CN117779085A - Preparation of C by electrocatalytic conversion of biomass-derived molecules 2 Alcohol process - Google Patents
Preparation of C by electrocatalytic conversion of biomass-derived molecules 2 Alcohol process Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 92
- 239000002028 Biomass Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 22
- 230000008569 process Effects 0.000 title claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 68
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940075397 calomel Drugs 0.000 claims abstract description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 7
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 4
- 239000008103 glucose Substances 0.000 claims abstract description 4
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-hydroxyfuran-2-carbaldehyde Chemical compound OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 claims abstract description 3
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims abstract description 3
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims abstract description 3
- 206010056474 Erythrosis Diseases 0.000 claims abstract description 3
- 229930091371 Fructose Natural products 0.000 claims abstract description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 3
- 239000005715 Fructose Substances 0.000 claims abstract description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940120731 pyruvaldehyde Drugs 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 11
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 11
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 125000003172 aldehyde group Chemical group 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- 230000035484 reaction time Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 241000534000 Berula erecta Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 210000000497 foam cell Anatomy 0.000 description 1
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- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing C by electrocatalytic conversion of biomass derived molecules 2 Alcohol method. The method packageThe method comprises the following steps: at room temperature, in an H electrolytic cell which is divided into a cathode tank and an anode tank by an ion exchange membrane, carrying out electrocatalytic conversion biomass derivative molecular reaction for 5-200 minutes in a three-electrode system to obtain C 2 An alcohol; wherein the calomel electrode is a reference electrode and the platinum net is a counter electrode, and the working electrode is a high-activity metal electrode or a metal oxide electrode; the reaction substrate biomass derived molecules are specifically one or more of glycolaldehyde, glyoxylic acid, glycollic acid, glycerol, glyceraldehyde, pyruvaldehyde, erythrose, glucose, fructose, benzaldehyde, furfural or 5-hydroxy furfural. The invention reasonably designs the catalyst structure, and realizes the hydrogenation of aldehyde groups and the hydrogenolysis of hydroxyl groups in biomass derived molecules with high selectivity, thereby obtaining ethanol or glycol with high selectivity.
Description
Technical Field
The invention relates to a method for preparing C by electrocatalytic conversion of biomass-derived molecules 2 Alcohol method.
Background
In recent years, the problems of energy crisis, global warming and the like are more and more prominent, and the search for a sustainable development technology of low carbon emission is urgent. C (C) 2 Alcohols, such as ethanol, ethylene glycol, are a large number of chemicals that are widely used. In recent years, more and more research has focused on the preparation of C from renewable raw materials 2 An alcohol. Biomass is a variety of organisms produced by photosynthesis, compared to traditional fossil raw materials, and is a very potential renewable energy source. As technology matures, biomass can be converted to a variety of platform molecules, such as furfural, 5-hydroxymethylfurfural, glycolaldehyde, and the like. Further, researchers have transformed these platform molecules into a broad range of commodity chemicals. In paper American Institute of Chemical Engineers 2015,61,224, the hydrogenation of glycolaldehyde, a glucose derivative, was achieved by means of a Ru-based catalyst using 6MPa hydrogen at about 400K by a thermocatalytic process to obtain ethylene glycol. Based on this study, paper Joule 2019,3,1937-1948 converts glucose-derived glycolaldehyde to ethanol using 6MPa hydrogen at about 500K over a Pt-based catalyst with ethylene glycol as an intermediate. In patent (CN 108602737 a), ethylene glycol is produced by hydrogenating glycolaldehyde molecules using about 10MPa hydrogen at about 150 ℃. However, the above thermochemical reaction process has disadvantages of high reaction energy consumption, use of high-pressure hydrogen gas as a hydrogen source, and reliance on a noble metal catalyst. At present, a green and efficient way for biological treatment is urgently neededConversion of mass derived molecules to C for a wide range of uses 2 An alcohol.
Compared with the traditional thermocatalytic reaction, the electrocatalytic reduction process has the advantages of mild reaction conditions, renewable electric power as energy input, liquid water as a green hydrogen source and the like. By reasonable design of the catalyst, high product selectivity can be achieved. However, no related studies have been reported to date to electrochemically convert biomass-derived molecules into bulk chemicals such as ethanol or ethylene glycol.
