CN110318068B - Anode coating for ion-exchange membrane electrolyzer - Google Patents
Anode coating for ion-exchange membrane electrolyzer Download PDFInfo
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- CN110318068B CN110318068B CN201910474913.XA CN201910474913A CN110318068B CN 110318068 B CN110318068 B CN 110318068B CN 201910474913 A CN201910474913 A CN 201910474913A CN 110318068 B CN110318068 B CN 110318068B
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- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 239000003014 ion exchange membrane Substances 0.000 title claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000010936 titanium Substances 0.000 claims abstract description 50
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 11
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims description 58
- 238000005507 spraying Methods 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 14
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical group Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000004584 weight gain Effects 0.000 claims description 12
- 235000019786 weight gain Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 7
- 238000005488 sandblasting Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 4
- 241001392754 Calliostoma iridium Species 0.000 claims description 3
- VJBKZXSCTKATMV-UHFFFAOYSA-J Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Ir+4] Chemical compound Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Ir+4] VJBKZXSCTKATMV-UHFFFAOYSA-J 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000007590 electrostatic spraying Methods 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- -1 ruthenium trichloride iridium tetrachloride platinum chloride Chemical compound 0.000 claims description 2
- JZHBGUMBONMHQS-UHFFFAOYSA-F tetrachlorotitanium;zirconium(4+);tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].[Zr+4] JZHBGUMBONMHQS-UHFFFAOYSA-F 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 229910019020 PtO2 Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910000457 iridium oxide Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 229910002835 Pt–Ir Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- AAQSSIHZEVZWNS-UHFFFAOYSA-N [Ti].[Sn].[Pt] Chemical compound [Ti].[Sn].[Pt] AAQSSIHZEVZWNS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- IWSBKLCKLQAURY-UHFFFAOYSA-N iridium palladium Chemical compound [Pd][Ir] IWSBKLCKLQAURY-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B01J35/33—
-
- 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
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Abstract
The invention relates to an anode coating for an ion membrane electrolytic cell, which is characterized in that the formula of the anode coating is a combined formula of ruthenium, iridium, platinum and titanium, wherein the ruthenium content is 35-45 mol%, the iridium content is 5-15 mol%, the platinum content is 5-10 mol%, the titanium content is 35-45 mol%, other additives with the mol% less than 4% can be contained in the formula, and the other additives are zirconium chloride or palladium chloride. The anode coating for the ion membrane electrolytic cell is used for an active anode and meets the following requirements: the oxygen evolution potential is high, the catalytic capability is strong, the conductivity is higher, and the oxygen evolution side reaction is not easy to occur; the performance is stable, the corrosion resistance is realized, the service life is long, and the electrode can be used continuously after being recoated after being out of service; the cost of the electrode is effectively controlled; the product quality is improved, and the chlorine gas has high purity and low oxygen content.
Description
Technical Field
The invention relates to an anode coating for an ion membrane electrolytic cell. In particular to a noble metal oxide coating of a titanium-based anode for brine electrolysis of an ion membrane electrolyzer suitable for the chlor-alkali industry.
Background
The chlor-alkali industry is a basic chemical industry, and currently, the ion membrane method is adopted for producing alkali, namely, brine is electrolyzed by an ion membrane electrolytic cell to produce caustic soda, chlorine, hydrogen and the like.
Anodic reaction of 2Cl－-2e－＝Cl2↑
4OH－-4e－＝O2↑+2H2O
Cathode reaction 2H2O+2e－＝H2↑+2OH－
Reaction of dissolved chlorine with sodium hydroxide reverse-permeated at cathode
3Cl2+6NaOH＝5NaCl+NaClO3+3H2O
Generated NaClO3Has strong oxidizing property.
In chlor-alkali production, salt (NaCl) and electricity are the main costs, with direct current consumption of 2000-. The factors of electricity consumption are mainly:
1. the structure of the electrolytic cell;
2. the chlorine evolution potential of the anode;
3. hydrogen evolution potential of the cathode.
