CN114574881A - Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances - Google Patents
Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances Download PDFInfo
- Publication number
- CN114574881A CN114574881A CN202210222136.1A CN202210222136A CN114574881A CN 114574881 A CN114574881 A CN 114574881A CN 202210222136 A CN202210222136 A CN 202210222136A CN 114574881 A CN114574881 A CN 114574881A
- Authority
- CN
- China
- Prior art keywords
- alditol
- carbon felt
- electrocatalytic oxidation
- oxidation
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 47
- 230000003647 oxidation Effects 0.000 title claims abstract description 46
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 32
- 150000005846 sugar alcohols Chemical class 0.000 title claims abstract description 32
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 239000002253 acid Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 nitroxide free radical compound Chemical class 0.000 claims abstract description 37
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 43
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 33
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 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 description 28
- 239000008103 glucose Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052753 mercury Inorganic materials 0.000 claims description 14
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 14
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002484 cyclic voltammetry Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 8
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 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 description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- UXBLSWOMIHTQPH-UHFFFAOYSA-N 4-acetamido-TEMPO Chemical group CC(=O)NC1CC(C)(C)N([O])C(C)(C)C1 UXBLSWOMIHTQPH-UHFFFAOYSA-N 0.000 claims description 3
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 3
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims description 3
- 206010056474 Erythrosis Diseases 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- OCIQOBBYJWEKSA-UHFFFAOYSA-N 1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidine-4-carbonitrile Chemical group CC1(C)CC(C#N)CC(C)(C)N1[O] OCIQOBBYJWEKSA-UHFFFAOYSA-N 0.000 claims description 2
- XUXUHDYTLNCYQQ-UHFFFAOYSA-N 4-amino-TEMPO Chemical group CC1(C)CC(N)CC(C)(C)N1[O] XUXUHDYTLNCYQQ-UHFFFAOYSA-N 0.000 claims description 2
- CYQGCJQJIOARKD-UHFFFAOYSA-N 4-carboxy-TEMPO Chemical group CC1(C)CC(C(O)=O)CC(C)(C)N1[O] CYQGCJQJIOARKD-UHFFFAOYSA-N 0.000 claims description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims description 2
- WSGDRFHJFJRSFY-UHFFFAOYSA-N 4-oxo-TEMPO Chemical group CC1(C)CC(=O)CC(C)(C)N1[O] WSGDRFHJFJRSFY-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 6
- 230000003213 activating effect Effects 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 abstract description 29
- 239000002028 Biomass Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 238000005575 aldol reaction Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 49
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 239000002243 precursor Substances 0.000 description 18
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 12
- 230000004913 activation Effects 0.000 description 12
- 239000000174 gluconic acid Substances 0.000 description 12
- 235000012208 gluconic acid Nutrition 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000003011 anion exchange membrane Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 238000004811 liquid chromatography Methods 0.000 description 9
- 239000002135 nanosheet Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229940097043 glucuronic acid Drugs 0.000 description 4
- 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 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OIYFAQRHWMVENL-UHFFFAOYSA-N 2-(4-oxopyran-3-yl)acetic acid Chemical compound OC(=O)CC1=COC=CC1=O OIYFAQRHWMVENL-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical group 0.000 description 2
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical class [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- QKXWNEXHGMFIGB-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(C(O)=O)CC(C)(C)N1 QKXWNEXHGMFIGB-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- 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
- 229910002545 FeCoNi Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 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 1
- 239000005715 Fructose Substances 0.000 description 1
- 229910002640 NiOOH Inorganic materials 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
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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Abstract
A process for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substance includes such steps as loading transition metal on carbon felt as anode, loading platinum plate as cathode, separating two electrodes of electrolytic cell by anionic membrane to form electrocatalytic reactor, and electrocatalytic oxidation of alditol substance by DC low voltage in electrolyte containing nitroxide free radical compound or its derivative, alditol substance and inorganic salt. Compared with the existing strong base electrocatalysis system, the system can effectively reduce the occurrence of side reactions such as aldol reaction and the like under mild conditions of weak base, obviously improve the selectivity of glucaric acid, and simultaneously co-produce hydrogen, and has universality in the aspect of molecular oxidation of alditol biomass.