Disclosure of Invention
The invention aims at overcoming the defects of high energy consumption, harsh reaction conditions, high-pressure hydrogen and the like in the current thermal catalytic reaction technology, and provides a method for preparing C by electrocatalytic conversion of biomass derived molecules 2 A method for preparing alcohol. The method adopts an electrochemical method and adopts a cheap transition metal catalytic electrode to convert biomass derived molecules into ethanol or glycol with high selectivity by using electric energy as energy input at normal temperature and normal pressure. The invention reasonably designs the catalyst structure, and realizes the hydrogenation of aldehyde groups and the hydrogenolysis of hydroxyl groups in biomass derived molecules with high selectivity, thereby obtaining ethanol or glycol with high selectivity.
In order to solve the technical problems, the invention adopts the following technical scheme:
preparation of C by electrocatalytic conversion of biomass-derived molecules 2 A method of alcohol comprising the steps of:
at room temperature, in an H electrolytic cell which is divided into a cathode tank and an anode tank by an ion exchange membrane, carrying out electrocatalytic conversion biomass derivative molecular reaction for 5-200 minutes in a three-electrode system to obtain C 2 An alcohol;
wherein the calomel electrode is a reference electrode and the platinum net is a counter electrode, and the working electrode is a high-activity metal electrode or a metal oxide electrode; the area of the working electrode is 0.1-50 cm -2 ；
When the electrolysis is carried out under constant voltage reaction, the reaction potential ranges from 0V to-2V vs RHE, and preferably from-0.3V to-2V vs RHE;
alternatively, when electrolysis is a constant current reaction, the currentThe density is 1-300 mA cm -2 ；
The electrolyte is an aqueous solution containing a reaction substrate and an electrolyte, and the concentration of the electrolyte is 0.01-5M; the concentration of the reaction substrate is 5-500 mM; the electrolyte is KHCO 3 One or more of potassium dihydrogen phosphate or dipotassium hydrogen phosphate;
the reaction substrate biomass derived molecules are specifically one or more of glycolaldehyde, glyoxylic acid, glycollic acid, glycerol, glyceraldehyde, pyruvaldehyde, erythrose, glucose, fructose, benzaldehyde, furfural or 5-hydroxy furfural;
the high-activity metal electrode is a catalytic electrode loaded with a metal simple substance and prepared by an electrodeposition method, and the metal oxide electrode is a catalytic electrode loaded with a metal oxide and prepared by steps such as electrooxidation;
the metal simple substance is copper, zinc or nickel, and the metal oxide is copper oxide, cuprous oxide, zinc oxide or nickel oxide;
the carriers are carbon paper, carbon cloth, foam nickel sheets, foam copper sheets, foam zinc sheets or porous titanium sheets;
the C is 2 The alcohol is ethanol or glycol;
the room temperature is 30+/-5 ℃.
The preparation method of the high-activity metal electrode comprises the following steps:
step 1: according to the proportion that each 5-30 g of soluble transition metal salt is dissolved in 20-80 mL of water, a precursor solution A is obtained; wherein the soluble transition metal salt is specifically copper sulfate, zinc nitrate or nickel sulfate;
step 2: in a two-electrode electrolytic cell, a catalyst carrier is used as a working electrode, a graphite rod is used as a counter electrode, a solution A is used as an electrolyte, and the concentration of the electrolyte is 1-100 mA cm -2 Carrying out reaction for 60-3000 s under the reducing current;
the catalyst carrier is specifically carbon paper, carbon cloth, foam nickel sheet, foam copper sheet, foam zinc sheet or porous titanium sheet, and the area is 0.1-50 cm -2 ；
Step 3: and respectively cleaning the working electrode by using deionized water and ethanol, and drying by using nitrogen to obtain the high-activity metal electrode.
