CN116590758A - Treatment method for preparing cathode plate for high-purity manganese - Google Patents
Treatment method for preparing cathode plate for high-purity manganese Download PDFInfo
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- CN116590758A CN116590758A CN202310625424.6A CN202310625424A CN116590758A CN 116590758 A CN116590758 A CN 116590758A CN 202310625424 A CN202310625424 A CN 202310625424A CN 116590758 A CN116590758 A CN 116590758A
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- corrosion inhibition
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 94
- 239000011572 manganese Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000005498 polishing Methods 0.000 claims abstract description 71
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- 230000007797 corrosion Effects 0.000 claims abstract description 54
- 230000005764 inhibitory process Effects 0.000 claims abstract description 52
- 238000002161 passivation Methods 0.000 claims abstract description 52
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 23
- 230000003746 surface roughness Effects 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 135
- 239000000243 solution Substances 0.000 claims description 94
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 90
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 72
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 46
- 239000012964 benzotriazole Substances 0.000 claims description 46
- 239000002994 raw material Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims description 28
- 235000006408 oxalic acid Nutrition 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 17
- 238000011010 flushing procedure Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003929 acidic solution Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000006061 abrasive grain Substances 0.000 claims 1
- 238000007517 polishing process Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009865 steel metallurgy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
- C25C7/08—Separating of deposited metals from the cathode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/30—Electrolytic production, recovery or refining of metals by electrolysis of melts of manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Abstract
The invention relates to a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps of: (1) Carrying out demanganization on the stripped cathode plate to obtain a demanganization cathode plate; (2) If the surface roughness Ra of the demanganized cathode plate obtained in the step (1) is less than or equal to 1.6 mu m, performing corrosion inhibition passivation treatment on the demanganized cathode plate to obtain a treated cathode plate; and (3) if the surface roughness Ra of the demanganized cathode plate obtained in the step (1) is more than 1.6 mu m, performing chemical mechanical polishing treatment on the demanganized cathode plate to obtain a treated cathode plate. The treatment method provided by the invention can enable the cathode plate to be easier to strip from the cathode plate in the subsequent electrolytic manganese preparation, greatly improves the stripping efficiency, effectively reduces the residual manganese amount on the cathode plate, and is beneficial to improving the purity of manganese products.
Description
Technical Field
The invention relates to the field of metal electrolysis, in particular to a treatment method for preparing a cathode plate for high-purity manganese.
Background
The metal manganese is used as a purifying agent and a deoxidizing agent in the iron and steel industry and nonferrous metal smelting and an additive in the alloy smelting, and is widely applied to the fields of iron and steel metallurgy, nonferrous metallurgy industry, electronic industry and the like. With the rapid development of industry, the amount of electrolytic manganese is greatly increased, and particularly the amount of high-purity manganese is accelerated to increase.
Currently, the industrial production of manganese metal uses an electrolytic (wet) process. However, the purity of electrolytic manganese obtained by the prior art is difficult to exceed 4N (99.99%), and the content of Fe, zn, S, se and other impurities in the electrolytic manganese is generally high. In order to optimally produce chips below 28nm, high-purity manganese with purity of more than 4N5 is required to be adopted on a high-purity copper-manganese alloy interconnection line, and the content of gases such as C, N, O, H, S and the like is required to be less than 5ppm. Moreover, in the existing electrolytic manganese process, the phenomenon of rough groove surface and hairiness can occur after the cathode plate is used for a long time, so that the electrolytic manganese is difficult to strip from the cathode plate, and the normal production of the electrolytic manganese is finally influenced, so that the cathode plate is required to be treated and then put into the normal electrolytic production.
In the electrolytic manganese production process, the cathode plate is generally made of 304 stainless steel. The electrolytic manganese cathode plate for first use generally requires pretreatment including: degreasing treatment, electrochemical polishing treatment and sodium silicate solution soaking treatment. Common treatment operations for the electrolytic manganese cathode plate after leaving the tank generally comprise: (1) Immersing the cathode plate in an anode solution to remove the manganese residue on the plate surface; (2) The cathode plate is soaked by adopting a mixed solution of nitric acid and potassium dichromate, then the cathode plate is washed, the cathode plate with a bright and smooth surface after washing is returned for use, and the cathode plate with a whitish surface is completely dried and then polished by adopting a mixed solution of sulfuric acid and phosphoric acid. In the above processing method, there are problems including: (1) The adopted agents such as potassium dichromate, phosphoric acid, sulfuric acid, sodium silicate and the like are easy to introduce Cr, si, P, na and other elements into electrolytic manganese production, so that the purity of manganese products is reduced; (2) Electrolytic manganese is not easy to be stripped from the cathode plate, the production efficiency is lower, and the loss of manganese is larger.