Description
Technical Field
The invention relates to the field of organic electrochemical catalysis, in particular to a method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances.
Background
The biomass resource with high oxygen content is an ideal raw material for preparing oxygenated chemicals. Among them, cellulose has a very important position in the field of catalytic conversion of biomass. Based on the hydrolysis of cellulose to prepare glucose, the glucose is oxidized to prepare glucaric acid through gluconic acid, and then the glucaric acid is subjected to hydrogenolysis to prepare the important chemical raw material adipic acid, so that the method is a conversion path with economic benefits. Furthermore, 5-Hydroxymethylfurfural (HMF) is a platform chemical prepared by acid-catalyzed dehydration of glucose or fructose or hydrolysis-dehydration of polysaccharides. The hydroxyl or aldehyde group on HMF is oxidized to produce valuable chemicals, especially 2, 5-furandicarboxylic acid (FDCA), which is considered to be a replacement for terephthalic acid in synthetic polymeric materials due to its structure and properties similar to terephthalic acid. And similarly, the preparation of the xylaric acid by oxidizing xylose and the preparation of the glyceric acid by oxidizing glycerol have great application prospects.
In order to realize the core purpose of preparing polybasic acid by the oxidation of the biomass molecules, the common point is that the selective oxidation of aldehyde functional groups and hydroxyl functional groups is required to be realized, so a set of oxidation scheme for preparing polybasic carboxylic acid with high selectivity is required to be designed.
However, the existing method for preparing polycarboxylic acid has the problems of low selectivity, complex side reaction and the like. The production of glucaric acid from glucose is taken as an example. The existing methods for producing glucaric acid comprise a microbial fermentation method and a chemical oxidation method, wherein the microbial fermentation method has the defects of long fermentation time (more than 2 days), low selectivity (the yield of glucaric acid is less than 20%), difficulty in separating products (a large amount of microbial biomass and hundreds of byproducts with similar properties are produced together), and the like.
The chemical oxidation method is used for producing the grapeThe main industrial method for glucaric acid, chemical oxidation, is either with HNO in the absence of a catalyst3Stoichiometric oxidation of glucose, either by O in the presence of noble metals (e.g., Au, Pt, Pd and Ru) at 45-120 deg.C2(air) catalytic oxidation of glucose. For example, one or more of these studies glucose oxidation on an Au-based catalyst at 120 ℃ and 0.3MPa of oxygen produced 92% gluconic acid and less than 5% glucaric acid. Gold et al reported that a bimetallic PtCu catalyst oxidizes glucose to glucaric acid at 45 ℃ and 0.1MPa oxygen with a yield of 45%. The traditional glucose catalytic oxidation for preparing glucaric acid has several disadvantages: (1) large amounts of toxic oxidizing agents (more than twice the stoichiometric ratio) are required; (2) the selectivity to glucaric acid is low (glucaric acid selectivity is less than 60%); (3) various by-products of similar chemical nature are produced (e.g. tartaric acid, glycolic acid, tartronic acid and oxalic acid); (4) using high pressure oxygen, hiding safety risks; (5) the scarcity of noble metal (e.g., Pt, Ru, Rh, and Pd) based catalysts presents a high cost. Therefore, the development of a green and efficient preparation method of the glucaric acid has important application value.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances, which takes glucose as a representative compound, couples a transition metal-based catalyst with a nitroxide free radical compound, and performs electrooxidation on the glucose at an anode to realize high-selectivity preparation of glucaric acid, and simultaneously performs high-efficiency hydrogen evolution at a cathode. The system of the invention has the advantages of mild reaction conditions, normal temperature and pressure, extremely high catalytic efficiency, simple operation, low raw material cost, low reaction energy consumption and the like, and has industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing polycarboxylic acid by electrocatalytic oxidation of alditol includes such steps as loading transition metal on carbon felt as anode, loading platinum plate as cathode, separating two electrodes of electrolytic cell by anionic membrane to form electrocatalytic reactor, and electrocatalytic oxidation of alditol by DC low-voltage in the presence of electrolyte containing nitroxide free radical compound or its derivative, alditol substance and inorganic salt.