The preparation method of the metal oxide electrode comprises the following steps:
step 1: according to the proportion that each 1-100 g of soluble electrolyte is dissolved in 20-1000 mL of water, a precursor solution B is obtained; the soluble electrolyte is one or more of potassium hydroxide, monopotassium phosphate and dipotassium phosphate;
step 2: in a two-electrode electrolytic cell, a catalyst carrier is used as a working electrode, a graphite rod is used as a counter electrode, a solution B is used as an electrolyte, and the concentration of the electrolyte is 1-100 mA cm -2 Carrying out oxidation reaction for 30-3000s under the current density; the catalyst carrier is specifically carbon paper, carbon cloth, foam nickel sheet, foam copper sheet, foam zinc sheet or porous titanium sheet, and the area is 1-50 cm -2 ；
Step 3: cleaning the working electrode in the step 2 by using deionized water and ethanol respectively, and drying by using nitrogen for standby;
step 4: roasting the electrode obtained in the step 3 for 1-10 h at 200-500 ℃;
step 5: in a three-electrode electrolytic cell, the electrode obtained in the step 4 is used as a working electrode, a graphite rod is used as a counter electrode, a calomel electrode is used as a reference electrode, a solution B is used as an electrolyte, and the concentration of the electrolyte is 1-100 mA cm -2 Carrying out reduction reaction for 30-3000s under the current density;
step 6: and (5) respectively cleaning the working electrode in the step (5) by using deionized water and ethanol, and drying by using nitrogen to obtain the metal oxide electrode.
The invention has the substantial characteristics that:
in order to solve the defects of high energy consumption, harsh reaction conditions, high-pressure hydrogen and the like in the current thermal catalytic reaction technology, the invention innovatively provides a method for preparing C by converting biomass derived molecules through electrocatalytic conversion 2 A method for preparing alcohol. The catalytic electrode according to the invention is produced by electrochemical means. The method is simple and easy for mass production. The electrode prepared by the invention has specific adsorption to specific functional groups of biomass derived molecules, thereby realizing high-selectivity hydrogenation and high-selectivity hydrogenation to aldehyde groupsHydrogenolysis of the p-hydroxy group with high selectivity. The method not only makes up the inherent defects of the thermocatalytic reaction, but also solves the problem of selective hydrogenolysis reaction which cannot be realized in the thermocatalytic process. The optimal Faraday efficiency of the invention for preparing single target product ethanol (or glycol) by electrocatalytic conversion of biomass derived molecules is higher than 70%, the selectivity is higher than 80%, the conversion rate of reaction substrates is higher than 80%, and the reaction current density is higher than 100mA cm -2 Meets the basic requirement of further popularization and industrial application.
The beneficial effects of the invention are as follows:
(1) The catalyst prepared by the invention has specific adsorption to specific functional groups of biomass-derived molecules, thereby realizing high-selectivity hydrogenation of aldehyde groups and high-selectivity hydrogenolysis of hydroxyl groups.
(2) The catalyst used in the invention is cheap metal, and the price is far lower than noble metal Pt or Ru used in the thermocatalytic reaction. The catalyst preparation method is simple and is easy for large-scale production.
(3) The invention provides a method for preparing ethanol or ethylene glycol by electrocatalytically converting biomass-derived molecules for the first time. The selectivity of the ethanol or glycol of the single product is higher than 80%, the conversion rate of the reaction substrate is higher than 80%, and the reaction current density is higher than 100mA cm -2 Meets the basic requirement of further popularization and industrial application. Compared with the thermal catalysis method for carrying out the hydrogenation process, the reaction condition of the hydrogenation process is milder, the energy input is renewable electric power, and the hydrogen source is from water. Compared with the biological fermentation biomass conversion process, the process route is more efficient. Compared with the traditional ethanol and glycol preparation routes, such as a coal chemical industry or an ethylene oxide route, the process route does not depend on fossil resources as raw materials.
Drawings
FIG. 1 is a scanning electron microscope image and a transmission electron microscope image of the high-activity Cu metal electrode prepared in example 1; fig. 1a is a scanning electron microscope image of a high-activity Cu metal electrode, and fig. 1b is a transmission electron microscope image of a high-activity Cu metal electrode.
FIG. 2 shows Cu obtained in example 3 x O-metal oxide electricityScanning electron microscopy and transmission electron microscopy of poles, wherein FIG. 2a is Cu x Scanning electron microscopy of O-metal oxide electrode, FIG. 2b is Cu x Transmission electron microscopy of the O-metal oxide electrode.
FIG. 3 is a graph showing the relationship between the conversion of the reaction substrate, the yield of the product and the coulombic quantity in example 6.
FIG. 4 is a graph showing the conversion of the reaction substrate, the yield of the product and the coulombic amount in example 8.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to the examples. Experimental methods, in which specific conditions are not specified in examples, are generally available commercially according to conventional conditions as well as those described in handbooks, or according to general-purpose equipment, materials, reagents, etc. used under conditions suggested by manufacturers, unless otherwise specified.
