CN117737755A - Method for preparing maleic acid by electrocatalytic oxidation - Google Patents
Method for preparing maleic acid by electrocatalytic oxidation Download PDFInfo
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- CN117737755A CN117737755A CN202311748299.4A CN202311748299A CN117737755A CN 117737755 A CN117737755 A CN 117737755A CN 202311748299 A CN202311748299 A CN 202311748299A CN 117737755 A CN117737755 A CN 117737755A
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- mesoporous
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- nafion
- maleic acid
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- 238000000034 method Methods 0.000 title claims abstract description 67
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 59
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title claims abstract description 59
- 239000011976 maleic acid Substances 0.000 title claims abstract description 59
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 54
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 112
- 239000000463 material Substances 0.000 claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 57
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 20
- 239000002910 solid waste Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 87
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- 239000012528 membrane Substances 0.000 claims description 43
- 239000002131 composite material Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- -1 silica compound Chemical class 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims description 5
- 238000007781 pre-processing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 238000010812 external standard method Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 5
- 229930091371 Fructose Natural products 0.000 description 5
- 239000005715 Fructose Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000968352 Scandia <hydrozoan> Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- HBTFASPVVFSRRI-UHFFFAOYSA-N manganese(2+);dinitrate;hydrate Chemical compound O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O HBTFASPVVFSRRI-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- HZQULVNEUCEVQV-UHFFFAOYSA-N scandium(3+);trinitrate;hydrate Chemical compound O.[Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HZQULVNEUCEVQV-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a method for preparing maleic acid by electrocatalytic oxidation, which comprises the following steps: s1, preparing mesoporous oxide/carbon paper material and pretreated Nafion-117 ion exchange membranes; s2 assembling an H-shaped electrolytic cell, wherein in the H-shaped electrolytic cell, a working electrode is made of the mesoporous oxide/carbon paper material, and electrolyte in a cathode area is H 2 SO 4 Solution, electrolyte of anode region is H 2 SO 4 The mixed solution of the solution and the 5-hydroxymethylfurfural solution is characterized in that the cathode area and the anode area are separated by the pretreated Nafion-117 ion exchange membrane; and S3, after the assembly is completed, placing the H-shaped electrolytic cell into a water bath kettle for water bath heating, and applying voltage to the H-shaped electrolytic cell to enable the 5-hydroxymethylfurfural solution to undergo electrocatalytic oxidation reaction, so that maleic acid is obtained after the reaction is completed. The method for preparing the maleic acid by utilizing the biomass solid waste electrocatalytic oxidation provided by the invention has the advantages of environment-friendly and simple process, mild reaction conditions and high reaction efficiency.
Description
Technical Field
The invention belongs to the technical field of preparation of maleic acid, and particularly relates to a method for preparing maleic acid by electrocatalytic oxidation.
Background
Maleic acid is a monoclinic colorless crystal at normal temperature and has a variety of applications in the chemical industry, mainly for the manufacture of unsaturated polyester resins and the production of tartaric acid, fumaric acid and other compounds, including as intermediates for certain resins and plastics, and in water treatment, medicine and food industry. As chemical intermediates, maleic acid is used to prepare maleic anhydride, which in turn produces various organic compounds including acrylic acid, phthalic acid, and maleimide, etc., which play an important role in the preparation of polymers, dyes, pharmaceuticals, and pesticides. In terms of water treatment, maleic acid can be used to prevent scale formation; in the food industry, it is used as a food acidulant and a sour modifier for improving the taste of foods and beverages; in addition, maleic acid plays a role in the preparation of medicines. Thus, the versatility of maleic acid makes it an essential compound in industry.
At present, the process for preparing maleic acid is mostly a chemical catalytic method, and acrylic acid or furfural is used as a raw material to react with oxygen under the action of a catalyst to generate maleic acid. Typical catalysts include vanadates, tungstates, metal oxides, and the like, and specific reaction mechanisms involve the combination of carbon-carbon double bonds in acrylic acid with oxygen to form the desired maleic acid. The yield of the maleic acid prepared by the chemical catalytic method is about 60%, and severe reaction conditions such as high temperature, high pressure, use of acid, alkali metal catalyst, halogen element, organic solvent and the like are often required to be provided, so that the problems of high equipment cost, high energy consumption, poor selectivity, environment friendliness and the like exist.
Therefore, how to provide a method for preparing maleic acid by electrocatalytic oxidation, the process is environment-friendly and simple, the reaction condition is mild, the reaction efficiency is high, and the method is a problem to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, maleic acid is prepared by a traditional chemical catalytic method, the yield is low, harsh reaction conditions are required to be provided, and the method has the advantages of high equipment cost, high energy consumption, poor selectivity, environment friendliness and the like.