The preparation method of the transition metal loaded carbon felt comprises the following steps: dissolving urea and nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment, then adding the pretreated carbon felt, performing hydrothermal reaction, keeping the temperature for a certain time at a certain temperature, taking out, washing with ethyl alcohol and water in sequence, and finally drying and calcining.
The method for treating the pretreated carbon felt comprises the following steps: the carbon felt is sequentially subjected to ultrasonic treatment under absolute ethyl alcohol and distilled water to remove surface impurities, then the carbon felt is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, a NaOH solution is used as an electrolyte, a timed potential method is adopted for oxidation treatment, and after the treatment is finished, the carbon felt is subjected to ultrasonic washing with a large amount of distilled water to remove residual NaOH.
The certain temperature is 150-200 ℃, the certain time is 12-24 hours, and the calcining temperature is 300-500 ℃; the molar ratio of the urea to the nitrate is 1: 1-1: 5.
The transition metal comprises at least one of Fe, Co, Ni, Cu, Zn and Mn.
The nitroxide free radical or the derivative thereof comprises at least one of 2,2,6, 6-tetramethylpiperidine 1-oxyl, 4-oxo-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 4-amino-2, 2,6, 6-tetramethylpiperidine 1-oxyl, 4-cyano-2, 2,6, 6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl, 4-carboxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl and 4-acetamido-2, 2,6, 6-tetramethylpiperidine 1-oxyl free radical.
The alditol substances include at least one of glucose, 5-hydroxymethylfurfural, xylose, cellulose, hemicellulose, erythrose, glycerol and glycolaldehyde.
The concentration of the alditol substances is 10-2000 mmol/L, and the molar ratio of the nitroxide free radical compound or the derivative thereof to the alditol substances is 1: 10-1: 1000.
The inorganic salt comprises at least one of sodium hydroxide, potassium hydroxide, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium carbonate and sodium bicarbonate, and the concentration of the electrolyte is 0.1-1 mol/L.
The transition metal-loaded carbon felt needs to be activated in a reaction system before use, and the activation treatment comprises the following steps: taking a carbon felt loaded with transition metal as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode, and Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50-100 times, and the scanning frequency is 50-100 mV s-1。
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the invention can realize the regulation of the respective yields of the gluconic acid and the glucaric acid by coupling the two catalysts under the condition that the total yields of the products of the gluconic acid and the glucaric acid are not changed (> 91%). The transition metal loaded carbon felt catalyst oxidizes glucose to generate gluconic acid, and the gluconic acid is further oxidized to glucaric acid under the action of the nitroxide radical or the derivative catalyst thereof, so that the aim of regulating and controlling the respective yields of the gluconic acid and the glucaric acid is fulfilled.
2. The transition metal-loaded carbon felt is prepared by in-situ growth by a hydrothermal method, for example, spherical FeOx metal nanoparticles are grown and loaded on carbon felt CF, and the catalyst has the advantages of simple preparation process, low preparation cost, simple and easily-controlled catalytic system, extremely high catalytic efficiency and easy industrialization.
3. The transition metal loaded carbon felt catalyst prepared by the invention has the advantages of large specific surface area of a multi-stage structure, more active sites, excellent conductivity of the carbon felt, contribution to charge transfer, enhanced catalytic efficiency, oxidation resistance, corrosion resistance and excellent stability.
4. The catalytic system can be carried out at normal temperature and low voltage, the requirements of the traditional process on the equipment of reaction temperature and pressure are not needed, and the process is simpler.
Drawings
FIG. 1 is a schematic structural diagram of the apparatus of the present invention.
FIG. 2 is a product distribution diagram of an electrocatalytic system containing nitroxyl radical compounds only.
