing 0.1g lignin oligomer, 0.1g catalyst B and 0.9g propanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 28.76C% and the dimer yield was 28.18C%.
Example 12:
placing 0.1g lignin oligomer, 0.1g catalyst C and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 30.45C% and the dimer yield was 38.56C%.
Example 13:
placing 0.1g lignin oligomer, 0.1g catalyst D and 9.9g decalin in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 33.44C% and the dimer yield was 37.62C%.
Example 14:
placing 0.1g lignin oligomer, 0.1g catalyst C and 2.4g water in a reactor, washing with helium gas, pressurizing and sealing; then, heating the reactor to 300 ℃, preserving heat and reacting for 0.25h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 11.29C% and the dimer yield was 8.37C%.
Example 15:
placing 0.1g lignin oligomer, 0.1g catalyst C and 2.4g isopropanol alcohol in a reactor, washing with helium gas, pressurizing and sealing; then, heating the reactor to 300 ℃, preserving heat and reacting for 0.5h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 18.80C% and the dimer yield was 13.70C%.
Example 16:
placing 0.1g lignin oligomer, 0.1g catalyst C and 2.4g propanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 1h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 23.63C% and the dimer yield was 17.77C%.
Example 17:
placing 0.1g lignin oligomer, 0.1g catalyst C and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; heating the reactor to 300 ℃, preserving heat and reacting for 4 hours, placing the reactor in ice water for rapid cooling after the reaction is finished so as to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 37.76C% and the dimer yield was 57.97C%.
Example 18:
placing 0.1g lignin oligomer, 0.1g catalyst C and 2.4g tetralin in a reactor, washing with helium gas, pressurizing and sealing; heating the reactor to 300 ℃, preserving heat and reacting for 8 hours, placing the reactor in ice water for rapid cooling after the reaction is finished so as to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 33.27C% and the dimer yield was 40.99C%.
Example 19:
placing 0.1g lignin oligomer, 0.05g catalyst C and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; heating the reactor to 250 ℃, preserving heat and reacting for 0.5h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 10.38C% and the dimer yield was 7.23C%.
Example 20:
placing 0.1g lignin oligomer, 0.2g catalyst C and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then, heating the reactor to 350 ℃, preserving heat and reacting for 0.5h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 37.90C% and the dimer yield was 43.88C%.
Example 21:
placing 0.1g lignin oligomer, 0.4g catalyst C and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then, heating the reactor to 400 ℃, preserving heat and reacting for 0.5h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting liquid-phase products, and determining the components of the products by GC-MS and GC-FID; the result is: the monomer yield was 42.47C% and the dimer yield was 44.72C%.
Example 22:
placing 0.1g lignin oligomer, 0.1g catalyst E and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 29.77C% and the dimer yield was 35.44C%.
Example 23:
placing 0.1g lignin oligomer, 0.1g catalyst F and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 32.12C% and the dimer yield was 41.68C%.
Example 24:
placing 0.1G lignin oligomer, 0.1G catalyst G and 2.4G methanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 27.92C% and the dimer yield was 32.69C%.
Example 25:
placing 0.1g lignin oligomer, 0.1g catalyst H and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 27.38C% and the dimer yield was 35.43C%.
Example 26:
placing 0.1g lignin oligomer, 0.1g catalyst I and 2.4g methanol in a reactor, washing with helium gas, pressurizing and sealing; then heating the reactor to 300 ℃ and carrying out heat preservation reaction for 2h, after the reaction is finished, placing the reactor in ice water for rapid cooling to stop the reaction, then filtering, collecting a liquid-phase product, and determining the composition of the liquid-phase product through GC-MS and GC-FID; the result is: the monomer yield was 28.74C% and the dimer yield was 35.47C%.
Finally, it should be understood that the embodiments described herein are merely illustrative of the principles of embodiments of the present invention; other variations are possible within the scope of the invention; thus, by way of example, and not limitation, alternative configurations of embodiments of the invention may be considered consistent with the teachings of the present invention; accordingly, the embodiments of the invention are not limited to the embodiments explicitly described and depicted.
Claims (10)
1. A cheap metal catalyst for synchronously upgrading lignin oligomer by virtue of hydro-depolymerization is characterized in that magnesium-aluminum hydrotalcite is taken as a main body of the catalyst, one or more of cheap metals are taken as active components, the content of the active components is 3-30 mol% in terms of metal elements, and the ratio of divalent metal to trivalent metal in the catalyst is 2-4.
2. The cheap metal catalyst used for the simultaneous upgrading of the hydro-depolymerization of the lignin oligomer according to claim 1, wherein the cheap metal is one or more of copper, nickel and cobalt.
3. The preparation method of the cheap metal catalyst for the simultaneous upgrading of the lignin oligomer depolymerization by hydrogenation according to the claims 1-2, characterized by comprising the following steps:
(1) under stirring, adding M2+、Mg2+、Al3+The mixed solution and NaOH solution are respectively dripped with Na2CO3In the solution, controlling the temperature and pH of the mixed solution to precipitate the mixed solution;
(2) after the dropwise addition is finished, aging the mixed solution under a stirring state, and then filtering, washing and drying the mixed solution;
(3) and calcining the ground catalyst powder, and then reducing and passivating to obtain the cheap metal catalyst.
4. The method for preparing the cheap metal catalyst used for the simultaneous upgrading of the hydro-depolymerization of the lignin oligomer according to claim 3, wherein the temperature of the mixed liquor in the step (3.1) is controlled to be 50-70 ℃ and the pH value is 9-11.
5. The method for preparing the cheap metal catalyst used for the simultaneous upgrading of the lignin oligomer depolymerization by hydrogenation according to claim 3, wherein the cheap metal catalyst in step (3.3) needs to be in the presence of H2Reduction in the atmosphere with 1% O2And carrying out passivation treatment.
6. The use of the inexpensive metal catalyst for the simultaneous upgrading of lignin oligomer depolymerization according to claim 1, wherein; the method comprises the following steps:
(1) putting lignin oligomer, hydrogen-donating solvent and cheap metal catalyst into a reactor;
(2) washing with inert gas, pressurizing, sealing the reactor, heating to a specified temperature, and carrying out heat preservation reaction;
(3) and after the reaction is finished, rapidly cooling the reactor by adopting an ice water bath to stop the reaction, filtering a liquid-phase product, and removing a hydrogen donor solvent to obtain the high-grade liquid fuel.
7. The use of the cheap metal catalyst for the simultaneous upgrading of lignin oligomer depolymerization according to claim 6, characterized in that; the lignin oligomers include oligomers produced by lignin degradation in 5 processes, pyrolysis, hydrogenolysis, oxidation, base catalysis, and acid catalysis.
8. The use of the cheap metal catalyst for the simultaneous upgrading of lignin oligomer depolymerization according to claim 6, characterized in that; the hydrogen donor solvent is one or more of water, methanol, ethanol, propanol, isopropanol, tetralin and decalin;
9. the use of the cheap metal catalyst for the simultaneous upgrading of lignin oligomer depolymerization according to claim 6, characterized in that; the inert gas is one of nitrogen, helium, neon and argon; the number of times of gas washing is 3-5.
10. The use of the cheap metal catalyst for the simultaneous upgrading of lignin oligomer depolymerization according to claim 6, characterized in that; the reaction temperature is more than or equal to 250 ℃, and the reaction time is 0.25-8 h.
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