CN1077758A - Graphite anode for electrolysis of chloride aqueous solution and method for producing same - Google Patents
Graphite anode for electrolysis of chloride aqueous solution and method for producing same Download PDFInfo
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- CN1077758A CN1077758A CN 93104846 CN93104846A CN1077758A CN 1077758 A CN1077758 A CN 1077758A CN 93104846 CN93104846 CN 93104846 CN 93104846 A CN93104846 A CN 93104846A CN 1077758 A CN1077758 A CN 1077758A
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- graphite
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- vinylbenzene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000010439 graphite Substances 0.000 title claims abstract description 93
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 93
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 239000007864 aqueous solution Substances 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- -1 alkyl methacrylic ester Chemical compound 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000005251 gamma ray Effects 0.000 claims description 5
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 4
- 231100000987 absorbed dose Toxicity 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-RNFDNDRNSA-N cesium-137 Chemical compound [137Cs] TVFDJXOCXUVLDH-RNFDNDRNSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 12
- 238000003847 radiation curing Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 229920006163 vinyl copolymer Polymers 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000006243 chemical 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
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229920002521 macromolecule Polymers 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
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention relates to a long-life graphite anode for electrolysis of aqueous chloride solutions, in particular aqueous sodium chloride solutions, and to a method for producing the same. The electrode uses a common graphite anode as a base material, a metal oxide layer and a vinyl copolymer are coated outside the graphite anode, the vinyl copolymer is formed by copolymerizing more than two monomers, and the graphite anode has the advantages of corrosion resistance, difficult peeling and the like. The copolymerization process of the vinyl monomer adopts radiation curing, so that the process is simple, no solvent is volatilized, the environment is not polluted, and in addition, the production is safe because no solvent is used.
Description
The present invention relates to a kind of anode and manufacture method thereof, graphite anode and the manufacture method thereof used especially for sodium chloride electrolysis.
In electrolysis of chloride industry, graphite is a kind of good conductivity, inexpensive electrode materials, in a large number as the electrolytic anode of aqueous chloride solution, especially sodium chloride aqueous solution.It is more much lower than the cost of metal anode material, and raw material sources are abundant, the manufacturing technology maturation, and manufacturing processed current consumption is more much smaller than metal anode.But its anti-electrolytic corrosion is poor, the life-span short, and the general sodium chloride electrolysis diaphram tank life-span only about 7 months, makes factory's dismounting electrolyzer frequent, and the consumable anode quantity of material is big, needs artificial many.Bath voltage is higher slightly than metal anode on the other hand, power consumption height during use.
People once attempted siccative oil such as oleum lini, tung oil and paraffin etc. are immersed in the graphite hole, so that the corrosive nature that causes owing to the hole oxidation when reducing electrolysis, but because siccative oil solidifies difficulty, siccative oil and paraffin poor heat resistance, when high temperature (for example 100 ℃) electrolysis, easily soften, decompose or exosmose, so planting the life-span of impregnated graphite goods prolongs not too remarkable, after the more important thing is this class material of graphite impregnation, the chlorine overpotential raises, electrolyzer presses liter, power consumption is increased, so fail industrial applications.Russian patent 975833 is a base material with the common graphite, the oxide compound of dip-coating VII family and VIII family metal, and dip-coating polystyrene or polyester or mineral glue again, the graphite anode material of making is at lesser temps (80 ℃) and low current density (5 kilo-ampere/rice