Fig. 3 is a product distribution diagram of an electrocatalytic system with only transition metal LDH nanosheets.
FIG. 4 is a product distribution diagram of a coupled electrocatalytic system containing noble metal and nitroxide radical compounds.
FIG. 5 is a product distribution diagram of an electrocatalytic system with separation of transition metal and nitroxide free radical compounds.
Fig. 6 is SEM images of carbon felt-supported transition metal Ni LDH (a, b), and before (c) and after (d) reaction thereof.
FIG. 7 shows a carbon felt (a) and a carbon felt-supported transition metal precursor Ni (OH)2(b) XRD patterns of Ni-CF before (c) reaction, after (d) reaction and after (e) regeneration.
FIG. 8 is a cyclic voltammogram of a TEMPO, carbon felt supported transition metal Ni-CF, Ni-CF and TEMPO coupling system.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
As shown in figure 1, the electrocatalytic reaction uses an H-type two-chamber electrochemical electrolytic cell, the two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation to be used as a power supply and a test instrument, a carbon felt loaded with transition metal is used as an anode and fixed in an anode chamber, a platinum sheet electrode is used as a cathode and fixed in a cathode chamber, and under an anode chamber electrolyte containing a nitroxide free radical compound or a derivative thereof, alditol substances and inorganic salts, the terminal aldehyde group and hydroxyl group of the alditol substances are catalytically oxidized step by using two combined catalysts in the system through direct current low voltage, so that polycarboxylic acid is prepared with high selectivity, and hydrogen is co-produced by the cathode.
Embodiment 1 a method for constructing an electrocatalysis system coupling Fe LDH nanosheet and nitroxide radical compound for preparing polyacids by biomass oxidation.
Pretreating a carbon felt: carrying out ultrasonic treatment on a commercial carbon felt for 4min under absolute ethyl alcohol and distilled water in sequence, washing to remove surface impurities, then carrying out oxidation treatment by adopting a timed potentiometric method by taking the carbon felt as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and a 1M NaOH solution as an electrolyte, and after the treatment is finished, carrying out ultrasonic washing on the carbon felt for 30min by using a large amount of distilled water to remove residual NaOH. The potential of the chronopotentiometry is 1.9V (vs. RHE), and the processing time is 10 min.
Dissolving 0.2g of urea and 0.1g of ferric nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment for 10min, and uniformly mixing to obtain a yellow clear solution. Transferring the solution to a polytetrafluoroethylene lining, putting a piece of pretreated carbon felt, sealing in a hydrothermal autoclave, and keeping the temperature at 150 ℃ for 12 hours. Cooling, washing with ethanol and distilled water for multiple times in sequence to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, and raising the temperature to 300 ℃ at a rate of 5 ℃/min in air atmosphere and keeping for 4h to obtain the final Fe2O3-a CF catalyst. Said Fe2O3-CF catalyst of Fe2O3Is spherical, and grows uniformly and compactly on the carbon felt substrate.
Before the catalyst is used in its entirety, it is necessary to perform an activation treatment in the reaction system. Said Fe2O3Before and after 1000 CV cycles of the CF catalyst cyclic voltammetry, no obvious change is found in the polarization curve of the material, which indicates that the catalyst has good stability.
The Fe prepared above is added2O3the-CF is coupled with 4-acetamido-2, 2,6, 6-tetramethylpiperidine 1-oxyl radical (ACT) to construct a catalytic system for preparing glucaric acid. The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, Fe2O3the-CF catalyst is used as a working electrode and is fixed in the anode chamber, and the electrolyte of the anode chamber is 0.1M Na2CO3A mixture of 0.1mM ACT and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Formal formBefore reaction, Fe2O3the-CF catalyst is subjected to an activation treatment. With Fe2O3-CF as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1。
When the product is analyzed by liquid chromatography, the glucose conversion rate in example 1 reaches 97.6%, the glucaric acid yield is 82.1%, and the faradaic efficiency can reach 79.3%.