In order to solve the above problems, the present invention provides a method for preparing maleic acid by electrocatalytic oxidation, the method comprising: s1, preparing a mesoporous oxide/carbon paper material, and preprocessing a Nafion-117 ion exchange membrane to obtain the preprocessed Nafion-117 ion exchange membrane; s2 assembling an H-shaped electrolytic cell, wherein in the H-shaped electrolytic cell, a working electrode is made of the mesoporous oxide/carbon paper material, and electrolyte in a cathode area is H 2 SO 4 Solution, electrolyte of anode region is H 2 SO 4 The mixed solution of the solution and the 5-hydroxymethylfurfural solution is characterized in that the cathode area and the anode area are separated by the pretreated Nafion-117 ion exchange membrane; and S3, after the assembly is completed, placing the H-shaped electrolytic cell into a water bath kettle for water bath heating, and applying voltage to the H-shaped electrolytic cell to enable the 5-hydroxymethylfurfural solution to undergo electrocatalytic oxidation reaction, so that maleic acid is obtained after the reaction is completed.
As still further technical solution of the present invention, the preparation of the mesoporous oxide/carbon paper material includes: preparing a mesoporous oxide material, adding the mesoporous oxide material into a beaker containing ethanol and Nafion solution, stirring to obtain solution A, dripping the solution A on carbon paper, and then airing the carbon paper at room temperature to obtain the mesoporous oxide/carbon paper material.
As still further technical solutions of the present invention, the mesoporous oxide material includes mesoporous scandium oxide, mesoporous Kongnie composite oxide, mesoporous Kongtie composite oxide, mesoporous Konggu composite oxide, or mesoporous Kongmeng composite oxide.
As still further technical solutions of the present invention, the preparation of the mesoporous oxide material includes: s101, preparing a mesoporous silica template; s102, dissolving 1g of nitrate hydrate in 12mL of ethanol to obtain a solution B, adding 0.5g of mesoporous silica template into the solution B, stirring, drying and grinding to obtain a metal nitrate@mesoporous silica compound; s103, calcining the metal nitrate@mesoporous silica composite at 550-650 ℃ for 2 hours to obtain a metal oxide@mesoporous silica composite; s104, adding the metal oxide@mesoporous silica compound into 50-100 mL of 1-2 mol/L sodium hydroxide solution, stirring at 70-90 ℃, cooling to room temperature after stirring, centrifuging and drying to obtain a precipitate; and S105, repeating the step S104 for three times on the precipitate to obtain the mesoporous oxide material.
According to the still further technical scheme, the 5-hydroxymethylfurfural solution is prepared from biomass solid waste serving as a raw material.
As a still further technical solution of the present invention, in step S2: in the H-type electrolytic cell, a reference electrode is Ag/AgCl, a counter electrode is a platinum wire, the concentration of the 5-hydroxymethylfurfural solution is 10 mmol/L-500 mmol/L, and the H is 2 SO 4 The concentration of the solution is 0.1mol/L to 2mol/L.
As a still further technical solution of the present invention, in step S3: the temperature of the water bath heating is 25-300 ℃.
As a still further technical solution of the present invention, in step S3: the voltage is 1.6V-2V, and the time of the electrocatalytic oxidation reaction is 0.5 h-100 h.
As a still further technical solution of the present invention, in step S1, the pretreatment of the Nafion-117 ion exchange membrane includes: nafion-117 membrane was placed in 3wt% H 2 O 2 Heating at 100deg.C for 1 hr, and taking outAnd then placing the Nafion-117 membrane into deionized water and heating the deionized water at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, placing the Nafion-117 membrane into 1mol/L sulfuric acid and heating the Nafion-117 membrane at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, and finally placing the Nafion-117 membrane into deionized water and heating the Nafion-117 membrane at 100 ℃ for 1h.
As a still further technical solution of the present invention, in step S1: the width of the carbon paper is 1 cm-3 cm, and the length of the carbon paper is 1 cm-3 cm.
