CN116478776A - Method for preparing organic acid industrial cleaning agent by electrocatalytic glycol - Google Patents
Method for preparing organic acid industrial cleaning agent by electrocatalytic glycol Download PDFInfo
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- CN116478776A CN116478776A CN202310066115.XA CN202310066115A CN116478776A CN 116478776 A CN116478776 A CN 116478776A CN 202310066115 A CN202310066115 A CN 202310066115A CN 116478776 A CN116478776 A CN 116478776A
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- Prior art keywords
- cleaning agent
- industrial cleaning
- electrocatalytic
- electrolyte
- organic acid
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 38
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 50
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019253 formic acid Nutrition 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- 239000003225 biodiesel Substances 0.000 claims 1
- 239000008157 edible vegetable oil Substances 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229960004275 glycolic acid Drugs 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229910003321 CoFe Inorganic materials 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- 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
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
Abstract
The invention discloses a method for preparing an organic acid industrial cleaning agent by electrocatalytic glycol, which comprises the steps of taking a conductive substrate carrying an anode catalyst as an anode, taking a cathode catalyst as a cathode, assembling the conductive substrate and electrolyte into an electrolytic cell, adding a certain amount of glycol into the electrolyte, oxidizing the glycol at the anode under a certain voltage condition to generate glycolic acid which is a main component of the organic acid industrial cleaning agent, and reducing water at the cathode to generate hydrogen. And then adjusting the pH value of the reaction solution to be slightly acidic, and adding a certain amount of formic acid to obtain the process cleaning agent. The invention takes oxygen atoms and hydrogen atoms in water molecules as sources of active oxygen and active hydrogen in oxidation-reduction reaction, can prepare the organic acid industrial cleaning agent at normal temperature and normal pressure without additional oxidation-reduction reagent, and simultaneously coproduces hydrogen, thereby providing a new thought and method for preparing the organic acid industrial cleaning agent at normal temperature and normal pressure in a green and efficient way.
Description
Technical Field
The invention belongs to the technical field of production of industrial cleaning agents for organic acids, and particularly relates to a method for preparing an industrial cleaning agent for organic acids by electrocatalytic ethylene glycol.
Background
Industrial cleaners are special cleaners used industrially to remove dirt and stain. Since acid washing is an important process in chemical cleaning, organic acid industrial cleaners have been an important place among various industrial cleaners. Glycolic acid is an excellent organic acid industrial cleaning agent, can fully react with rust scale, calcium, magnesium and other inorganic salts in equipment to be cleaned to achieve the purpose of scale removal in the chemical cleaning process by using the glycolic acid, and is used as organic acid, has low corrosiveness to the equipment to be cleaned and does not generate precipitates such as organic acid iron and the like; because the cleaning agent does not contain chloride ions, the cleaning agent has good cleaning effect on austenitic steel, and more importantly, the decomposed products have volatility, and even a small amount of the decomposed products remain in equipment, the equipment cannot be damaged, so that the chemical cleaning with glycolic acid has lower danger, and the operation is more convenient.
The ethylene glycol can be prepared from coal, and the cost is low, so that the preparation of the glycolic acid by oxidizing the ethylene glycol is an economic method, and accords with the concept of changing waste into valuable. In addition, ethylene glycol is also a key monomer for polyethylene terephthalate (PET) plastics. The current annual output of PET is about 7000 ten thousand tons, but only less than 20% of it is recycled and the others are landfilled or discarded, which both pollutes the environment and wastes a large amount of ethylene glycol (nat. Commun.,2021,12,4679). The oxidation products of ethylene glycol include glycolic acid, oxalic acid and formic acid, and it has been reported that the addition of formic acid to glycolic acid industrial cleaners provides better cleaning (Hebei electric technology, 2008,27 (4): 46-47.). Thus, if ethylene glycol can be oxidized to glycolic acid with high selectivity, and a certain amount of formic acid is added, the industrial cleaning agent can be prepared.