Dissolving 1g of urea and 1g of nickel nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment for 10min, and uniformly mixing to obtain a green clear solution. Transferring the solution into a polytetrafluoroethylene lining, putting a carbon felt, sealing in a hydrothermal autoclave, and keeping the temperature at 160 ℃ for 16 h. And after cooling, washing the precursor with ethanol and distilled water for multiple times in sequence to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, and carrying out temperature programming to 400 ℃ at the speed of 5 ℃/min in air atmosphere and keeping the temperature for 4h to obtain the final NiO-CF catalyst. Before the catalyst is used in its entirety, it is necessary to perform an activation treatment in the reaction system.
And (3) coupling the NiO-CF prepared by the method with 4-acetamido-2, 2,6, 6-tetramethylpiperidine 1-oxyl free radical (ACT) to construct a catalytic system for preparing the glucaric acid. The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, NiO-CF catalyst is used as working electrode, and fixed in anode chamber, electrolyte of anode chamber is 0.1M Na2CO3A mixture of 0.1mM ACT and 200mM glucose; the reference electrode and the counter electrode are fixed in the cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before the formal reaction, the NiO-CF catalyst needs to be activated. NiO-CF is taken as a working electrode, a platinum sheet is taken as a counter electrode, a mercury/mercury oxide electrode is taken as a reference electrode,0.1M Na2CO3the solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1。
The liquid chromatography analysis of the product shows that the conversion rate of glucose in example 2 reaches 98.1%, the yield of glucaric acid is 83.7%, and the faradic efficiency can reach 81.3%.
Dissolving 1.5g of urea and 1g of cobalt nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment for 10min, and uniformly mixing to obtain a red clear solution. Transferring the solution to a polytetrafluoroethylene lining, putting a carbon felt, sealing in a hydrothermal autoclave, and keeping the temperature at 170 ℃ for 20 h. Cooling, washing with ethanol and distilled water for multiple times to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, and raising the temperature to 450 ℃ at a rate of 5 ℃/min in air atmosphere and keeping the temperature for 4h to obtain the final Co3O4-a CF catalyst. Before the catalyst is used in its entirety, it is necessary to perform an activation treatment in the reaction system.
Mixing the above Co3O4-CF is coupled with 2,2,6, 6-tetramethylpiperidine 1-oxyl (TEMPO) to construct an electrocatalytic system. The system uses H-type electrochemical electrolytic cell with two chambers separated by anion exchange membrane, and a lead connected with electrochemical workstation as power supply and test instrument, and Co3O4the-CF catalyst is used as a working electrode and is fixed in the anode chamber, and the electrolyte of the anode chamber is 0.1M Na2CO3A mixture of 0.1mM TEMPO and 500mM xylose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before the formal reaction, Co3O4the-CF catalyst is subjected to an activation treatment. With Co3O4-CF as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, 0.1M Na2CO3The solution is electrolyte solution, and is activated by cyclic voltammetryThe bit range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1。
The liquid chromatography analysis of the product shows that the xylose conversion rate in example 3 reaches 98.6%, the yield of the xylaric acid is 89.7%, and the faradic efficiency can reach 86.4%.
Embodiment 4 method for constructing electrocatalysis system by coupling Cu LDH nanosheet and nitroxide free radical compound for preparing polyacid through biomass oxidation
Dissolving 2g of urea and 2g of copper nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment for 10min, and uniformly mixing to obtain a blue clear solution. Transferring the solution to a polytetrafluoroethylene lining, putting a carbon felt, sealing in a hydrothermal autoclave, and keeping the temperature at 180 ℃ for 24 hours. Cooling, washing with ethanol and distilled water for multiple times in sequence to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, and carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min in the air atmosphere and keeping for 2h to obtain the final CuO-CF catalyst. Before the catalyst is used in its entirety, it is necessary to perform an activation treatment in the reaction system.