The beneficial effects are that: the invention provides a method for preparing maleic acid by electrocatalytic oxidation, which comprises the steps of firstly preparing mesoporous oxide/carbon paper material, preprocessing Nafion-117 ion exchange membrane, taking the mesoporous oxide/carbon paper material as a working electrode, and taking H as a raw material 2 SO 4 The solution is the electrolyte of the cathode area, H 2 SO 4 The mixed solution of the solution and the 5-hydroxymethyl furfural solution is electrolyte of an anode region, an electrochemical catalytic reactor is formed together, and a pretreated Nafion-117 ion exchange membrane is used for separating the anode region from the cathode region so as to complete the assembly of the H-type electrolytic cell; after the assembly is completed, the H-shaped electrolytic cell is placed into a water bath kettle to be heated in a water bath, and voltage is applied to the H-shaped electrolytic cell, so that the 5-hydroxymethylfurfural solution is subjected to electrocatalytic oxidation reaction under a certain working voltage and current density, the 5-hydroxymethylfurfural solution in an anode region is oxidized into maleic acid, and hydrogen is generated in a cathode region. The invention prepares the maleic acid through electrocatalytic oxidation, the electric energy can be converted based on renewable energy sources such as solar energy, wind energy and the like, and the method is clean and sustainable energy source with potential, so that the electrocatalytic energy can be driven by clean and environment-friendly renewable electric energy, no pollutant can be directly discharged, the process is environment-friendly and simple, the reaction condition is mild, compared with the traditional thermodynamic control reaction, the more accurate control of the reaction process can be realized, the selectivity of the reaction is improved, and secondly, the electrocatalytic can provide controllable electron transport, thereby being beneficial to reducing the generation of side reaction, improving the efficiency of the reaction, and the electrochemical in-situ obtaining the product of the oxidation process, thereby realizing the high-efficiency utilization of the 5-hydroxymethylfurfural and simultaneously generating high-value hydrogen. Compared with the traditional processCompared with the preparation method, the preparation method has the advantages of high selectivity, high efficiency, green pollution-free property, low cost, simple operation and the like of the maleic acid, and has wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present description or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing maleic acid by electrocatalytic oxidation in an embodiment of the invention;
FIG. 2 is a linear sweep voltammogram of the electrocatalytic process of example 2 of the present invention;
FIG. 3 is an SEM image of a mesoporous scandia material synthesized in example 2 of the present invention;
FIG. 4 is a graph showing the yields of maleic acid produced at various voltages from a solution of 5-hydroxymethylfurfural in an example of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Meanwhile, throughout the specification, unless otherwise specifically indicated, the terms used herein should be construed as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
As shown in fig. 1, a first embodiment provides a method for preparing maleic acid by electrocatalytic oxidation, which includes: s1, preparing a mesoporous oxide/carbon paper material and a 5-hydroxymethylfurfural solution, and preprocessing a Nafion-117 ion exchange membrane to obtain the preprocessed Nafion-117 ion exchange membrane; s2 assembling an H-shaped electrolytic cell, wherein in the H-shaped electrolytic cell, a working electrode is made of the mesoporous oxide/carbon paper material, and electrolyte in a cathode area is H 2 SO 4 Solution, electrolyte of anode region is H 2 SO 4 The mixed solution of the solution and the 5-hydroxymethylfurfural solution is characterized in that the cathode area and the anode area are separated by the pretreated Nafion-117 ion exchange membrane; and S3, after the assembly is completed, placing the H-shaped electrolytic cell into a water bath kettle for water bath heating, and applying voltage to the H-shaped electrolytic cell to enable the 5-hydroxymethylfurfural solution to undergo electrocatalytic oxidation reaction, so that maleic acid is obtained after the reaction is completed.
Specifically, the invention provides a method for preparing maleic acid by electrocatalytic oxidation, which comprises the steps of firstly preparing mesoporous oxide/carbon paper material, pretreating Nafion-117 ion exchange membrane, and then taking the mesoporous oxide/carbon paper material as a working electrode and H as a raw material 2 SO 4 The solution is the electrolyte of the cathode area, H 2 SO 4 The mixed solution of the solution and the 5-hydroxymethyl furfural solution is electrolyte of an anode region, an electrochemical catalytic reactor is formed together, and a pretreated Nafion-117 ion exchange membrane is used for separating the anode region from the cathode region so as to complete the assembly of the H-type electrolytic cell; after the assembly is completed, the H-shaped electrolytic cell is placed into a water bath kettle to be heated in a water bath, and voltage is applied to the H-shaped electrolytic cell, so that the 5-hydroxymethylfurfural solution is subjected to electrocatalytic oxidation reaction under a certain working voltage and current density, the 5-hydroxymethylfurfural solution in an anode region is oxidized into maleic acid, and hydrogen is generated in a cathode region. The invention prepares the maleic acid through electrocatalytic oxidation, and the electric energy can be converted based on renewable energy sources such as solar energy, wind energy and the like, thus being clean and sustainable energy sources with potential, leading the electrocatalytic energy to be driven by clean, environment-friendly and renewable electric energy without directly discharging pollutants, and being industrialThe technological process is environment friendly and simple, and has mild reaction condition, and compared with traditional thermodynamic control reaction, the technological process has the advantages of being capable of realizing more accurate control of the reaction process, improving the reaction selectivity, providing controllable electron transport by the electrocatalytic process, being beneficial to reducing the generation of side reactions, improving the reaction efficiency, obtaining the product of the oxidation process in situ by electrochemistry, realizing the high-efficiency utilization of 5-hydroxymethylfurfural, and generating high-value hydrogen. Compared with the traditional process, the preparation method provided by the invention has the advantages of high selectivity, high efficiency, greenness, no pollution, low cost, simplicity in operation and the like of the maleic acid, and has a wide application prospect.
In some possible embodiments, the preparing a mesoporous oxide/carbon paper material includes: preparing a mesoporous oxide material, adding the mesoporous oxide material into a beaker containing ethanol and Nafion solution, stirring to obtain uniform solution A, uniformly dripping the solution A on carbon paper, and airing the carbon paper at room temperature to obtain the mesoporous oxide/carbon paper material.
As will be appreciated by those skilled in the art, adding the mesoporous oxide material into a beaker containing ethanol and Nafion solution, stirring, dissolving the powdered catalyst mesoporous oxide material with ethanol, allowing the ethanol to evaporate rapidly, and allowing the Nafion solution to act as a binder, when solution a is applied dropwise to carbon paper, adhering the mesoporous oxide material to the carbon paper, and air drying to obtain the mesoporous oxide/carbon paper material of the carbon paper supported catalyst.