The electrocatalytic method is driven by renewable energy, takes oxygen atoms and hydrogen atoms in water as sources of active oxygen and active hydrogen in oxidation-reduction reaction, is green and efficient, and has been widely paid attention in recent years. Thus, if it were possible to use electrocatalytic ethylene glycol to prepare glycolic acid industrial cleaners, it would make a significant contribution to the sustainable development of society.
Disclosure of Invention
The invention provides a method for preparing an organic acid industrial cleaning agent by electrocatalytic glycol, which aims to realize full utilization of excess glycol and convert the glycol into the organic acid industrial cleaning agent with higher value, thereby changing waste into valuable.
The invention is realized by the following technical scheme:
a method for preparing an organic acid industrial cleaning agent by electrocatalytic glycol comprises the following steps:
assembled electrolytic cell
Taking a conductive substrate carrying an anode catalyst as an anode, taking a cathode catalyst as a cathode, and assembling the cathode catalyst and electrolyte into an electrolytic cell;
(II) electrocatalytic reactions
Adding glycol into the electrolyte, oxidizing the glycol at the anode under the voltage condition to generate glycolic acid, formic acid or oxalic acid, and reducing water at the cathode to generate hydrogen;
detecting the electrolyte after the reaction by using a high performance liquid chromatogram, wherein the selectivity of the glycolic acid in the electrolyte after the reaction is 70% -95%;
(III) preparation of Industrial cleaning agent
And (3) regulating the pH value of the electrolyte after the reaction to be slightly acidic (4) by utilizing an acidic solution, determining the mass fraction of the glycolic acid and the formic acid in the electrolyte after the reaction according to the selectivity result of the glycolic acid and the formic acid obtained in the step (II), and then adding a certain amount of formic acid to ensure that the mass fraction ratio of the glycolic acid to the formic acid is (5-1): 1.
in the above technical solution, the anode catalyst is one or more of noble metal, hydroxide-supported noble metal or oxide-supported noble metal.
In the above technical solution, the noble metal is one or more of platinum, gold, silver, ruthenium, iridium, palladium, copper or rhodium.
In the technical scheme, the hydroxide is nickel-based, cobalt-based, copper-based hydroxide or hydrotalcite material; the oxide is nickel oxide, cobalt oxide, iron oxide, aluminum oxide, copper oxide, bismuth oxide, manganese dioxide or titanium dioxide.
In the above technical scheme, the conductive substrate is any one of carbon cloth, carbon paper, foam nickel, nickel sheet, nickel net, foam copper, copper sheet, copper net, titanium sheet, titanium net, stainless steel sheet, stainless steel net, ITO conductive glass or FTO conductive glass.
In the technical scheme, the electrolyte is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate and sodium carbonate, and the concentration of the electrolyte in the electrolyte is 20 g/L-300 g/L.
In the above technical scheme, the cathode catalyst is a platinum-based catalyst; when the cathode catalyst is powder, the cathode is composed of a conductive substrate supported cathode catalyst.
In the technical scheme, the concentration of the glycol in the electrolyte is 1 g/L-50 g/L.
In the technical scheme, the voltage of the electrocatalytic reaction in the step (II) is 0.5-3V vs RHE.
In the technical scheme, the acid solution in the step (III) is hydrochloric acid, sulfuric acid or phosphoric acid solution, and the concentration of the solution is 20 g/L-600 g/L.
The beneficial effects of the invention are as follows:
the invention provides a method for preparing an organic acid industrial cleaning agent by electrocatalytic glycol, which uses oxygen atoms and hydrogen atoms in water as sources of active oxygen and active hydrogen in oxidation-reduction reaction by using the electrocatalytic method, is green and efficient, and simultaneously reduces water into hydrogen at a cathode, thereby further improving the industrial application potential of the organic acid industrial cleaning agent and providing a new thought and method for green and efficient preparation of the organic acid industrial cleaning agent.