The CuO-CF prepared by the method is coupled with 4-carboxyl-2, 2,6, 6-tetramethylpiperidine 1-oxyl free radical (CBT) to construct an electrocatalytic system. The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, CuO-CF catalyst is used as working electrode, and fixed in anode chamber, electrolyte of anode chamber is 0.1M Na2CO3A mixture of 1mM CBT and 1000mM 5-Hydroxymethylfurfural (HMF); the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before the formal reaction, the CuO-CF catalyst needs to be activated. Using CuO-CF as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1。
The product was analyzed by liquid chromatography, and in example 4, the conversion of HMF was 99.4%, the yield of FDCA was 96.8%, and the faradaic efficiency was 92.9%.
Embodiment 5 method for constructing coupled electrocatalysis system of FeCoNi LDHs nanosheet and nitroxide free radical compound for preparing polybasic acid by biomass oxidation
Dissolving 2g of urea, 1g of ferric nitrate, 1g of cobalt nitrate and 1g of nickel nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment for 10min, and uniformly mixing to obtain a red clear solution. Transferring the solution to a polytetrafluoroethylene lining, putting a carbon felt, sealing in a hydrothermal autoclave, and keeping the temperature at 190 ℃ for 24 hours. Cooling, washing with ethanol and distilled water for multiple times in sequence to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, and carrying out temperature programming at a speed of 5 ℃/min to 500 ℃ in air atmosphere and keeping for 2h to obtain the final FeCoNiOx-a CF catalyst. Before the catalyst is used in its entirety, it is necessary to perform an activation treatment in the reaction system.
FeCoNiO prepared by the methodx-CF is coupled with 4-acetamido-2, 2,6, 6-tetramethylpiperidine 1-oxyl radical (ACT) to construct an electrocatalytic system. The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, FeCoNiOxthe-CF catalyst is used as a working electrode and is fixed in the anode chamber, and the electrolyte of the anode chamber is 0.1M Na2CO3A mixture of 2mM ACT and 1000mM xylose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). FeCoNiO before formal reactionxthe-CF catalyst is subjected to an activation treatment. With FeCoNiOx-CF as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1。
The liquid chromatography analysis of the product shows that the xylose conversion rate in example 5 reaches 98.9%, the yield of the xylaric acid is 91.2%, and the Faraday efficiency can reach 86.7%.
Comparative example 1 electrocatalytic System containing nitroxyl radical Compounds alone
The electrocatalysis system only contains nitroxyl free radical compound, the system uses H-type two-chamber electrochemical electrolytic cell, the two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, carbon felt is used as working electrode and fixed in anode chamber, electrolyte of anode chamber is 0.1M Na2CO3A mixture of 1mM TEMPO and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before formal reaction, the carbon felt needs to be activated. Using carbon felt as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1The product was then subjected to liquid chromatography.
As shown in FIG. 2, this comparative example adjusted the molar ratio of TEMPO to glucose and examined the effect of TEMPO on the reaction. The product distribution is shown in fig. 2, the final product of the electrocatalytic reaction system only containing the nitroxyl radical compound mainly comprises gluconic acid and byproducts, and the final glucaric acid selectivity under the reaction system is not high.
Comparative example 2 electrocatalytic system with only transition metal LDH nanosheets
An electrocatalytic system containing only transition metal LDH nanosheets (M-CF). The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, M-CF is used as working electrode, and fixed in anode chamber, electrolyte of anode chamber is 0.1M Na2CO3And 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before the formal reaction, M-CF is subjected to activation treatment. M-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, wherein the potential range is 0.7-1.7V (vs) 50 times of circulation and 50mV s of scanning frequency-1The product was then subjected to liquid chromatography.
As shown in FIG. 3, this comparative example was also examined for the influence of different metals on the reaction. The product distribution is shown in figure 3, the transition metal LDH nanosheet (M-CF) can selectively oxidize aldehyde groups to an intermediate product gluconic acid, so that the final product of the reaction system is mainly gluconic acid. However, the effect of the oxidation of hydroxyl groups is poor, so glucaric acid is hardly obtained in the end of the reaction system.