In some possible embodiments, the mesoporous oxide material comprises mesoporous scandium oxide, a mesoporous Kongnie composite oxide, a mesoporous Kongtie composite oxide, a mesoporous Konggu composite oxide, or a mesoporous Kongmeng composite oxide.
The mesoporous composite oxide is composed of mesoporous scandium oxide and one of scandium and transition metals such as nickel, iron, cobalt and manganese, has a stable mesoporous structure and a high specific surface area, can provide more active sites in the catalytic process, and can increase the contact range of the mesoporous scandium oxide and reactants, so that the catalytic activity is obviously improved, the mesoporous composite oxide can be used for electrocatalytic oxidation of 5-hydroxymethylfurfural, and is an efficient and low-cost electrocatalyst.
In some possible embodiments, the preparing a mesoporous oxide material includes: s101, preparing a mesoporous silica template; s102, dissolving 1g of nitrate hydrate in 12mL of ethanol to obtain a solution B, adding 0.5g of mesoporous silica template into the solution B, stirring, drying and grinding to obtain a metal nitrate@mesoporous silica compound; s103, calcining the metal nitrate@mesoporous silica composite at 550-650 ℃ for 2 hours to obtain a metal oxide@mesoporous silica composite; s104, adding the metal oxide@mesoporous silica compound into 50-100 mL of 1-2 mol/L sodium hydroxide solution, stirring at 70-90 ℃, cooling to room temperature after stirring, centrifuging and drying to obtain a precipitate; and S105, repeating the step S104 for three times on the precipitate to obtain the mesoporous oxide material.
Firstly, preparing a mesoporous silica template, then dissolving nitrate hydrate in ethanol to obtain a solution B, adding the mesoporous silica template into the solution B, stirring to enable the nitrate hydrate to fill the pore canal of the mesoporous silica template, drying and grinding to obtain a powdery metal nitrate@mesoporous silica compound, and facilitating subsequent reaction; calcining the metal nitrate@mesoporous silica composite at a high temperature to oxidize and decompose the nitrate into oxide, thereby obtaining a metal oxide@mesoporous silica composite; then adding the metal oxide@mesoporous silica composite into a sodium hydroxide solution, stirring at a certain temperature, cooling to room temperature, centrifuging and drying to obtain a precipitate, and reacting the silica with sodium hydroxide to remove the silica in the metal oxide@mesoporous silica composite; and finally repeating the step S104 for three times on the precipitate, so that the precipitate reacts with sodium hydroxide solution for multiple times to fully remove the silicon dioxide, and obtaining the mesoporous oxide material without the silicon dioxide. The mesoporous oxide material prepared by a template method has a larger specific surface area and rich pore channel structures, and can improve the electrocatalytic oxidation reaction efficiency of 5-hydroxymethylfurfural.
In some possible embodiments, the 5-hydroxymethylfurfural solution is prepared from biomass solid waste as a raw material. Specifically, the beta- (1, 4) glycosidic bond is broken to obtain glucose by hydrolyzing cellulose solid waste of agriculture and forestry biomass under an acidic condition, then the glucose is isomerized to convert polyhydroxy aldehyde into fructose with a polyhydroxy ketone structure, and 3 molecules of water of the fructose are removed to convert the fructose into 5-hydroxymethylfurfural solution.
The method is characterized in that the biomass solid waste is used as a raw material to prepare the 5-hydroxymethylfurfural solution, and the biomass solid waste can be recycled, so that a new way for high-value utilization of the biomass solid waste is provided, the raw material cost is reduced, the method is environment-friendly, and the method has great significance in developing the carbon circulation industry and supporting the double-carbon target.
In some possible embodiments, in step S2: in the H-type electrolytic cell, a reference electrode is Ag/AgCl, a counter electrode is a platinum wire, the concentration of the 5-hydroxymethylfurfural solution is 10 mmol/L-500 mmol/L, and the H is 2 SO 4 The concentration of the solution is 0.1mol/L to 2mol/L.
In some possible embodiments, in step S3: the temperature of the water bath heating is 25-300 ℃; the voltage is 1.6V-2V, and the time of the electrocatalytic oxidation reaction is 0.5 h-100 h.
In some possible embodiments, in step S1, the pre-treating the Nafion-117 ion exchange membrane comprises: nafion-117 membrane was placed in 3wt% H 2 O 2 Heating at 100deg.C for 1 hr, taking out Nafion-117 membrane, placing Nafion-117 membrane into deionized water, and heating at 100deg.C for 1 hr to remove residual H 2 O 2 And taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into 1mol/L sulfuric acid and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, and finally putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h to remove residual sulfuric acid.
In some possible embodiments, in step S1: the width of the carbon paper is 1 cm-3 cm, and the length of the carbon paper is 1 cm-3 cm.
In order to further describe the technical scheme of the present application in detail to support the technical problems to be solved by the present application, a specific example of a method for preparing maleic acid by using biomass solid waste electrocatalytic oxidation is described below, as in examples 2-7.