TiO2Is an important inorganic functional material, namely nano TiO2The membrane electrode has unique photoelectric and electrochemical properties, and can further change the performance of the titanium-based coating.
Iridium dioxide (IrO)2) The electrode has high oxygen precipitation potential and strong corrosion resistance, has wide application prospect as an anode material in an acid medium, and can lead IrO to be added with elements such as Ru, Sn, Ta, Zr, Co and the like2The electrode performance is improved.
Ruthenium oxide and iridium oxide are few conductive oxides.
RuO2Has the following characteristics:
1. the consumption rate is extremely low;
2. high current operation has good durability;
3. the chlorine overpotential is not influenced by other reactions;
4. the ceramic material has the characteristics of ceramic and high melting point;
5. the adhesiveness with titanium base is strong.
The following table shows the chlorine evolution rate R (Cl) for different electrodes2)％
| Electrode for electrochemical cell | Coating components: mol% of | R(Cl2) |
| Ti/RuO2 | 100 | 75 |
| Ti/IrO2 | 100 | 19 |
| Ti/RuO2、IrO2 | 40：60 | 42 |
| Ti/RuO2、TiO2 | 40：60 | 92 |
| Ti/IrO2、TiO2 | 20：80 | 95 |
| Ti/RuO2、IrO2、TiO2 | 20：20：60 | 93 |
The high-temperature sintering temperature is 450 ℃, the potential is 1.38v (VS. Ag/AgCl)0.3mol/l NaOH +0.1mol/l HClO4The detection temperature was 25 ℃.
The traditional titanium-based ruthenium-titanium coating in the chlor-alkali production is inspected by production practice, and the defects are found as follows: the electrode life is short and the oxygen content in the produced chlorine is too high, which affects the purity of the chlorine and causes a decrease in current efficiency. Therefore, there is a need to increase the oxygen evolution potential of the active coating, decrease the chlorine evolution potential, and increase the electrode life.
Disclosure of Invention
The invention aims to overcome the defects and provide an anode coating for an ion membrane electrolytic cell.
The purpose of the invention is realized as follows:
the anode coating for ion film electrolyzer has the composition of Ru, Ir, Pt and Ti, and contains Ru in 35-45 mol%, Ir in 5-15 mol%, Pt in 5-10 mol% and Ti in 35-45 mol%.
Preferably, the formulation of the anode coating for the ion-exchange membrane electrolyzer contains less than 4 mol% of other additives, the other additives being zirconium chloride or palladium chloride.
Preferably, the carrier of ruthenium is ruthenium trichloride, the carrier of iridium is iridium tetrachloride or chloroiridate, the carrier of platinum is chloroplatinic acid or platinum chloride, and the carrier of titanium is titanium tetrachloride.
Preferably, the preparation method of the coating liquid of the anode coating layer for the ion membrane electrolytic cell is to use raw materials to prepare the coating liquid, wherein the raw materials comprise the following components:
a. ruthenium trichloride; b. titanium tetrachloride; c. iridium tetrachloride or chloroiridate; d. chloroplatinic acid or platinum chloride; e. the additive can be selected from zirconium chloride or palladium chloride; f. a solvent selected from aqueous hydrochloric acid, ethylene glycol monobutyl ether or n-butanol;
wherein, the ruthenium trichloride refers to a hydrochloric acid aqueous solution of ruthenium trichloride with the concentration of 80-120g/L or solid ruthenium trichloride with the concentration of 37%; the titanium tetrachloride refers to a chemically pure standard reagent of titanium tetrachloride, and the iridium tetrachloride refers to an iridium tetrachloride hydrochloric acid aqueous solution containing 80-120g/L of iridium.