2) down can prolongs life; United States Patent (USP) 2075060A introduces a kind of polystyrene or polyethylene, polymethylmethacrylate, polyvinyl chloride or vibrin, polyacrylic ester, furane resin with after the metal oxide-coated graphite; Also use a kind of petroleum pitch, coal-tar pitch, Yatall MA or oleum lini; Also use the mixture of polyethylene and paraffin, the mixture of polystyrene and polymethylmethacrylate.The polymkeric substance of introducing must be the flowing fluid state, otherwise can't implement dipping process.This technology adopts three kinds of methods to introduce polymkeric substance to graphite for this reason: (1) is dissolved in organic solvent, makes solution, and after graphite was immersed in pressurization, dry removing desolvated; (2) polymkeric substance high temperature (more than the melt temperature) fusion keeps pressurizeing under the liquid state and immerses in the graphite, is cooled to then below the dropping point temperature; (3) use liquid monomer (referring to be in a liquid state under the normal temperature) or contain the liquid condensation unit of polymerizing catalyst or oligopolymer as soaker, thermopolymerization (or condensation) becomes solid-state after the dipping.Above-mentioned two kinds of technology all can prolong the life-span of graphite anode.The problem that exists is: (1) uses the olefin polymer dip-coating, for example polyethylene, polystyrene and paraffin wax hydro carbons, poor adhesion to graphite, especially in long-term electrolytic process under high temperature and the strong mobile ionogen effect, polymkeric substance and metal oxide come off from graphite surface easily, and particularly polystyrene can quicken to come off because of ionogen effect swelling, cause the chlorine overpotential to raise, and influence the anodic life-span; (2) polymers soln dipping method is because high polymeric solution viscosity height must use a large amount of organic solvent dilutings (general solvent more than 80%), volatilized again then, this has not only improved cost, and environment is had pollution, produce also dangerously, technology is also complicated; (3) polymkeric substance high-temperature fusion impregnation technology is very complicated, because the high molecular polymer fusing point is mostly more than 120 ℃ or 130 ℃, even up to more than 200 ℃, cause decomposition, oxidation of superpolymer etc. under the high melt temperature sometimes, and in whole technological process, all to maintain high temperature, to keep the molten state of superpolymer, make technology further complicated; (4) if liquid monomer or condensation unit, though the impregnation technology process realizes that easily the monomer that immerses behind the graphite anode will be realized polymerization, and is just very difficult, so it must adopt High Temperature High Pressure, not only complex process is also high to equipment requirements.
The object of the invention provides graphite anode and the manufacture method thereof that a kind of life-span is long, the chlorine overpotential is low, the simple electrolysis of aqueous chloride solution of processing is used.
The present invention implements like this: it is made up of graphite body and outer metal oxide layer and the copolymer layer of graphite body, metal oxide layer is oxide compound or its mixture of VII, VIII or II, IV family metallic element, the invention is characterized in that polymer layer is an ethylenic copolymer.Graphite body: metal oxide: ethylenic copolymer=100: 0.3～10: 0.5～20(weight ratio, down together).The outer metal oxide layer that applies of graphite body be meant Mn, Co, Ni, Fe, Ru, Rh, Pd or II family, the IV family metal of VII family in the periodic table of elements, VIII family metal Zn, Ti, Sn water-insoluble and have oxide compound or its mixture of electro catalytic activity.Copolymer layer is an ethylenic copolymer, and it is the multipolymer that is formed by following monomer mixture copolymerization: vinylbenzene or be dissolved with the vinylbenzene of polystyrene (1～25%, weight ratio)
(representing with a) adds vinylformic acid or alkyl acrylate or acrylic acid hydroxy alkyl ester (representing with b)
, wherein R=H ,-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
2H
4OH ,-C
3H
6OH.Their weight proportion is as follows: a: b=100: 1～80(weight ratio).Acrylic acid content is suitable, too high meeting occur copolymer layer swelling, come off.
For multipolymer being solidified easily and crosslinked, and promote the reduction of chlorine overpotential, in a, b, can add epoxy alkyl acrylate or epoxy alkyl methacrylic ester (representing) with c
, R wherein
1=H ,-CH
3, R
2=-CH
2-,-C
2H
4-,-C
3H
6-.Their proportioning is as follows: a: b: c=100: 1～80: 1～900(weight ratio).
Can add divinylbenzene (representing) in addition with d
Reduce swelling capacity to increase degree of crosslinking, and improve the physical strength of copolymer layer, their proportioning is as follows: a: b: d=100: 1～80: 1～25(weight ratio).