Example 2
This example prepares maleic acid by electrocatalytic oxidation by the following steps:
preparing a mesoporous scandium oxide/carbon paper material, and preprocessing a Nafion-117 ion exchange membrane to obtain the preprocessed Nafion-117 ion exchange membrane; in this embodiment, the mesoporous oxide/carbon paper material is a mesoporous scandium oxide/carbon paper material;
wherein, the preparation of the mesoporous scandium oxide/carbon paper material comprises the following steps: preparing a mesoporous scandium oxide material, adding 4mg of the mesoporous scandium oxide material into a beaker containing 900 mu L of ethanol and 100 mu L of Nafion solution, stirring to obtain solution A, dripping the solution A on carbon paper with the width of 1cm and the length of 2cm, and airing the carbon paper at room temperature to obtain the mesoporous scandium oxide/carbon paper material. The preparation of the mesoporous scandium oxide material comprises the following steps of; s101, preparing a mesoporous silica template; s102, dissolving 1g scandium nitrate hydrate in 12mL of ethanol to obtain a solution B, adding 0.5g of the mesoporous silica template into the solution B, stirring, drying and grinding to obtain a metal scandium nitrate@mesoporous silica compound; s103, calcining the metal scandium nitrate@mesoporous silica composite at 650 ℃ for 2 hours to obtain a metal scandium oxide@mesoporous silica composite; s104, adding the metal scandium oxide@mesoporous silica compound into 50mL of 2mol/L sodium hydroxide solution, fully stirring at 70 ℃, cooling to room temperature after stirring, centrifuging and drying to obtain a precipitate; and S105, repeating the step S104 for three times on the precipitate to obtain the mesoporous scandium oxide material. Pretreatment of Nafion-117 ion exchange membranes included: nafion-117 membrane was placed in 3wt% H 2 O 2 Heating at 100deg.C for 1 hr, taking out Nafion-117 membrane, and placing Nafion-117 membrane into deionized waterHeating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating is completed, putting the Nafion-117 membrane into 1mol/L sulfuric acid and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating is completed, and finally putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h to obtain the pretreated Nafion-117 ion exchange membrane.
An H-shaped electrolytic cell is assembled, wherein in the H-shaped electrolytic cell, a working electrode is made of mesoporous scandium oxide/carbon paper material, a reference electrode is Ag/AgCl, a counter electrode is a platinum wire, and electrolyte in a cathode area is 10mL of 1mol/L H 2 SO 4 Solution, electrolyte of anode region is 1mol/L H 2 SO 4 A mixed solution of the solution and 10mmol/L of the 5-hydroxymethylfurfural solution, wherein the volume of the mixed solution is 10mL, and the cathode area and the anode area are separated by the pretreated Nafion-117 ion exchange membrane; wherein the 5-hydroxymethylfurfural solution is commercially available;
after the assembly is completed, the H-shaped electrolytic cell is placed into a water bath kettle to be heated in a water bath at 60 ℃, and a voltage of 1.7V is applied to the H-shaped electrolytic cell, so that the 5-hydroxymethylfurfural solution is subjected to electrocatalytic oxidation reaction for 6 hours, and maleic acid is obtained after the reaction is completed.
Performance test:
carrying out cycle performance electrolysis test on 5-Hydroxymethylfurfural (HMF) by using a Gamry electrochemical workstation under the voltage of 1.70V by using a three-electrode system, and carrying out cycle electrolysis for 6 hours without replacing a working electrode in the electrolysis process; in the electrolysis process, when the electric charge quantity reaches 58C, the electrolyte in the anode region is taken out and diluted, a high performance liquid chromatography test is carried out, and the concentration of reactants and products in the solution is measured through a standard curve by using an external standard method, so that the yield of maleic acid and the Faraday efficiency of electrocatalytic reaction are respectively 94.2% and 90.4%, and the result shows that the mesoporous scandium oxide has excellent catalytic performance on HMF oxidation under the voltage.
Example 3
This example prepares maleic acid by electrocatalytic oxidation by the following steps:
preparation of mesoporous ScFeO 3 Carbon paperPretreating a Nafion-117 ion exchange membrane to obtain the pretreated Nafion-117 ion exchange membrane; in this embodiment, the mesoporous oxide/carbon paper material is mesoporous ScFeO 3 Carbon paper material;
wherein, the mesoporous ScFeO is prepared 3 The carbon paper material comprises: preparation of mesoporous ScFeO 3 Material, 4mg of the mesoporous ScFeO 3 Adding the material into a beaker containing 900 mu L of ethanol and 100 mu L of Nafion solution, stirring to obtain solution A, dripping the solution A on carbon paper with the width of 1cm and the length of 2cm, and airing the carbon paper at room temperature to obtain mesoporous ScFeO 3 Carbon paper material. The preparation of mesoporous ScFeO 3 The material comprises; s101, preparing a mesoporous silica template; s102, 1g scandium nitrate and ferric nitrate hydrate are dissolved in 12mL ethanol to obtain a solution B, 0.5g of the mesoporous silica template is added into the solution B, and the mixture is stirred, dried and ground to obtain ScFe (NO) 3 ) 6 A mesoporous silica composite; s103 the ScFe (NO) 3 ) 6 Calcining the mesoporous silica composite at 650 ℃ for 2 hours to obtain ScFeO 3 A mesoporous silica composite; s104, the ScFeO is processed 3 Adding 100mL of 1.5mol/L sodium hydroxide solution into the mesoporous silica compound, fully stirring at 80 ℃, cooling to room temperature after stirring, centrifuging and drying to obtain a precipitate; s105 repeating the step S104 for three times on the precipitate to obtain the mesoporous ScFeO 3 A material. Pretreatment of Nafion-117 ion exchange membranes included: nafion-117 membrane was placed in 3wt% H 2 O 2 Heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into 1mol/L sulfuric acid and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, and finally putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h to obtain the pretreated Nafion-117 ion exchange membrane.