As a preferable method, the method of manufacturing the active anode is as follows:
the method comprises the steps of firstly manufacturing an anode titanium mesh, wherein the anode titanium mesh adopts a pretreated titanium mesh base material, then uniformly coating a coating liquid on the titanium mesh base material, adopting a multi-pass coating method, drying after each pass of coating, then sintering at high temperature, and repeating the steps and then sintering to form stable noble metal oxide crystals on the surface of the titanium mesh base material.
Preferably, the specific steps for manufacturing the anode titanium mesh are as follows:
adopting a titanium plate expanded mesh of TA1 as a base material mesh of the electrode; the thickness of the titanium plate is 1-1.2mm, the thickness of the titanium mesh is 1-1.2mm, the mesh has diamond meshes, the pitch of the meshes is 3 x 6mm, 3.5 x 6mm, 4.5 x 8mm or 5 x 10mm, etc., preferably the thickness is 1mm, and the pitch is 3 x 6 mm;
the specific process flow is as follows:
1. shearing a titanium net;
2. degreasing treatment;
3. clamping the titanium net by using a clamping fixture, putting the titanium net into a heat treatment furnace for heat treatment, heating the titanium net in the heat treatment furnace to 450-530 ℃, and then cooling the titanium net out of the furnace;
4. carrying out sand blasting treatment on the front and back surfaces of the titanium mesh to form a rough surface by using an automatic conveying type sand blasting machine;
5. pickling the titanium mesh by using a sulfuric acid aqueous solution with the temperature of 80-85 ℃ and the weight of 20-25%;
6. cleaning the titanium mesh with pure water;
7. and (5) drying.
Preferably, the specific steps of uniformly coating the coating liquid on the titanium mesh substrate to finally form stable noble metal oxide crystals on the surface of the titanium mesh substrate are as follows:
the pretreated titanium mesh base material is subjected to automatic electrostatic spraying, drying and high-temperature sintering in an oxidation furnace for multiple times according to the coating weight requirement, and the spraying weight gain on the titanium mesh base material after the final sintering is 25-35g/m2Finally, sintering operation and inspection are carried out, wherein the drying temperature is 80-90 ℃, the high-temperature sintering temperature of the oxidation furnace is 400-500 ℃, the high-temperature sintering time of the oxidation furnace is 0.5-1h, the temperature of the final sintering operation is 480-530 ℃, slow temperature rise and slow temperature reduction are carried out during the sintering operation, and the sintering time is 8-12 h;
spraying, drying and sintering for 8-12 times of circulation operation according to the total weight gain after sintering, wherein the spraying amount of each time is 40-60ml/m2Weighing after each sintering, and increasing the weight by 2-4g/m2。
Compared with the prior art, the invention has the beneficial effects that:
the anode coating for the ion membrane electrolytic cell is used for an active anode and meets the following requirements:
1. the oxygen evolution potential is high, the catalytic capability is strong, the conductivity is higher, and the oxygen evolution side reaction is not easy to occur;
2. the performance is stable, the corrosion resistance is realized, the service life is long, and the electrode can be used continuously after being recoated after being out of service;
3. the cost of the electrode is effectively controlled;
4. the product quality is improved, and the chlorine gas has high purity and low oxygen content (below 0.8 percent).
Detailed Description
The Pt electrode has the characteristic of high oxygen evolution overpotential.
And sintering the platinum electrode. The sintered Pt-Ir alloy electrode not only retains the characteristic of high oxygen evolution potential of the platinum electrode, but also can be used as a cathode and an anode.
For example, a catalytic active component of a coating is prepared by adding a chloride of an element such as iridium palladium, platinum titanium tin, etc. to a coating solution containing ruthenium trichloride and titanium trichloride. Has low chlorine discharge potential, higher oxygen discharge potential and better anti-oxidation corrosion performance.