The present invention is described in detail below with reference to examples to provide a method for preparing a catalytic electrode and a method for preparing ethanol and ethylene glycol by electrocatalytically converting biomass-derived molecules, but they should not be construed as limiting the scope of the invention.
Example 1
Preparation of C for electrocatalytic conversion of biomass-derived molecules 2 The preparation method of the high-activity Cu metal electrode of the alcohol comprises the following steps:
step 1: 25.8g of copper sulfate was accurately weighed and dissolved in 40mL of water (copper sulfate concentration: 4.04M), to obtain a precursor solution A.
Step 2: in a two-electrode cell, copper foam was used as the working electrode, the electrode area was 6cm 2 . Graphite rod as counter electrode, solution A as electrolyte, at 10mA cm -2 The reaction was carried out at a reduction current for 1000s.
Step 3: and (3) respectively cleaning the working electrode in the step (2) by using deionized water and ethanol, and drying by using nitrogen to obtain the Cu catalyst electrode.
Fig. 1 is a scanning electron microscope (fig. 1 a) and a transmission electron microscope (fig. 1 b) of the high-activity Cu metal electrode prepared in example 1. As can be seen from fig. 1a, the electrode surface is an island-like structure of particles. The island-like particle structure increases the electrode reactive sites. From FIG. 1b, it can be seen that the 0.21nm lattice fringes correspond to the Cu (111) crystal plane, indicating that the synthesized high-activity Cu metal electrode is elemental copper. The raman spectrum and DFT calculation result show that the surface of the high-activity Cu metal electrode is more prone to adsorb aldehyde groups of biomass-derived molecules (e.g., glycolaldehyde), thereby being more beneficial to hydrogenation of the aldehyde groups to ethylene glycol products. At the same time, DFT calculation also indicates that the high-activity Cu metal electrode has lower energy barrier for controlling the reaction speed of glycol production by glycolaldehyde hydrogenation, which is also beneficial to the conversion of reactants into glycol.
Example 2
Preparation of C for electrocatalytic conversion of biomass-derived molecules 2 The preparation method of the high-activity Ni metal electrode of the alcohol comprises the following steps:
step 1: 27.1g of nickel sulfate was accurately weighed and dissolved in 50mL of water to obtain a precursor solution B (nickel sulfate concentration: 3.5M).
Step 2: in a two-electrode cell, foam nickel was used as the working electrode, the electrode area was 20cm 2 . Graphite rod as counter electrode, solution B as electrolyte, at 20mA cm -2 The reaction was carried out at a reducing current for 600s.
Step 3: and (3) respectively cleaning the working electrode in the step (2) by using deionized water and ethanol, and drying by using nitrogen to obtain the high-activity Ni catalyst electrode.
Example 3
Preparation of C for electrocatalytic conversion of biomass-derived molecules 2 The preparation method of the metal oxide electrode of the alcohol comprises the following steps:
step 1: the precursor solution C (potassium hydroxide concentration: 1M) was obtained by dissolving 50mL of potassium hydroxide in each 2.805g of water. The precursor solution D (dipotassium hydrogen phosphate concentration: 420.2mM, potassium dihydrogen phosphate concentration: 37.6 mM) was obtained by dissolving each 18.3g of dipotassium hydrogen phosphate and 1.28g of potassium dihydrogen phosphate in 250mL of water.
Step 2: in a two-electrode cell, copper foam was used as the working electrode, with an area of 6cm -2 . Graphite rod as counter electrode, solution C as electrolyte, at 10mA cm -2 Current densityThe oxidation reaction was carried out at a temperature of 600s.
Step 3: and (3) respectively cleaning the working electrode in the step (2) by using deionized water and ethanol, and drying by using nitrogen for standby.
Step 4: and (3) roasting the electrode obtained in the step (3) in a muffle furnace at the temperature of 250 ℃ for 2 hours.
Step 5: in a three-electrode electrolytic cell, the electrode obtained in the step 4 is used as a working electrode, a graphite rod is used as a counter electrode, a calomel electrode is used as a reference electrode, a solution D is used as an electrolyte, and the concentration of the electrolyte is 20mA cm -2 The reduction reaction was carried out at a current density for 600s.