Assembling an H-shaped electrolytic cell, wherein in the H-shaped electrolytic cell, a working electrode isMesoporous ScFeO 3 The carbon paper material, the reference electrode is Ag/AgCl, the counter electrode is a platinum wire, and the electrolyte in the cathode area is 10mL of 1mol/L H 2 SO 4 Solution, electrolyte of anode region is 1mol/L H 2 SO 4 A mixed solution of the solution and 10mmol/L of the 5-hydroxymethylfurfural solution, wherein the volume of the mixed solution is 10mL, and the cathode area and the anode area are separated by the pretreated Nafion-117 ion exchange membrane; wherein the 5-hydroxymethylfurfural solution is commercially available;
after the assembly is completed, the H-shaped electrolytic cell is placed into a water bath kettle to be heated in a water bath at 70 ℃, and a voltage of 1.7V is applied to the H-shaped electrolytic cell, so that the 5-hydroxymethylfurfural solution is subjected to electrocatalytic oxidation reaction for 8 hours, and maleic acid is obtained after the reaction is completed.
Performance test:
carrying out cycle performance electrolysis test on 5-hydroxymethylfurfural by using a Gamry electrochemical workstation under the voltage of 1.70V by using a three-electrode system, and carrying out cycle electrolysis for 8 hours without replacing a working electrode in the electrolysis process; in the electrolysis process, when the electric charge quantity reaches 58 ℃, the electrolyte in the anode region is taken out and diluted, high performance liquid chromatography test is carried out, and the concentration of reactants and products in the solution is measured through a standard curve by using an external standard method, so that the yield of the maleic acid and the Faraday efficiency of the electrocatalytic reaction are calculated to be 93.1 percent and 89.7 percent respectively, which shows that the mesoporous ScFeO under the voltage 3 Has excellent catalytic performance on HMF oxidation.
Example 4
This example prepares maleic acid by electrocatalytic oxidation by the following steps:
preparation of mesoporous ScMnO 3 Pretreating a Nafion-117 ion exchange membrane to obtain the pretreated Nafion-117 ion exchange membrane; in this embodiment, the mesoporous oxide/carbon paper material is mesoporous ScMnO 3 Carbon paper material;
wherein, the mesoporous ScMnO is prepared 3 The carbon paper material comprises: preparation of mesoporous ScMnO 3 Material, 4mg of the mesoporous ScMnO 3 The material was added to a volume of 900. Mu.L of ethyl acetateStirring alcohol and 100 mu L of Nafion solution in a beaker to obtain solution A, dripping the solution A on carbon paper with the width of 1cm and the length of 2cm, and airing the carbon paper at room temperature to obtain mesoporous ScMnO 3 Carbon paper material. Preparation of mesoporous ScMnO 3 The material comprises; s101, preparing a mesoporous silica template; s102, 1g of scandium nitrate and manganese nitrate hydrate are dissolved in 12mL of ethanol to obtain a solution B, 0.5g of the mesoporous silica template is added into the solution B, and the mixture is stirred, dried and ground to obtain ScMn (NO) 3 ) 6 A mesoporous silica composite; s103 the ScMn (NO 3 ) 6 Calcining the mesoporous silica composite at 650 ℃ for 2 hours to obtain ScMnO 3 A mesoporous silica composite; s104 the ScMnO 3 Adding the @ mesoporous silica compound into 50mL of 2mol/L sodium hydroxide solution, fully stirring at 70 ℃, cooling to room temperature after stirring, centrifuging, and drying to obtain a precipitate; s105 repeating the step S104 for three times on the precipitate to obtain the mesoporous ScMnO 3 A material. Pretreatment of Nafion-117 ion exchange membranes included: nafion-117 membrane was placed in 3wt% H 2 O 2 Heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into 1mol/L sulfuric acid and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, and finally putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h to obtain the pretreated Nafion-117 ion exchange membrane.