The iridium oxide has no outstanding electro-catalysis performance on the generation of chlorine, but the oxygen evolution electrochemical activity of the iridium oxide in an acid medium is inferior to that of RuO2And the medium can maintain high stability and show excellent electrolytic durability. This is believed to be due to the fact that Ir is reversible with respect to oxygen adsorption, while structurally, IrO2Is a peroxy type structure (IrO)2+ δ) its catalytic structure is not destroyed by the influx of oxygen. Because iridium oxide has good corrosion resistance to oxygen, strong anti-oxidation capability and higher oxygen evolution overpotential than ruthenium, iridium oxide has been used as an intermediate layer to improve the formulation of titanium ruthenium coating.
The electrochemical active surface area of the coating reaches the maximum value when the Ir content is 60 percent, and in an electrical property test: the voltammetric capacity of the coating with the Ir content of 20-60 percent is increased by 100 percent IrO along with the generation of oxygen evolution2The coating was reduced, indicating IrO2The addition of (2) allows the titanium electrode to have better electrolytic durability.
PtO2Can significantly change the appearance of the coating and reduce the porosity of the coating, and simultaneously, with PtO2The increase of the content changes the electrochemical behavior of the coating from PtO2Plays a dominant role when PtO2The content is 10-40 mol%, after a strong oxygen release process, the volt-ampere electric quantity of the coating is obviously reduced, and PtO2The addition of (b) reduces the electrocatalytic activity of the coating.
Deactivation factor of the coated titanium anode:
1. consumption of dissolution of the oxide coating;
2. the coating falls off;
3. passivation of titanium substrates (TiO formation between titanium base and coating2A film).
The anode coating adopts a method of adopting an intermediate layer, and has the functions of: the binding force is enhanced, the passivation is avoided,
the intermediate layer may be:
1. the metal layer Pt directly serves as an intermediate layer;
2. a metal oxide as an intermediate layer;
3. a mixture of metal and metal oxide (Ir-containing interlayer) as the interlayer.
Therefore, based on the summary of theory and experimental results, the formula of the anode coating for the ion membrane electrolytic cell is preferably a ruthenium, iridium, platinum and titanium combined formula, wherein the ruthenium content (Ru35-45 mol%), the iridium content (Ir5-15 mol%), the platinum content (Pt5-10 mol%), the titanium content (Ti35-45 mol%), and other additives with 4 mol% weight percentage can be added, and the other additives are zirconium chloride or palladium chloride, and the stable rutile structure is formed by selecting a proper proportion.
The formula is preferably selected from ruthenium content (Ru37-43 mol%), iridium content (Ir9-15 mol%), platinum content (Pt6-9 mol%), titanium content (Ti35-40 mol%) and other additives 3-4 mol%.
Specifically, the carrier of ruthenium is ruthenium trichloride, the carrier of iridium is iridium tetrachloride or chloroiridate, the carrier of platinum is chloroplatinic acid or platinum chloride, and the carrier of titanium is titanium tetrachloride.
The method for manufacturing the anode coating for the ionic membrane electrolytic cell for the active anode comprises the following steps:
firstly, manufacturing an anode titanium mesh (titanium mesh substrate pretreatment);
adopting a titanium plate expanded mesh of TA1 as a base material mesh of the electrode; the thickness of the titanium plate is 1-1.2mm, the thickness of the titanium mesh is 1-1.2mm, the mesh has diamond meshes, the pitch of the meshes is 3 x 6mm, 3.5 x 6mm, 4.5 x 8mm or 5 x 10mm, etc., preferably the thickness is 1mm, and the pitch is 3 x 6 mm;
the base material net is subjected to the working procedures of shearing, degreasing, high-temperature annealing and leveling, sand blasting, acid washing, cleaning and the like, so that a flat, clean and pitted base material is provided, and the bonding strength and the specific surface area of a coating are maximized;
the specific process flow is as follows:
1. shearing a titanium net;
2. degreasing treatment (soaking with industrial cleaning agent, cleaning after degreasing, and drying in the air);
3. clamping titanium nets (60-100 sheets are a batch) by using a mould, putting the titanium nets into a heat treatment furnace for heat treatment, wherein the mould comprises an upper fixing plate and a lower fixing plate which are rectangular, stacking 60-100 sheets of titanium nets between the upper fixing plate and the lower fixing plate, and then tightening pull rods at four corners of the upper fixing plate and the lower fixing plate so as to clamp the mould and the titanium nets; heating the titanium mesh in a heat treatment furnace to 450-530 ℃, and then cooling the titanium mesh with the furnace and discharging the titanium mesh;
4. carrying out sand blasting treatment on the front and back surfaces of the titanium mesh to form a rough surface by using an automatic conveying type sand blasting machine;
5. pickling the titanium mesh by using a sulfuric acid aqueous solution with the temperature of 80-85 ℃ and the weight of 20-25%;
6. cleaning the titanium mesh with pure water;
7. and (5) drying.