Drawings
FIG. 1 is a schematic illustration of the reaction principle of the present invention;
FIG. 2 is a scanning electron microscope image of the anode catalyst in example 1 of the present invention;
FIG. 3 is a high performance liquid chromatogram of the ethylene glycol oxidation product after acid adjustment in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the anode catalyst in example 2 of the present invention;
FIG. 5 is a high performance liquid chromatogram of the ethylene glycol oxidation product after acid adjustment in example 2 of the present invention;
FIG. 6 is a scanning electron microscope image of the anode catalyst in example 3 of the present invention;
FIG. 7 is a high performance liquid chromatogram of the ethylene glycol oxidation product after acid adjustment in example 3 of the present invention.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be further described below by means of specific embodiments in combination with the accompanying drawings of the specification.
Example 1
(1) Preparation of anode and cathode
A. Preparation of anode (foam nickel-supported AuAg alloy)
The preparation method of the foam nickel-loaded AuAg alloy comprises the following specific steps: a three-electrode system was composed of 10mM chloroauric acid and 1mM silver nitrate solution, and 0.1M boric acid was added as an electrolyte, using nickel foam as a working electrode, a platinum sheet as a counter electrode, and a saturated calomel electrode as a reference electrode, and electrodeposited at-1V for 900s to obtain a nickel foam-supported AuAg alloy.
The scanning electron microscope image of the AuAg alloy of the anode catalyst is shown in figure 2, the AuAg alloy is in a particle shape, and the particle size is about 100nm.
B. Preparation of cathode (platinum sheet)
The platinum sheet with the cutting size of 15 mm-2 mm is washed clean by deionized water after cutting, and can be used.
(2) Preparing electrolyte
6.2g of ethylene glycol was added to 100mL of an aqueous NaOH solution having a mass concentration of 60g/L to obtain an electrolytic solution.
(3) Electrocatalytic reaction
And (3) placing the anode (the AuAg alloy loaded by the foam nickel) and the cathode (the platinum sheet) obtained in the step (1) into the electrolyte obtained in the step (2) to form an electrolytic cell, and then electrolyzing under the bias of 1.1V vs RHE at normal temperature and normal pressure until the current cannot be recovered, namely, the glycol completely reacts, so as to complete the preparation of the glycolic acid.
(4) Detection of
After the reaction was completed, the electrolyte solution after the reaction was adjusted to ph=4 with sulfuric acid solution. 1mL of the solution was filtered to remove impurities, and the product was detected by high performance liquid chromatography, as shown in FIG. 3, with a glycolic acid selectivity of 90% and a formic acid selectivity of 9%.
(5) Adding formic acid
Adding formic acid into the reaction liquid until the mass fraction ratio of glycolic acid to formic acid is 3:1, preparing the organic acid industrial cleaning agent.
Example 2
(1) Preparation of anode and cathode
A. Preparation of anode (foam Nickel Supported Pt/NiO)
Firstly, preparing foam nickel-loaded NiO, which comprises the following specific steps: first, ni (OH) supported on foam nickel was prepared 2 The specific method comprises the following steps: firstly, ultrasonic treatment is carried out on foam nickel in ethanol for 5 minutes, then the foam nickel is soaked in dilute hydrochloric acid for 1 hour, then ultrasonic treatment is carried out in deionized water for 5 minutes, finally the foam nickel is put into a reaction kettle filled with deionized water, and the reaction is carried out for 5 days at 60 ℃ to obtain Ni (OH) loaded with the foam nickel 2 The nickel foam-supported NiO was then calcined at 400 ℃ for 2 hours.
Then, preparing foam nickel-loaded Pt/NiO, which comprises the following specific steps: preparing a 10mM chloroplatinic acid solution, adding 0.1461g sodium chloride, and forming a three-electrode system by using NiO loaded by foam nickel as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode; by electrodeposition: 600s were deposited at-1V to obtain an anode, i.e., foam nickel supported Pt/NiO.
The scanning electron microscope graph of the obtained anode catalyst Pt/NiO is shown in FIG. 4, the morphology of the Pt/NiO is that the NiO nanosheet array loads Pt particles, and the particle size is about 200nm.