The multipolymer macromole that the present invention applies is different from the polymer macromolecule that single monomer obtains, here this heat-resisting, corrosion resistant chemical stability of existing vinylbenzene unit, also contain and strong vinylformic acid of graphite adhesion power or unit, can also include epoxy alkyl ester units or bi-vinyl monomeric unit with alkyl (or hydroxyalkyl) ester class.They are under the radiation effect that the present invention adopts, has the function that makes macromolecules cross-linking to some extent, therefore this radiation copolymerization thing is in the same place with metal oxide and graphite adhesion securely, (comprise intrapore top layer) on the graphite top layer and form fine and close anti-corrosion layer, make this anode in electrolytic process, have the longer life-span.This top layer also has certain wetting ability, and electro catalytic activity metal oxide difficult drop-off, and this also is the low important factor of chlorine overpotential.Product of the present invention is except that life-span length, chlorine overpotential hang down, and it also has lower than resistance, can bear bigger current density; Ultimate compression strength and folding strength height can reduce the carrying loss, and keep electrolyzer and be in the normal upright state all the time at electrolysis anode in service; Void content is low, than great, can reduce because the electrolysis loss that the pore oxidation causes.
The preparation method of graphite anode of the present invention is immersed in (normal pressure～33Pa), 100～140 ℃ of dryings, become to have electro catalytic activity, be insoluble to electrolytical metal oxide in 250～450 ℃ of roastings in the metal salt solution to graphite body earlier; Again normal pressure or the decompression under (normal pressure～33Pa) be immersed in the vinyl liquid monomer mixture; The graphite body of the handling irradiator of packing into, use source of radiation irradiation at last, solidify the back take out promptly obtain long-life, cross the low graphite anode product of chloride potential.
Metal salt solution of the present invention is meant the metal of periodic table of elements VII, VIII family such as Mn, Co, Ni, Fe, Ru, Rh, Pd etc. or II, the metal of IV family such as the salts solution of Zn, Ti, Sn etc., as nitrate, acetate solution.Vinyl liquid monomer mixture is meant vinylbenzene or is dissolved with the vinylbenzene of polystyrene (is a) to add vinylformic acid or alkyl acrylate or acrylic acid hydroxy alkyl ester (being b).In addition, in said mixture, also can add epoxy alkyl acrylate or epoxy alkyl methacrylic ester (being c), or add divinylbenzene (being d).
The present invention adopts radiation curing, and complex apparatus and the technologic difficulty of having avoided general chemistry, thermopolymerization to bring can realize polymerization at normal temperatures and pressures easily.Make both safety of production process, also economize energy consumption, greatly reduce cost.The source of radiation that the radiation copolymerization solidification process uses is to make material produce ionized high-energy ionization radiation source, gamma ray projector as cobalt-60, caesium-137, low-energy electronic accelerator, χ gamma ray source etc., especially gamma ray projector, it has stronger penetrativity, can shine the big blocky graphite material of thickness easily, normal temperature and pressure causes the liquid monomer that immerses graphite hole and top layer down, make it polymerization, and can produce to a certain degree cross-link bond, make multipolymer mechanism intensity height, and cannot not be molten insoluble compact solid.Above-mentioned energetic ray does not cause illuminated material to produce nuclear reaction and induced radioactivity with respect to nuclear reaction genus low energy.This class radiation source assembly has safe, free from environmental pollution characteristics.
The total absorbed dose that the present invention adopts must reach to solidify and be as the criterion with anode, is generally 5～60kGy, and more suitable total absorbed dose is 8～30kGy.
Method of the present invention is owing to adopt radiation curing, therefore can use liquid monomer, thereby the high-temperature fusion process and the complicated impregnation technology of molten polymer have been avoided using, and, therefore do not need solubilizing agent owing to use liquid monomer, there is not solvent evaporates yet, so can save the consumption of solvent, reduce cost, environment has not been polluted yet, produced also safety.