Secondly, preparing coating liquid of the anode coating;
preparing a chloride aqueous solution of an anode coating for the ionic membrane electrolytic cell according to a formula to form a coating liquid;
the raw materials are used: a. ruthenium trichloride (aqueous hydrochloric acid solution of ruthenium trichloride of 80-120g/L or solid ruthenium trichloride of 37% content); b. titanium tetrachloride, chemically pure standard reagent; c. iridium tetrachloride (an iridium tetrachloride hydrochloric acid aqueous solution containing 80 to 120g/L of iridium) or chloroiridic acid; d. chloroplatinic acid or platinum chloride; e. other additives such as zirconium chloride, palladium chloride and the like (the raw material e can be added or not added) with the weight of less than 4mol percent; f. a solvent selected from aqueous hydrochloric acid, ethylene glycol monobutyl ether or n-butanol;
thirdly, manufacturing an anode coating
And uniformly coating the coating liquid on the titanium mesh substrate, drying after each coating, then sintering at high temperature, and repeating the steps (8-12 times) to form stable noble metal oxide crystals on the surface of the titanium mesh substrate by adopting a multi-pass coating method.
The pretreated titanium mesh base material is subjected to automatic electrostatic spraying, drying and high-temperature sintering in an oxidation furnace for multiple times according to the coating weight requirement, and the spraying weight gain on the titanium mesh base material after the final sintering is 25-35g/m2And finally, sintering operation and inspection are carried out, wherein the drying temperature is 80-90 ℃, the high-temperature sintering temperature of the oxidation furnace is 400-500 ℃, the high-temperature sintering time of the oxidation furnace is 0.5-1h, the temperature of the final sintering operation is 480-530 ℃, slow temperature rise and slow temperature reduction are carried out during the sintering operation, and the sintering time is 8-12 h.
The specific process flow is as follows:
spraying, drying and sintering for 8-12 times of circulation operation according to the total weight gain after sintering, wherein the spraying amount of each time is 40-60ml/m2Weighing after each sintering, and increasing the weight by 2-4g/m2，
Example 1:
a titanium mesh substrate: mesh pitch 3 x 6mm, thickness 1 mm;
coating liquid of anode coating layer: ruthenium trichloride, iridium tetrachloride, chloroplatinic acid, titanium tetrachloride and hydrochloric acid aqueous solution, wherein the raw materials are prepared according to the atomic percentage of Ru43, Ir9, Pt8 and Ti 40;
the mass ratio of each finally used raw material is calculated as follows:
ruthenium trichloride: iridium tetrachloride: chloroplatinic acid: titanium tetrachloride 88.3: 15.7: 16.8: 158.7.
preparing an anode coating: spraying, drying and sintering for 10 times of circulation operation, wherein the spraying amount of each time is 55-60ml/m2Weighing after each sintering, and increasing the weight by 3.5-4g/m2Spraying weight gain of 35-40g/m on the titanium mesh substrate after the last sintering2。
Product testing indexes are as follows:
1. chlorine evolution potential detection results: 1.09V to 1.10V (indexes are that the current density is 4 KA/square meter, the saturated saline water has the temperature of 90 ℃ plus or minus 1 ℃ and is less than or equal to 1.13V VS SCE);
2. the result of the enhanced weight loss test is as follows: less than 4mg (index: 30% WtNaoH solution (CP grade), test block 10C square meter, temperature 90 deg.C + -1 deg.C, current density 20 KA/square meter, electrolysis for 4 hours, weight loss less than 6.3 mg);
3. tests in experimental small cell units: the electrolysis voltage is lower than that of the anode used currently; the purity of the chlorine is more than 98.8 percent (without an acid process), and the oxygen content is less than 0.6 percent.