Step 6: cleaning the working electrode in the step 5 by deionized water and ethanol respectively, and drying by nitrogen to obtain Cu x O metal oxide electrode.
By means of the electrooxidation of step 2, a precursor of the catalytic electrode is first obtained, which has a high oxidation state. Further, the metal oxide electrode having a mixture phase is finally obtained by the firing in step 4 and the reduction treatment in step 5. FIG. 2 shows Cu obtained in example 3 x Scanning electron microscopy (fig. 2 a) and transmission electron microscopy (fig. 2 b) of the O-metal oxide electrode. As can be seen from fig. 2a, the electrode surface is in a coral strip-like structure. As can be seen from FIG. 2b, the planar spacing of the lattice fringes is 0.24nm and 0.21nm, corresponding to Cu, respectively 2 O (111) and Cu (111) planes. This means that in addition to the elemental copper, cu is also present in the electrode 2 O. The results of Raman spectrum and DFT calculation show that Cu x The O-metal oxide electrode surface is more prone to adsorb hydroxyl groups of biomass-derived molecules (e.g., glycolaldehyde), thereby facilitating hydrogenolysis of hydroxyl groups. At the same time DFT calculations also indicate Cu x The O metal oxide electrode has lower energy barrier for controlling the speed of the hydroxyl hydrogenolysis reaction of glycolaldehyde, which is also beneficial to the conversion of glycolaldehyde into intermediate acetaldehyde. The intermediate product acetaldehyde is further hydrogenated to produce the target product ethanol.
Example 4
The method for preparing glycol by electrocatalytically converting biomass-derived molecules is specifically as follows:
step 1:3g of glycolaldehyde, 18.3g of dipotassium hydrogen phosphate and 1.28g of potassium dihydrogen phosphate were dissolved in 250mL of water to obtain a solution E (substrate concentration: 200mM, dipotassium hydrogen phosphate concentration: 420.2mM, potassium dihydrogen phosphate concentration: 37.6 mM).
Step 2: in an H cell separated into a cathode cell and an anode cell by an ion exchange membrane, the electrode obtained in example 1 was used as a working electrode, a platinum mesh was used as a counter electrode, a calomel electrode was used as a reference electrode, a solution E was used as an electrolyte, and the concentration of glycolaldehyde as a reaction substrate was 200mM. The reaction was carried out at-0.6V vs RHE using Chen Hua 760 electrochemical workstation with a current density of about 105mA cm -2 . The area of the working electrode is 1cm -2 . The reaction temperature was room temperature. The reaction time was 20 minutes.
Step 3: the solution after the completion of the reaction was analyzed by high performance liquid chromatography equipped with a differential detector (Shodex R1-201H). The column was a Berle Aminex HPX-87H with a constant temperature of 40 ℃. The mobile phase was 5mM aqueous sulfuric acid. The target product glycol Fabry-Perot efficiency was measured to be over 70%.
Example 5
The method for preparing ethanol by electrocatalytically converting biomass-derived molecules is specifically as follows:
step 1:3g of glycolaldehyde, 18.3g of dipotassium hydrogen phosphate and 1.28g of potassium dihydrogen phosphate were dissolved in 250mL of water to obtain a solution E.
Step 2: in an H cell separated into a cathode cell and an anode cell by an ion exchange membrane, the electrode obtained in example 3 was used as a working electrode, a platinum mesh was used as a counter electrode, a calomel electrode was used as a reference electrode, a solution E was used as an electrolyte, and the concentration of glycolaldehyde as a reaction substrate was 200mM. The reaction is carried out at-0.7V vs RHE using Chen Hua 760 electrochemical workstation, and the current density is about 130mA cm -2 . The area of the working electrode is 1cm -2 . The reaction temperature was room temperature. The reaction time was 80 minutes.
Step 3: the solution after completion of the reaction was analyzed by high performance liquid chromatography in the same manner as in example 4. The Faraday efficiency of the target product ethanol exceeds 70%.
Example 6
The method for preparing glycol by electrocatalytically converting biomass-derived molecules is specifically as follows:
step 1:3g of glycolaldehyde, 18.3g of dipotassium hydrogen phosphate and 1.28g of potassium dihydrogen phosphate were dissolved in 250mL of water to obtain a solution E.