An H-shaped electrolytic cell is assembled, wherein in the H-shaped electrolytic cell, a working electrode is mesoporous ScMnO 3 The carbon paper material, the reference electrode is Ag/AgCl, the counter electrode is a platinum wire, and the electrolyte in the cathode area is 10mL of 1mol/L H 2 SO 4 Solution, electrolyte of anode region is 1mol/L H 2 SO 4 A mixed solution of the solution and 10mmol/L of the 5-hydroxymethylfurfural solution, wherein the volume of the mixed solution is 10mL, and the Nafion-117 ion exchange is carried out between the cathode region and the anode region after pretreatmentFilm changing and separating; wherein the 5-hydroxymethylfurfural solution is commercially available;
after the assembly is completed, the H-shaped electrolytic cell is placed into a water bath kettle to be heated in a water bath at 80 ℃, and a voltage of 1.8V is applied to the H-shaped electrolytic cell, so that the 5-hydroxymethylfurfural solution is subjected to electrocatalytic oxidation reaction for 12 hours, and maleic acid is obtained after the reaction is completed.
Performance test:
carrying out cycle performance electrolysis test on 5-hydroxymethylfurfural by using a Gamry electrochemical workstation under the voltage of 1.8V by using a three-electrode system, and carrying out cycle electrolysis for 12h without replacing a working electrode in the electrolysis process; in the electrolysis process, when the electric charge quantity reaches 58 ℃, the electrolyte in the anode region is taken out and diluted, high performance liquid chromatography test is carried out, and the concentration of reactants and products in the solution is measured through a standard curve by using an external standard method, so that the yield of the maleic acid and the Faraday efficiency of the electrocatalytic reaction are respectively 92.7 percent and 87.4 percent, which shows that the mesoporous ScMnO under the voltage 3 Has excellent catalytic performance on HMF oxidation.
Example 5
This example prepared maleic acid by electrocatalytic oxidation according to example 2, with the difference that the 5-hydroxymethylfurfural was prepared starting from fructose, and the rest of the steps were the same as in example 2.
Performance test:
carrying out cycle performance electrolysis test on 5-hydroxymethylfurfural by using a Gamry electrochemical workstation under the voltage of 1.7V by using a three-electrode system, and carrying out cycle electrolysis for 6 hours without replacing a working electrode in the electrolysis process; in the electrolysis process, when the electric charge quantity reaches 58C, the electrolyte in the anode region is taken out and diluted, a high performance liquid chromatography test is carried out, and the concentration of reactants and products in the solution is measured through a standard curve by using an external standard method, so that the yield of maleic acid and the Faraday efficiency of electrocatalytic reaction are respectively 90.5% and 85.7%, and the result shows that the mesoporous scandium oxide has excellent catalytic performance on the oxidation of HMF prepared by taking fructose as a raw material under the voltage.
Example 6
This example prepared maleic acid by electrocatalytic oxidation according to example 2, with the difference that the 5-hydroxymethylfurfural was prepared starting from glucose, and the rest of the steps were the same as in example 2.
Performance test:
carrying out cycle performance electrolysis test on 5-hydroxymethylfurfural by using a Gamry electrochemical workstation under the voltage of 1.7V by using a three-electrode system, and carrying out cycle electrolysis for 6 hours without replacing a working electrode in the electrolysis process; in the electrolysis process, when the electric charge quantity reaches 58C, the electrolyte in the anode region is taken out and diluted, a high performance liquid chromatography test is carried out, and the concentration of reactants and products in the solution is measured through a standard curve by using an external standard method, so that the yield of maleic acid and the Faraday efficiency of electrocatalytic reaction are respectively 91.8% and 87.1%, and the result shows that the mesoporous scandium oxide has excellent catalytic performance on the oxidation of HMF prepared by taking glucose as a raw material at the voltage.
Example 7
The embodiment is different from embodiment 2 in that the 5-hydroxymethylfurfural is prepared from wood chips, straws, wheat hulls and other agricultural and forestry biomass solid wastes as raw materials by electrocatalytic oxidation according to the method of embodiment 2, and the rest steps are the same as those of embodiment 2.
Performance test:
carrying out cycle performance electrolysis test on 5-hydroxymethylfurfural by using a Gamry electrochemical workstation under the voltage of 1.7V by using a three-electrode system, and carrying out cycle electrolysis for 6 hours without replacing a working electrode in the electrolysis process; in the electrolysis process, when the electric charge quantity reaches 58 ℃, the electrolyte in the anode region is taken out and diluted, a high performance liquid chromatography test is carried out, the concentration of reactants and products in the solution is measured through a standard curve by using an external standard method, and the yield of maleic acid and the Faraday efficiency of electrocatalytic reaction are respectively 89.3% and 84.2%, which show that mesoporous scandium oxide has excellent catalytic performance on HMF oxidation prepared by taking wood chips, straws, wheat husks and other agricultural and forest biomass solid wastes as raw materials.
In summary, compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The mesoporous metal oxide material prepared by a template method has larger specific surface area and rich pore canal structure by adopting mesoporous silicon dioxide as a template. In the catalytic process, the material can provide more active sites and increase the contact range between the material and reactants, so that the catalytic activity is obviously improved, and an efficient and low-cost electrocatalyst is provided for electrocatalytically oxidizing HMF.