From the product test indexes, the three detection indexes all obtain better results.
Example 2:
a titanium mesh substrate: mesh pitch 3.5 x 6mm, thickness 1 mm;
coating liquid of anode coating layer: solid ruthenium trichloride, titanium tetrachloride, iridium tetrachloride, zirconium chloride, platinum chloride and ethylene glycol monobutyl ether in a ratio of Ru37: Ir15: Pt 6: the atomic percentages of Ti39 and Zr3 form a formula material,
the mass ratio of each finally used raw material is calculated as follows:
ruthenium trichloride iridium tetrachloride platinum chloride: titanium tetrachloride zirconium chloride 76.0: 26.1: 12.6: 154.8: 7.7.
preparing an anode coating: spraying, drying and sintering for 10 times of circulation operation, wherein the spraying amount of each time is 45-50ml/m2Weighing after each sintering, and increasing the weight by 2.8-3.5g/m2Spraying the titanium mesh substrate with the weight gain of 28-35g/m after the final sintering2。
Product testing indexes are as follows:
1. chlorine evolution potential detection results: 1.10V-1.12V (indexes are that the current density is 4 KA/square meter, the saturated saline water has the temperature of 90 ℃ plus or minus 1 ℃ and is less than or equal to 1.13V VS SCE);
2. the result of the enhanced weight loss test is as follows: less than 5.5mg (index: 30% WtNaoH solution (CP grade), test block 10C square meter, temperature 90 deg.C + -1 deg.C, current density 20 KA/square meter, electrolysis for 4 hours, weight loss less than 6.3 mg);
3. tests in experimental small cell units: the electrolysis voltage is lower than that of the anode used currently; the purity of the chlorine is more than 98.6 percent (without an acid process), and the oxygen content is less than 0.7 percent.
Example 3:
a titanium mesh substrate: mesh pitch 4.5 x 8mm, thickness 1 mm;
coating liquid of anode coating layer: solid ruthenium trichloride, chloroiridic acid, chloroplatinic acid, titanium tetrachloride, palladium chloride and n-butyl alcohol are prepared into formula materials according to the atomic percentages of Ru40, Ir12, Pt9, Ti35 and Pd 4;
the mass ratio of each finally used raw material is calculated as follows:
ruthenium trichloride: chloro-iridic acid: chloroplatinic acid: titanium tetrachloride palladium chloride 82.1: 20.9: 18.9: 138.9: 26.3.
preparing an anode coating: spraying, drying and sintering for 10 times of circulation operation, wherein the spraying amount of each time is 40-45ml/m2Weighing after each sintering, and increasing the weight by 3-3.5g/m2Spraying the titanium mesh substrate with the weight gain of 30-35g/m after the final sintering2。
Product testing indexes are as follows:
1. chlorine evolution potential detection results: 1.10V-1.12V (indexes are that the current density is 4 KA/square meter, the saturated saline water has the temperature of 90 ℃ plus or minus 1 ℃ and is less than or equal to 1.13V VS SCE);
2. the result of the enhanced weight loss test is as follows: less than 5mg (index: 30% WtNaoH solution (CP grade), test block 10C square meter, temperature 90 deg.C + -1 deg.C, current density 20 KA/square meter, electrolysis for 4 hours, weight loss less than 6.3 mg);
3. tests in experimental small cell units: the electrolysis voltage is lower than that of the anode used currently; the purity of the chlorine is more than 98.8 percent (without an acid process), and the oxygen content is less than 0.6 percent.