B. Preparation of cathode (platinum sheet)
The platinum sheet with the cutting size of 15 mm-2 mm is washed clean by deionized water after cutting, and can be used.
(2) Preparing electrolyte
3.1g of ethylene glycol was added to 100mL of an aqueous KOH solution having a mass concentration of 80g/L to obtain an electrolyte.
(3) Electrocatalytic reaction
The anode (Pd/NiFe (OH) supported by titanium mesh) obtained in the step (1) x ) And a cathode (platinum sheet) is placed into the electrolyte obtained in the step (2) to form an electrolytic cell, and then the cell is electrolyzed under the bias of 1V vs RHE at normal temperature and normal pressure until the current cannot be recovered, namely, the glycol completely reacts, so that the preparation of the glycolic acid is completed.
(4) Detection of
After the reaction was completed, the electrolyte solution after the reaction was adjusted to ph=4 with hydrochloric acid solution. 1mL of the solution was filtered to remove impurities, and the product was detected by high performance liquid chromatography, as shown in FIG. 5, with a glycolic acid selectivity of 81% and a formic acid selectivity of 17%.
(5) Adding formic acid
Adding formic acid into the reaction liquid until the mass fraction ratio of glycolic acid to formic acid is 5:1, preparing the organic acid industrial cleaning agent.
Example 3
(1) Preparation of anode and cathode
A. Anode (titanium net supported Pd/CoFe (OH)) x ) Is prepared from
First, titanium mesh-supported CoFe (OH) was prepared x The specific method comprises the following steps: 80mL of a mixed solution of 0.25mmol of cobalt nitrate and 0.15mmol of ferrous sulfate is prepared, 1.25mmol of ammonium fluoride and 9mmol of uric acid are added, and after being stirred uniformly, the mixture is poured into a high-pressure reaction kettle, and then a cleaned titanium mesh is put into the solution. Reacting at 120 ℃ for 6 hours to prepare CoFe (OH) loaded by titanium mesh x . Then preparing Pd/NiFe (OH) loaded by titanium mesh x The specific method comprises the following steps: a10 mM potassium chloropalladate solution was prepared and 0.15M sodium chloride was added as an electrolyte, and CoFe (OH) supported on a titanium mesh was used x The three-electrode system is composed of a working electrode, a platinum sheet serving as a counter electrode and a saturated calomel electrode serving as a reference electrode, and is electrodeposited for 900s at-1V to obtain an anode, namely Pd/NiFe (OH) loaded by a titanium mesh x 。
The anode catalyst Pd/CoFe (OH) x As shown in FIG. 6, the scanning electron microscope image of (C) is Pd/CoFe (OH) x Is of the morphology CoFe (OH) x The nano-sheet array carries Pd particles with the particle size of about 200nm.
B. Preparation of cathode (platinum sheet)
The platinum sheet with the cutting size of 15 mm-2 mm is washed clean by deionized water after cutting, and can be used.
(2) Preparing electrolyte
12.4g of ethylene glycol was added to 100mL of KOH aqueous solution having a mass concentration of 100g/L to obtain an electrolyte.
(3) Electrocatalytic reaction
The anode (Pd/CoFe (OH) supported by titanium mesh) obtained in the step (1) x ) And a cathode (platinum sheet) is placed into the electrolyte obtained in the step (2) to form an electrolytic cell, and then the cell is electrolyzed under the bias of 1V vs RHE at normal temperature and normal pressure until the current cannot be recovered, namely, the glycol completely reacts, so that the preparation of the glycolic acid is completed.
(4) Detection of
After the reaction was completed, the electrolyte solution after the reaction was adjusted to ph=4 with a phosphoric acid solution. 1mL of the solution was filtered to remove impurities, and the product was detected by high performance liquid chromatography, as shown in FIG. 7, with a hydroxyacetic acid selectivity of 85% and a formic acid selectivity of 14%.