Embodiment
The graphite rod of example 1 30 * 35 * 200mm is put into impregnating autoclave, is evacuated down to 8 * 10
3Pa injects 25%(weight) cobalt nitrate aqueous solution, make it emptying behind the submergence graphite rod, stopped 10 minutes, the taking-up graphite rod is 130 ℃ of dryings 1 hour, again in 260 ℃ of roastings 30 minutes, cool to room temperature.Cooled graphite rod is put into impregnating autoclave, be evacuated to 1.6 * 10
4Pa, injected vinylbenzene, vinylformic acid and acrylic acid epoxy propyl ester (66.4: 33.6: 10, weight ratio) liquid mix monomer, emptying behind the graphite rod that submerges stopped 10 minutes, take out graphite rod, the irradiator of packing into, fill the nitrogen deoxygenation after, with cobalt-60 source of radiation irradiation, dose rate 21.6kGy/h, absorption dose 24.9kGy.In the long-lived anode of this radiation curing that obtains, metal oxide accounts for the 0.6%(weight of graphite), the 7.5%(weight of copolymer comprised graphite).
As anode, common graphite is ionogen as anode with 30g/l hydrochloric acid, at 85～95 ℃, current density 9.5A/dm with this long-lived graphite anode
2Condition under, electrolysis electricity is the 1000Ah(ampere hour altogether).Common graphite contrasts as anode under the same electrolytic condition.The electrolysis result, common graphite anodic loss (anode weightlessness) rate is 103mg/Ah, long-lived anodic wastage rate are 58.2mg/Ah, with the former ratio (loss ratio) be 0.565, life-span is 1.77 than (inverse of loss ratio), that is to say that common graphite anode life is 1, the then long-lived anodic life-span extends to 1.77 times.
The graphite rod of example 2 9.9 * 7.2 * 120mm is made long-lived anode under the condition identical with example 1, and wherein metal oxide accounts for the 0.83%(weight of graphite), the 7.4%(weight of copolymer comprised graphite).Make reference electrode with saturated calomel electrode, with the long-lived anode of making is the anode of electrolyzer (the side current potential is used) and the indicator electrode of measuring current potential, with the negative electrode of common graphite as electrolyzer, in 80 ± 1 ℃ of 3mol/L sodium chloride electrolysis matter, apply volts DS gradually from 0～6 volt, measure and calculate this anodic chlorine overpotential.Under the similarity condition, contrast with the anode of common graphite rod as electrolyzer.The result who obtains shows that long-lived anode reduces by 0.2 volt than common graphite anodic chlorine overpotential.
The graphite rod of example 3 and example 1 same size is made long-lived graphite rod by example 1 same operational condition, and different is that liquid monomer is the mixture of vinylbenzene and vinylformic acid (100: 30, weight ratio).Metal oxide accounts for the 0.58%(weight of graphite in the long-lived anode of making), the 6.3%(weight of copolymer comprised graphite).Down carry out electrolysis with common graphite with example 1 the same terms and contrast, its life-span ratio is 1.52.
The graphite rod of example 4 9.9 * 7.2 * 120mm is made long-lived anode bar by example 3 same operations, and different is to be dissolved with 12.5%(weight in the liquid monomer vinylbenzene component) polystyrene.Metal oxide and multipolymer account for the 0.3%(weight of graphite respectively in this longevity anode bar) and 2.6%(weight).This longevity anode bar and example 2 similarity conditions are measured the chlorine overpotential down and are contrasted with the common graphite anode, and the chlorine overpotential reduces by 0.15 volt as a result.
The graphite rod of example 5 9.9 * 7.2 * 120mm is made long-lived anode bar by the operation of example 1, and different is that liquid monomer is the mixture of vinylbenzene, divinylbenzene and vinylformic acid (100: 10: 50, weight ratio), absorption dose 8.3kGy.This long-lived anode bar is measured the chlorine overpotential and is contrasted with the common graphite rod under example 2 conditions, the chlorine overpotential reduces by 0.2 volt as a result.