The above is only a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. All the technical solutions formed by equivalent transformation or equivalent replacement fall within the protection scope of the present invention.
Claims (10)
1. The anode coating for the ion membrane electrolytic cell is characterized in that the formula of the anode coating is a combined formula of ruthenium, iridium, platinum and titanium, wherein the ruthenium content is 35-45 mol%, the iridium content is 5-15 mol%, the platinum content is 5-10 mol%, and the titanium content is 35-45 mol%.
2. The anodic coating for ionic membrane electrolysis cells according to claim 1, characterized in that it has, in its formulation, less than 4 mol% of other additives, zirconium chloride or palladium chloride.
3. The anodic coating for ionic membrane electrolysis cell according to claim 1 or 2, wherein the carrier of ruthenium is ruthenium trichloride, the carrier of iridium is iridium tetrachloride or chloroiridate, the carrier of platinum is chloroplatinic acid or platinum chloride, and the carrier of titanium is titanium tetrachloride.
4. The anode coating for ion-exchange membrane electrolyzer of claim 3 characterized in that its coating solution is prepared by compounding the following raw materials:
a. ruthenium trichloride; b. titanium tetrachloride; c. iridium tetrachloride or chloroiridate; d. chloroplatinic acid or platinum chloride; e. the additive can be selected from zirconium chloride or palladium chloride; f. a solvent selected from aqueous hydrochloric acid, ethylene glycol monobutyl ether or n-butanol;
wherein, the ruthenium trichloride refers to a hydrochloric acid aqueous solution of ruthenium trichloride with the concentration of 80-120g/L or solid ruthenium trichloride with the concentration of 37%; the titanium tetrachloride refers to a chemically pure standard reagent of titanium tetrachloride, and the iridium tetrachloride refers to an iridium tetrachloride hydrochloric acid aqueous solution containing 80-120g/L of iridium.
5. The anode coating for ion membrane electrolysis cell according to claim 4, wherein the method for making the active anode is as follows:
the method comprises the steps of firstly manufacturing an anode titanium mesh, wherein the anode titanium mesh adopts a pretreated titanium mesh base material, then uniformly coating a coating liquid on the titanium mesh base material, adopting a multi-pass coating method, drying after each pass of coating, then sintering at high temperature, and repeating the steps and then sintering to form stable noble metal oxide crystals on the surface of the titanium mesh base material.
6. The anode coating for the ion membrane electrolyzer of claim 5, characterized in that the specific steps for making the anode titanium mesh are as follows:
adopting a titanium plate expanded mesh of TA1 as a base material mesh of the electrode; titanium plate thickness 1-1.2mm, titanium net thickness 1-1.2mm, diamond mesh, mesh pitch 3 x 6mm, 3.5 x 6mm, 4.5 x 8mm or 5 x 10mm,
the specific process flow is as follows:
1. shearing a titanium net;
2. degreasing treatment;
3. clamping the titanium net by using a clamping fixture, putting the titanium net into a heat treatment furnace for heat treatment, heating the titanium net in the heat treatment furnace to 450-530 ℃, and then cooling the titanium net out of the furnace;
4. carrying out sand blasting treatment on the front and back surfaces of the titanium mesh to form a rough surface by using an automatic conveying type sand blasting machine;
5. pickling the titanium mesh by using a sulfuric acid aqueous solution with the temperature of 80-85 ℃ and the weight of 20-25%;
6. cleaning the titanium mesh with pure water;
7. and (5) drying.