(5) Adding formic acid
Adding formic acid into the reaction liquid until the mass fraction ratio of glycolic acid to formic acid is 1:1, preparing the organic acid industrial cleaning agent.
The design principle of the invention is as follows:
as shown in figure 1, the invention takes the conductive substrate carrying the anode catalyst as an anode electrocatalyst, takes oxygen atoms and hydrogen atoms in water molecules as sources of active oxygen and active hydrogen in oxidation-reduction reaction, can prepare the organic acid industrial cleaning agent at normal temperature and normal pressure without additional oxidation-reduction reagent, and simultaneously produces hydrogen at the cathode.
The chemical reaction equation is:
the anode reaction is as follows: c (C) 2 H 6 O 2 +4OH - -4e - →C 2 H 4 O 3 +2H 2 O；
The cathode reaction is as follows: 2H (H) 2 O+2e - →H 2 +2OH - 。
In response to the call of sustainable development society, the invention develops a production method for efficiently preparing the organic acid industrial cleaning agent by using oxygen atoms and hydrogen atoms in water molecules as sources of active oxygen and active hydrogen in redox reaction, and can prepare the organic acid industrial cleaning agent at normal temperature and normal pressure without additional redox reagents, thereby providing a new thought and method for efficiently and environmentally preparing the organic acid industrial cleaning agent.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A method for preparing an organic acid industrial cleaning agent by electrocatalytic glycol is characterized by comprising the following steps: the method comprises the following steps:
assembled electrolytic cell
Taking a conductive substrate carrying an anode catalyst as an anode, taking a cathode catalyst as a cathode, and assembling the cathode catalyst and electrolyte into an electrolytic cell;
(II) electrocatalytic reactions
Adding ethylene glycol into the electrolyte, oxidizing the ethylene glycol at an anode under a voltage condition, and reducing water at a cathode to generate hydrogen;
(III) preparation of Industrial cleaning agent
Adjusting the pH of the electrolyte after the reaction to be weak acid by using an acidic solution, and then adding formic acid into the electrolyte according to the mass fraction of glycolic acid and formic acid in the electrolyte so that the mass fraction ratio of the glycolic acid to the formic acid in the solution is (5-1): 1, obtaining the industrial cleaning agent.
2. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the anode catalyst is any one or more of noble metal, noble metal/hydroxide and noble metal/oxide.
3. The method for preparing biodiesel, lactic acid and hydrogen by electrochemical refining of edible oil according to claim 5, wherein the method comprises the following steps: the hydroxide is nickel-based, cobalt-based, copper-based hydroxide or hydrotalcite material; the oxide is nickel oxide, cobalt oxide, iron oxide, aluminum oxide, copper oxide, bismuth oxide, manganese dioxide or titanium dioxide.
4. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the conductive substrate is any one of carbon cloth, carbon paper, foam nickel, nickel sheet, nickel net, foam copper, copper sheet, copper net, titanium sheet, titanium net, stainless steel sheet, stainless steel net, ITO conductive glass or FTO conductive glass.
5. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the electrolyte is any one or more aqueous solutions of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate or sodium carbonate, and the concentration of the electrolyte in the electrolyte is 20 g/L-300 g/L.
6. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the cathode catalyst is a platinum-based catalyst; when the cathode catalyst is powder, the cathode is composed of a conductive substrate supported cathode catalyst.
7. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the concentration of ethylene glycol in the electrolyte is 1 g/L-50 g/L.
8. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the voltage of the electrocatalytic reaction in the step (II) is 0.5-3V vs RHE.
9. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: the acidic solution in the step (III) is hydrochloric acid, sulfuric acid or phosphoric acid solution, and the concentration of solute in the acidic solution is 20 g/L-600 g/L.
10. The method for preparing the organic acid industrial cleaning agent by electrocatalytic glycol according to claim 1, wherein the method comprises the following steps: in the step (iii), the ph=4 of the electrolyte after the reaction is adjusted by using an acidic solution.
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