The graphite rod of example 6 9.9 * 7.2 * 120mm and example 1 same operational condition are made long-lived anode bar, and different is that liquid monomer is the mixture of methyl acrylate, vinylformic acid and vinylbenzene (100: 50: 15, weight ratio).The anode bar chlorine overpotential of making is lower 0.15 volt than common graphite anode.
The graphite rod of example 7 30 * 35 * 200mm is put into impregnating autoclave, is evacuated to 8 * 10
3Pa injects 25%(weight) Xiao Suangu and the mixture of nickelous nitrate (the two Mol is than=2: 1), emptying behind the submergence graphite rod, stopped 15 minutes, 120 ℃ of bakings 1.5 hours, again in 260 ℃ of roastings 40 minutes, behind the cool to room temperature, put into impregnating autoclave, be evacuated to 1.6 * 10
4Pa, the liquid mix monomer of injection vinylbenzene and vinylformic acid (100: 30, weight ratio), do not have emptying behind the graphite rod, and stopped after 20 minutes and take out, put into irradiator, fill behind the nitrogen deoxygenation in dose rate 21.6kGy/n absorption dose 8.3kGy, radiation curing growth Shouyang utmost point.The oxide compound of cobalt and nickel accounts for the 0.77%(weight of graphite in this longevity anode), the 3.7%(weight of copolymer comprised graphite).With the contrast of common graphite anode electrolysis, the result should longevity ratio anode life be 1.44 under the condition identical with example 1.
The graphite cake of example 8 39 * 180 * 760mm is put into impregnating autoclave, is evacuated to 2.1 * 10
4Pa injects 25%(weight) cobalt nitrate aqueous solution, emptying behind the graphite cake that submerges stopped 20 minutes, the taking-up graphite cake 130 ℃ of heat dryings 2 hours, is put into impregnating autoclave after being cooled to room temperature, is evacuated to 2.1 * 10
4Pa, inject the liquid monomer mixture of vinylbenzene, vinylformic acid and acrylic acid epoxy propyl ester (70: 30: 10 weight ratios), do not have emptying behind the graphite cake, stopped 10 minutes, take out graphite cake, put into irradiator, use cobalt-60 source irradiation behind the inflated with nitrogen deoxygenation, dose rate 0.197kGy/h, total absorbed dose 30kGy obtain the long-lived anode of radiation curing.Its Main physical index and correlation data thereof are listed in following table:
Project unit's index
The long-lived anode common graphite of the present invention anode
Bulk specific weight/1.87 1.62
Void content % 9.79〉19.7
Than resistance 10
-6Ω m 5.19 6.23
Ultimate compression strength MPa 60.58 30.93
Folding strength MPa 27.49 16.00
By data in the table as can be known, the These parameters of the long-lived anode product of the present invention all is better than the common graphite anode, and its bulk specific weight reaches 1.87, and void content is reduced to 9.79%, is reduced to 5.19 * 10 than resistance
-6Ω m, ultimate compression strength is brought up to 60.58MPa, and folding strength is brought up to 27.49MPa.The electrolysis on 16 type sodium-chlor diaphram tanks of the long-lived anode of this radiation curing, electric current 10000A, the life-span ratio reaches 1.7, total run time 13 months, bath voltage is lower 0.105 volt than common graphite anode.
In sum, the present invention is the base material coated metal oxide with the common graphite anode, and make long-lived graphite anode by dipping and strong, the corrosion resistant ethylene monomer copolymer of radiation curing coating adhesive power, easy, the safety of manufacture method, product extends to 1.25～1.8 times 85～95 ℃ of electrolytic life-spans of sodium chloride aqueous solution than common graphite anode; The chlorine overpotential reduces by 0.1～0.3 volt.This electrode does not need high pressure in making processes, without solvent, so there is not environmental pollution, produce yet safety yet.
Claims (6)
1, a kind ofly is used for the graphite anode that electrolysis of aqueous chloride solution is used, it is made up of graphite body and outer metal oxide layer and the copolymer layer of graphite body, metal oxide layer is that oxide compound or its mixture of VII, VIII or II, IV family metallic element formed, it is characterized in that copolymer layer is an ethylenic copolymer, graphite body: metal oxide: ethylenic copolymer=100: 0.3～10: 0.5～20 (weight ratio).