Step 2: in an H cell separated into a cathode cell and an anode cell by an ion exchange membrane, the electrode obtained in example 1 was used as a working electrode, a platinum mesh was used as a counter electrode, a calomel electrode was used as a reference electrode, a solution E was used as an electrolyte, and the concentration of glycolaldehyde as a reaction substrate was 200mM. Using Cinhua 760 electrochemical workstation at a constant 100mA cm -2 The reaction was carried out at current. The area of the working electrode is 1cm -2 . The reaction temperature was room temperature. The reaction time was 100 minutes.
Step 3: solutions of different amounts of reaction charge were analyzed by high performance liquid chromatography in the same manner as in example 4.
FIG. 3 is a graph showing the change in conversion of a reaction substrate and yield of a product with the amount of coulombs of the reaction in example 6. It can be seen from the graph that the glycolaldehyde conversion rate and the glycol yield increase linearly with the amount of charge. When the charge exceeds 300C, there is no further dramatic increase in substrate turnover rate and ethylene glycol yield, suggesting that most of the reaction substrate has been converted. Finally, the conversion rate of glycolaldehyde can reach 83%, and the yield of glycol reaches 78.9%. The selectivity of the electrode to ethylene glycol is as high as 95.1%.
Example 7
The method for preparing glycol by electrocatalytically converting biomass-derived molecules is specifically as follows:
the procedure of example 4 was followed except that the electrode obtained in example 2 was used as a working electrode.
The solution after completion of the reaction was analyzed by high performance liquid chromatography in the same manner as in example 4. The target product glycol Fabry-Perot efficiency was measured to be over 70%.
Example 8
The method for preparing ethanol by electrocatalytically converting biomass-derived molecules is specifically as follows:
step 1:3g of glycolaldehyde, 18.3g of dipotassium hydrogen phosphate and 1.28g of potassium dihydrogen phosphate were dissolved in 250mL of water to obtain a solution E.
Step 2: at the position ofIn an H cell separated into a cathode cell and an anode cell by an ion exchange membrane, the electrode obtained in example 3 was used as a working electrode, a platinum mesh was used as a counter electrode, a calomel electrode was used as a reference electrode, a solution E was used as an electrolyte, and the concentration of glycolaldehyde as a reaction substrate was 200mM. Using Cinhua 760 electrochemical workstation at a constant 100mA cm -2 The reaction was carried out at current. The area of the working electrode is 1cm -2 . The reaction temperature was room temperature. The reaction time was 7000 seconds.
Step 3: solutions of different amounts of reaction charge were analyzed by high performance liquid chromatography in the same manner as in example 4.
FIG. 4 is a graph showing the change in conversion of a reaction substrate and yield of a product with the amount of coulombs of the reaction in example 8. It can be seen from the graph that the glycolaldehyde conversion rate increases linearly with increasing charge. The primary product is acetaldehyde. When the charge amount reached 300C, the acetaldehyde yield reached a peak. As the charge is further increased, the intermediate acetaldehyde is converted to ethanol. Finally, the conversion of the substrate glycolaldehyde reached 85.6% and the ethanol yield was 68.7%. The electrode selectivity to ethanol was 80.2%.
As can be seen from the above examples, the invention can prepare non-noble metal catalytic electrodes with different element compositions and oxidation states by adjusting the conditions of electrodeposition, electro-oxidation and electro-reduction. The conversion of biomass-derived molecules into ethanol and ethylene glycol is achieved by an electrocatalytic process. Compared with the traditional thermocatalytic method, the electrochemical method has the advantages of mild reaction conditions, renewable power as energy input, low-cost metal catalyst, high selectivity and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
The invention is not a matter of the known technology.