7. The anode coating for the ion membrane electrolyzer according to claim 5, characterized in that the specific steps of uniformly coating the coating liquid on the titanium mesh substrate to finally form stable noble metal oxide crystals on the surface of the titanium mesh substrate are as follows:
the pretreated titanium mesh base material is subjected to automatic electrostatic spraying, drying and high-temperature sintering in an oxidation furnace for multiple times according to the coating weight requirement, and the spraying weight gain on the titanium mesh base material after the final sintering is 25-35g/m2Finally, sintering operation and inspection are carried out, wherein the drying temperature is 80-90 ℃, the high-temperature sintering temperature of the oxidation furnace is 400-500 ℃, the high-temperature sintering time of the oxidation furnace is 0.5-1h, the temperature of the final sintering operation is 480-530 ℃, slow temperature rise and slow temperature reduction are carried out during the sintering operation, and the sintering time is 8-12 h;
spraying, drying and sintering for 8-12 times of circulation operation according to the total weight gain after sintering, wherein the spraying amount of each time is 40-60ml/m2Weighing after each sintering, and increasing the weight by 2-4g/m2。
8. The anodic coating for an ionic membrane electrolysis cell according to claim 7, wherein:
a titanium mesh substrate: mesh pitch 3 x 6mm, thickness 1 mm;
coating liquid of anode coating layer: ruthenium trichloride, iridium tetrachloride, chloroplatinic acid, titanium tetrachloride and hydrochloric acid aqueous solution, wherein the raw materials are prepared according to the atomic percentage of Ru43, Ir9, Pt8 and Ti 40;
the mass ratio of each finally used raw material is calculated as follows:
ruthenium trichloride: iridium tetrachloride: chloroplatinic acid: titanium tetrachloride 88.3: 15.7: 16.8: 158.7;
preparing an anode coating: spraying, drying and sintering for 10 times of circulation operation, wherein the spraying amount of each time is 55-60ml/m2Weighing after each sintering, and increasing the weight by 3.5-4g/m2Spraying weight gain of 35-40g/m on the titanium mesh substrate after the last sintering2。
9. The anodic coating for an ionic membrane electrolysis cell according to claim 7, wherein:
a titanium mesh substrate: mesh pitch 3.5 x 6mm, thickness 1 mm;
coating liquid of anode coating layer: solid ruthenium trichloride, titanium tetrachloride, iridium tetrachloride, zirconium chloride, platinum chloride and ethylene glycol monobutyl ether in a ratio of Ru37: Ir15: Pt 6: the atomic percentages of Ti39 and Zr3 form a formula material,
the mass ratio of each finally used raw material is calculated as follows:
ruthenium trichloride iridium tetrachloride platinum chloride: titanium tetrachloride zirconium chloride 76.0: 26.1: 12.6: 154.8: 7.7;
preparing an anode coating: spraying, drying and sintering for 10 times of circulation operation, wherein the spraying amount of each time is 45-50ml/m2Weighing after each sintering, and increasing the weight by 2.8-3.5g/m2Spraying the titanium mesh substrate with the weight gain of 28-35g/m after the final sintering2。
10. The anodic coating for an ionic membrane electrolysis cell according to claim 7, wherein:
a titanium mesh substrate: mesh pitch 4.5 x 8mm, thickness 1 mm;
coating liquid of anode coating layer: solid ruthenium trichloride, chloroiridic acid, chloroplatinic acid, titanium tetrachloride, palladium chloride and n-butyl alcohol are prepared into formula materials according to the atomic percentages of Ru40, Ir12, Pt9, Ti35 and Pd 4;
the mass ratio of each finally used raw material is calculated as follows:
ruthenium trichloride: chloro-iridic acid: chloroplatinic acid: titanium tetrachloride palladium chloride 82.1: 20.9: 18.9: 138.9: 26.3;
preparing an anode coating: spraying, drying and sintering for 10 times of circulation operation, wherein the spraying amount of each time is 40-45ml/m2Weighing after each sintering, and increasing the weight by 3-3.5g/m2Spraying the titanium mesh substrate with the weight gain of 30-35g/m after the final sintering2。
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| JP6835379B1 (en) * | 2020-11-18 | 2021-02-24 | 石福金属興業株式会社 | Manufacturing method of titanium substrate coated electrode for electrolysis |
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