Comparative example 3 coupled electrocatalytic system containing noble metal and nitroxide radical compound
A coupled electrocatalytic system comprising a noble metal and a nitroxyl radical compound. The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, M-CF is used as working electrode, and fixed in anode chamber, electrolyte of anode chamber is 0.1M Na2CO3A mixture of 1mM TEMPO and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before the formal reaction, M-CF is subjected to activation treatment. M-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1The product was then subjected to liquid chromatography.
The product distribution is shown in FIG. 4. first, the selective oxidation of glucose by noble metal catalyst (M-CF) alone is weak, and glucaric acid is hardly obtained. Secondly, after the noble metal catalyst (M-CF) is coupled with the nitroxide free radical compound, the coupling ratio of the noble metal catalyst (M-CF) and the nitroxide free radical compound is not obviously improved compared with a sole nitroxide free radical compound system, so that the coupling ratio of the noble metal catalyst (M-CF) and the nitroxide free radical compound cannot be used for preparing glucaric acid through high-selectivity oxidation.
Example 6 electrocatalytic System with separation of transition Metal and nitroxide free radical Compounds
Containing transition metals (e.g. Ni)) And nitroxide free radical compounds (TEMPO for example). The system uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, the wire is connected with electrochemical workstation as power supply and test instrument, M-CF is used as working electrode, and fixed in anode chamber, electrolyte of anode chamber is 0.1M Na2CO3A mixture of 0 or 1mM TEMPO and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte of the cathode chamber is 0.1M Na2CO3An aqueous solution of (a). Before the formal reaction, M-CF is subjected to activation treatment. M-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50 times, and the scanning frequency is 50mV s-1。
The product was analyzed by liquid chromatography and the product distribution was as shown in FIG. 5. Firstly, only adding a transition metal catalyst before reacting for 60min, and as can be seen from the figure, gradually converting glucose into an intermediate product gluconic acid; then, after 60min, taking out the transition metal catalyst and adding a nitroxide free radical compound, so that the gluconic acid gradually begins to convert to the glucuronic acid; finally, a transition metal catalyst is added after 120min, and the conversion of glucuronic acid to glucaric acid gradually starts.
The results prove that the transition metal catalyst can promote the oxidation reaction of aldehyde groups in glucose and glucuronic acid, the nitroxide free radical compound can accelerate the oxidation of C6 hydroxyl at the terminal position of the glucuronic acid, and the aldehyde group and the hydroxyl are cooperatively accelerated to be selectively oxidized, so that the occurrence of side reactions is reduced, and the glucaric acid can be prepared by high-selectivity oxidation.
Fig. 6 is SEM images of carbon felt-supported transition metal Ni LDH (a, b), and before (c) and after (d) the reaction, and it can be seen that the morphology of the carbon felt-supported transition metal catalyst is not changed much before and after the reaction, and the morphology of the catalyst is relatively stable.
FIG. 7 shows a carbon felt (a) loaded with a transition metal precursor Ni (OH)2(b) XRD patterns of Ni-CF before reaction (c), after reaction (d) and after regeneration (e) were observed before reactionAnd then, the surface of the carbon felt-loaded transition metal catalyst is reconstructed after reaction, so that the bulk phase part of the catalyst is changed, and the crystal form of the catalyst is recovered after the catalyst is reconstructed.
FIG. 8 is a cyclic voltammogram (CV diagram, sweep rate 10mV s) of a coupled system of TEMPO, carbon felt-supported transition metal Ni-CF, Ni-CF and TEMPO-1). As can be seen from the CV diagram, the oxidation capacity of the Ni and TEMPO coupling system is enhanced, and the oxidation process of Ni is probably related to the production of trivalent Ni species NiOOH to promote TEMPO circulation.