(2) The mesoporous metal oxide electrocatalyst provided by the invention is an efficient catalyst and can be used for the oxidation reaction of electrocatalytic HMF. Compared with the traditional Oxygen Evolution Reaction (OER), the electrocatalyst needs lower potential under the same current density, shows good HMF catalytic effect, and realizes 70% maleic acid yield and Faraday efficiency.
(3) The preparation method of the material provided by the invention is simple and feasible, the required raw materials are easy to obtain, and the preparation process is environment-friendly. In the technical field of electrocatalytic oxidation of 5-hydroxymethylfurfural, the method has remarkable application value and wide application prospect, and is suitable for industrial production.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A process for preparing maleic acid by electrocatalytic oxidation, said process comprising:
s1, preparing a mesoporous oxide/carbon paper material, and preprocessing a Nafion-117 ion exchange membrane to obtain the preprocessed Nafion-117 ion exchange membrane;
s2 assembling an H-shaped electrolytic cell, wherein in the H-shaped electrolytic cell, a working electrode is made of the mesoporous oxide/carbon paper material, and electrolyte in a cathode area is H 2 SO 4 Solution, electrolyte of anode region is H 2 SO 4 The mixed solution of the solution and the 5-hydroxymethylfurfural solution is characterized in that the cathode area and the anode area are separated by the pretreated Nafion-117 ion exchange membrane;
and S3, after the assembly is completed, placing the H-shaped electrolytic cell into a water bath kettle for water bath heating, and applying voltage to the H-shaped electrolytic cell to enable the 5-hydroxymethylfurfural solution to undergo electrocatalytic oxidation reaction, so that maleic acid is obtained after the reaction is completed.
2. The method for preparing maleic acid by electrocatalytic oxidation of biomass solid waste according to claim 1, wherein the preparing mesoporous oxide/carbon paper material comprises:
preparing a mesoporous oxide material, adding the mesoporous oxide material into a beaker containing ethanol and Nafion solution, stirring to obtain solution A, dripping the solution A on carbon paper, and then airing the carbon paper at room temperature to obtain the mesoporous oxide/carbon paper material.
3. The method for preparing maleic acid by utilizing biomass solid waste electrocatalytic oxidation according to claim 2, wherein the method comprises the following steps:
the mesoporous oxide material comprises mesoporous scandium oxide, mesoporous Kongnie composite oxide, mesoporous Kongtie composite oxide, mesoporous Konggu composite oxide or mesoporous Kongmeng composite oxide.
4. The method for preparing maleic acid by electrocatalytic oxidation of biomass solid waste as set forth in claim 3, wherein the preparing mesoporous oxide material comprises:
s101, preparing a mesoporous silica template;
s102, dissolving 1g of nitrate hydrate in 12mL of ethanol to obtain a solution B, adding 0.5g of mesoporous silica template into the solution B, stirring, drying and grinding to obtain a metal nitrate@mesoporous silica compound;
s103, calcining the metal nitrate@mesoporous silica composite at 550-650 ℃ for 2 hours to obtain a metal oxide@mesoporous silica composite;
s104, adding the metal oxide@mesoporous silica compound into 50-100 mL of 1-2 mol/L sodium hydroxide solution, stirring at 70-90 ℃, cooling to room temperature after stirring, centrifuging and drying to obtain a precipitate;
and S105, repeating the step S104 for three times on the precipitate to obtain the mesoporous oxide material.
5. The method for preparing maleic acid by utilizing biomass solid waste electrocatalytic oxidation according to claim 4, wherein the method comprises the following steps:
the 5-hydroxymethylfurfural solution is prepared from biomass solid waste serving as a raw material.
6. The method for preparing maleic acid by electrocatalytic oxidation of solid waste biomass as set forth in claim 5, wherein in step S2:
in the H-type electrolytic cell, a reference electrode is Ag/AgCl, a counter electrode is a platinum wire, the concentration of the 5-hydroxymethylfurfural solution is 10 mmol/L-500 mmol/L, and the H is 2 SO 4 The concentration of the solution is 0.1mol/L to 2mol/L.
7. The method for preparing maleic acid by electrocatalytic oxidation of solid waste of biomass as set forth in claim 6, wherein in step S3:
the temperature of the water bath heating is 25-300 ℃.
8. The method for preparing maleic acid by electrocatalytic oxidation of solid waste of biomass as set forth in claim 7, wherein in step S3:
the voltage is 1.6V-2V, and the time of the electrocatalytic oxidation reaction is 0.5 h-100 h.
9. The method for preparing maleic acid by electrocatalytic oxidation of solid waste biomass as set forth in claim 8, wherein the pretreatment of Nafion-117 ion exchange membrane in step S1 comprises:
nafion-117 membrane was placed in 3wt% H 2 O 2 And heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, putting the Nafion-117 membrane into 1mol/L sulfuric acid and heating at 100 ℃ for 1h, taking out the Nafion-117 membrane after heating, and finally putting the Nafion-117 membrane into deionized water and heating at 100 ℃ for 1h.
10. The method for preparing maleic acid by electrocatalytic oxidation of solid waste biomass as set forth in claim 9, wherein in step S1:
the width of the carbon paper is 1 cm-3 cm, and the length of the carbon paper is 1 cm-3 cm.
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