Claims (5)
1. Preparation of C by electrocatalytic conversion of biomass-derived molecules 2 A process for alcohol, characterized in that the process comprises the steps of:
at room temperature, in an H electrolytic cell which is divided into a cathode tank and an anode tank by an ion exchange membrane, carrying out electrocatalytic conversion biomass derivative molecular reaction for 5-200 minutes in a three-electrode system to obtain C 2 An alcohol;
wherein the calomel electrode is a reference electrode and the platinum net is a counter electrode, and the working electrode is a high-activity metal electrode or a metal oxide electrode;
when the electrolysis is a constant voltage reaction, the reaction potential ranges from 0V to-2V vs RHE;
alternatively, when electrolysis is a constant current reaction, the current density is 1-300 mA cm -2 ；
The electrolyte is an aqueous solution containing a reaction substrate and an electrolyte, and the concentration of the electrolyte is 0.01-5M; the concentration of the reaction substrate is 5-500 mM; the electrolyte is KHCO 3 One or more of potassium dihydrogen phosphate or dipotassium hydrogen phosphate;
the reaction substrate biomass derived molecules are specifically one or more of glycolaldehyde, glyoxylic acid, glycollic acid, glycerol, glyceraldehyde, pyruvaldehyde, erythrose, glucose, fructose, benzaldehyde, furfural or 5-hydroxy furfural;
the high-activity metal electrode is a catalytic electrode loaded with a metal simple substance and prepared by an electrodeposition method, and the metal oxide electrode is a catalytic electrode loaded with a metal oxide and prepared by steps such as electrooxidation;
the metal simple substance is copper, zinc or nickel, and the metal oxide is copper oxide, cuprous oxide, zinc oxide or nickel oxide;
the carriers are carbon paper, carbon cloth, foam nickel sheets, foam copper sheets, foam zinc sheets or porous titanium sheets.
2. Preparation of C for electrocatalytic conversion of biomass-derived molecules as claimed in claim 1 2 A process for the preparation of alcohols, characterized in that said C 2 The alcohol is ethanol or ethylene glycol.
3. Preparation of C for electrocatalytic conversion of biomass-derived molecules as claimed in claim 1 2 A process for alcohol, characterized in that said room temperature is 30 ℃ ± 5 ℃; when the electrolysis is carried out under constant voltage, the reaction potential is preferably-0.3V to-2V vs RHE.
4. Preparation of C for electrocatalytic conversion of biomass-derived molecules as claimed in claim 1 2 The alcohol method is characterized in that the preparation method of the high-activity metal electrode comprises the following steps:
step 1: according to the proportion that each 5-30 g of soluble transition metal salt is dissolved in 20-80 mL of water, a precursor solution A is obtained;
wherein the soluble transition metal salt is specifically copper sulfate, zinc nitrate or nickel sulfate;
step 2: in a two-electrode electrolytic cell, a catalyst carrier is used as a working electrode, a graphite rod is used as a counter electrode, a solution A is used as an electrolyte, and the concentration of the electrolyte is 1-100 mA cm -2 Carrying out reaction for 60-3000 s under the reducing current;
the catalyst carrier is specifically carbon paper, carbon cloth, foam nickel sheet, foam copper sheet, foam zinc sheet or porous titanium sheet;
step 3: and respectively cleaning the working electrode by using deionized water and ethanol, and drying by using nitrogen to obtain the high-activity metal electrode.
5. Preparation of C for electrocatalytic conversion of biomass-derived molecules as claimed in claim 1 2 The alcohol method is characterized in that the preparation method of the metal oxide electrode comprises the following steps:
step 1: according to the proportion that each 1-100 g of soluble electrolyte is dissolved in 20-1000 mL of water, a precursor solution B is obtained; the soluble electrolyte is one or more of potassium hydroxide, monopotassium phosphate and dipotassium phosphate;
step 2: in a two-electrode electrolytic cell, a catalyst carrier is used as a working electrode, a graphite rod is used as a counter electrode, a solution B is used as an electrolyte, and the concentration of the electrolyte is 1-100 mA cm -2 Carrying out oxidation reaction for 30-3000s under the current density; the catalyst carrier hasThe body is carbon paper, carbon cloth, foam nickel sheet, foam copper sheet, foam zinc sheet or porous titanium sheet;
step 3: cleaning the working electrode in the step 2 by using deionized water and ethanol respectively, and drying by using nitrogen for standby;
step 4: roasting the electrode obtained in the step 3 for 1-10 h at 200-500 ℃;
step 5: in a three-electrode electrolytic cell, the electrode obtained in the step 4 is used as a working electrode, a graphite rod is used as a counter electrode, a calomel electrode is used as a reference electrode, a solution B is used as an electrolyte, and the concentration of the electrolyte is 1-100 mA cm -2 Carrying out reduction reaction for 30-3000s under the current density;
step 6: and (5) respectively cleaning the working electrode in the step (5) by using deionized water and ethanol, and drying by using nitrogen to obtain the metal oxide electrode.
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