The invention couples a transition metal-based catalyst with a nitroxide radical compound to construct a set of electrocatalysis system for preparing polycarboxylic acid by oxidizing biomass with high selectivity. Realize the selective electrooxidation of various alditol substances, including glucose, 5-hydroxymethyl furfural, xylose, cellulose, hemicellulose, erythrose, glycerol, glycolaldehyde and other compounds. The invention takes glucose as a representative compound as a reactant of the system, and obtains glucaric acid with high yield. The system has the obvious advantages of mild reaction conditions, extremely high catalytic efficiency, universality in the aspect of aldehyde alcohol biomass molecular oxidation, environmental friendliness and the like.
Claims (10)
1. A method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances is characterized by comprising the following steps: the preparation method comprises the steps of taking a carbon felt loaded with transition metal as an anode, taking a platinum sheet electrode as a cathode, separating two electrodes of an electrolytic cell by an anion membrane to form an electrocatalytic reactor, and preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances through direct current low voltage under an electrolyte containing nitroxide free radical compounds or derivatives thereof, alditol substances and inorganic salts.
2. The method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol as recited in claim 1, wherein said transition metal loaded carbon felt is prepared by: dissolving urea and nitrate in deionized water, adding absolute ethyl alcohol, stirring, performing ultrasonic treatment, then adding the pretreated carbon felt, performing hydrothermal reaction, keeping the temperature for a certain time at a certain temperature, taking out, washing with ethyl alcohol and water in sequence, and finally drying and calcining.
3. The method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol as recited in claim 2, wherein said pre-treated carbon felt is treated by: the carbon felt is sequentially subjected to ultrasonic treatment under absolute ethyl alcohol and distilled water to remove surface impurities, then the carbon felt is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, a NaOH solution is used as an electrolyte, a timed potential method is adopted for oxidation treatment, and after the treatment is finished, the carbon felt is subjected to ultrasonic washing with a large amount of distilled water to remove residual NaOH.
4. The process of claim 2 for the electrocatalytic oxidation of alditols to polycarboxylic acids, wherein: the certain temperature is 150-200 ℃, the certain time is 12-24 hours, and the calcining temperature is 300-500 ℃; the molar ratio of the urea to the nitrate is 1: 1-1: 5.
5. The process of claim 1 for the electrocatalytic oxidation of alditols to polycarboxylic acids, wherein: the transition metal comprises at least one of Fe, Co, Ni, Cu, Zn and Mn.
6. The process of claim 1 for the electrocatalytic oxidation of alditols to polycarboxylic acids, wherein: the nitroxide radical or its derivative includes at least one of 2,2,6, 6-tetramethylpiperidine 1-oxyl, 4-oxo-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 4-amino-2, 2,6, 6-tetramethylpiperidine 1-oxyl, 4-cyano-2, 2,6, 6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl, 4-carboxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl, and 4-acetamido-2, 2,6, 6-tetramethylpiperidine 1-oxyl.
7. The process of claim 1 for the electrocatalytic oxidation of alditols to polycarboxylic acids, wherein: the alditol substances include at least one of glucose, 5-hydroxymethylfurfural, xylose, cellulose, hemicellulose, erythrose, glycerol and glycolaldehyde.
8. The process of claim 1 for the electrocatalytic oxidation of alditols to polycarboxylic acids, wherein: the concentration of the alditol substances is 10-2000 mmol/L, and the molar ratio of the nitroxide free radical compound or the derivative thereof to the alditol substances is 1: 10-1: 1000.
9. The process of claim 1 for the electrocatalytic oxidation of alditols to polycarboxylic acids, wherein: the inorganic salt comprises at least one of potassium sulfate, sodium hydroxide, potassium hydroxide, sodium sulfate, sodium chloride, potassium chloride, sodium carbonate and sodium bicarbonate, and the concentration of the electrolyte is 0.1-1 mol/L.
10. The method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol as recited in claim 1, wherein said transition metal-loaded carbon felt is activated in a reaction system before use, and said activating treatment comprises the following steps: taking a carbon felt loaded with transition metal as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode, and Na2CO3The solution is an electrolyte solution, and is activated by cyclic voltammetry, the potential range is 0.7-1.7V (vs. RHE), the cycle time is 50-100 times, and the scanning frequency is 50-100 mV s-1。
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