2, graphite anode as claimed in claim 1 is characterized in that the vinyl polymer coating is to be formed by following monomer copolymerizable:
Vinylbenzene or be dissolved with the vinylbenzene of polystyrene (1～25%, weight ratio)
(representing with a) adds vinylformic acid or alkyl acrylate or acrylic acid hydroxy alkyl ester (representing with b)
, wherein R=H ,-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
2H
4OH ,-C
3H
6OH, proportioning is as follows: a: b=100: 1～80(weight ratio).
3, graphite anode as claimed in claim 1 is characterized in that the vinyl polymer coating is to be formed by following monomer copolymerizable:
Vinylbenzene or the vinylbenzene (representing with a) that is dissolved with polystyrene (1～25%, weight ratio) add vinylformic acid or alkyl acrylate or acrylic acid hydroxy alkyl ester (representing with b) and add epoxy alkyl acrylate or epoxy alkyl methacrylic ester (representing with c)
R wherein
1=H ,-CH
3, R
2=-CH
2-,-C
2H
4-,-C
3H
6-, their proportioning is as follows: a: b: c=100: 1～80: 1～900(weight ratio).
4, graphite anode as claimed in claim 1 is characterized in that the vinyl polymer coating is to be formed by following monomer copolymerizable:
Vinylbenzene or the vinylbenzene (representing with a) that is dissolved with polystyrene (1～25%, weight ratio) add vinylformic acid or alkyl acrylate or acrylic acid hydroxy alkyl ester (representing with b) and add divinylbenzene (representing with d)
, its proportioning is as follows: a: b: d=100: 1～80: 1～25(weight ratio).
5, a kind of preparation method of graphite anode as claimed in claim 1 is characterized in that the step of this method is as follows:
(1) graphite body is immersed in the metal salt solution, pressure is normal pressure～33Pa, again 100～140 ℃ of dryings, then 250～450 ℃ of roastings, metal salt solution is meant the salts solution that can generate Mn, Co with electro catalytic activity, water-insoluble oxide compound, Ni, Fe, Ru, Rh, Pd, Zn, Ti, Sn
(2) the graphite body in (1) normal pressure or the decompression under (normal pressure～33Pa) be immersed in the vinyl liquid monomer mixture,
(3) graphite body of handling through (1), (2) is placed irradiator, carry out irradiation with source of radiation, the total absorbed dose rate is 5～60kGy.
6, preparation method as claimed in claim 5 is characterized in that source of radiation is the gamma ray projector of cobalt-60, caesium-137, low-energy electronic accelerator, χ gamma ray source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93104846 CN1077758A (en) | 1993-05-17 | 1993-05-17 | Graphite anode for electrolysis of chloride aqueous solution and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93104846 CN1077758A (en) | 1993-05-17 | 1993-05-17 | Graphite anode for electrolysis of chloride aqueous solution and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1077758A true CN1077758A (en) | 1993-10-27 |
Family
ID=4985408
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93104846 Pending CN1077758A (en) | 1993-05-17 | 1993-05-17 | Graphite anode for electrolysis of chloride aqueous solution and method for producing same |
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| Country | Link |
|---|---|
| CN (1) | CN1077758A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111962096A (en) * | 2020-08-13 | 2020-11-20 | 沧州信联化工有限公司 | Synthetic method and equipment for tetramethylammonium hydroxide |
-
1993
- 1993-05-17 CN CN 93104846 patent/CN1077758A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111962096A (en) * | 2020-08-13 | 2020-11-20 | 沧州信联化工有限公司 | Synthetic method and equipment for tetramethylammonium hydroxide |
| CN111962096B (en) * | 2020-08-13 | 2021-12-10 | 沧州信联化工有限公司 | Synthetic method and equipment for tetramethylammonium hydroxide |
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