Therefore, it is important to provide a cathode plate treatment method capable of improving the stripping efficiency of manganese, reducing the amount of residual manganese, and improving the purity of manganese products.
Disclosure of Invention
Compared with the prior art, the cathode plate treated by the treatment method is easy to strip off the cathode plate after being used for subsequent electrolytic manganese preparation operation, the residual manganese amount on the cathode plate is greatly reduced, the stripping efficiency of electrolytic manganese is improved, and the purity of manganese products is effectively improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps of:
(1) Carrying out demanganization on the stripped cathode plate to obtain a demanganization cathode plate;
(2) If the surface roughness Ra of the demanganized cathode plate obtained in the step (1) is less than or equal to 1.6 mu m, performing corrosion inhibition passivation treatment on the demanganized cathode plate to obtain a treated cathode plate;
and (3) if the surface roughness Ra of the demanganized cathode plate obtained in the step (1) is more than 1.6 mu m, performing chemical mechanical polishing treatment on the demanganized cathode plate to obtain a treated cathode plate.
In the treatment method provided by the invention, firstly, residual manganese on the stripped cathode plate is removed through manganese removal treatment to obtain a manganese-removed cathode plate; and then judging to perform corrosion inhibition passivation treatment or chemical mechanical polishing treatment according to the roughness condition of the surface of the demanganized cathode plate to obtain the treated cathode plate. After the treated cathode plate is used for preparing manganese by subsequent electrolysis, the electrolytic manganese is easy to strip from the cathode plate, so that the stripping efficiency is greatly improved, the residual manganese amount on the cathode plate is effectively reduced, and the purity of a manganese product is improved.
In the invention, high-purity manganese refers to manganese with purity more than or equal to 5N.
Preferably, the demanganization process of step (1) comprises: the stripped cathode plate is soaked by adopting acid solution and then washed.
In the invention, the washing is generally performed by deionized water.
Preferably, the pH of the acidic solution in step (1) is from 0.1 to 2, and may be, for example, 0.1, 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8 or 2, but is not limited to the values recited, and other non-recited values within the range of values are equally applicable.
In the present invention, it is preferable to control the pH of the acidic solution within a specific range, so that manganese remaining on the cathode plate can be effectively removed.
Preferably, the acidic solution comprises an anolyte obtained by an electrolytic manganese process.
In the invention, the acidic solution is preferably an anolyte obtained by an electrolytic manganese process, the pH of the anolyte is generally 0.1-2, and the anolyte comprises the following main components: manganese sulfate, ammonium sulfate, and sulfuric acid.
Preferably, the time for soaking with the acidic solution is 3-5min, for example, 3min, 4min or 5min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the corrosion inhibition passivation treatment in step (2) includes: soaking the demanganizing cathode plate by adopting corrosion inhibition passivation solution, and then flushing.
Preferably, the preparation raw materials of the corrosion inhibition passivation solution comprise nitric acid, imidazole, water-soluble benzotriazole and hydrogen peroxide.
In the invention, nitric acid, imidazole, water-soluble benzotriazole and hydrogen peroxide are preferably adopted as raw materials for preparing the corrosion inhibition passivation solution, wherein the nitric acid has a corrosion effect, the imidazole and the water-soluble benzotriazole have a corrosion inhibition effect, and the hydrogen peroxide can improve the activity of the reaction.
Preferably, the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 3-5% of nitric acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.3% of hydrogen peroxide and the balance of water.
In the invention, deionized water is generally adopted as water used in the corrosion inhibition passivation solution.
In the invention, the mass percentage of the preparation raw materials of the corrosion inhibition passivation solution is preferably controlled within a specific range, so that the stripping effect of electrolytic manganese from a cathode plate can be further improved, and the residual manganese amount is reduced.
The mass percent of the nitric acid is 3-5%, for example, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8% or 5%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable; the water-soluble benzotriazole may be 0.3-0.5% by mass, for example, 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48% or 0.5%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the imidazole content is 0.2-0.3% by mass, for example, 0.2%, 0.22%, 0.24%, 0.26%, 0.28% or 0.3%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the hydrogen peroxide may be present in an amount of 0.1 to 0.3% by mass, for example, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.28% or 0.3%, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the purity of the nitric acid used in the corrosion inhibition passivation solution is electronic grade.
Preferably, the purities of imidazole, water-soluble benzotriazole and hydrogen peroxide used in the corrosion inhibition passivation solution are all analytically pure.
Preferably, the time for soaking by the corrosion inhibition passivation solution is 40-60s, for example, 40s, 42s, 45s, 48s, 50s, 52s, 55s, 58s or 60s, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the chemical mechanical polishing treatment of step (2) includes: and (3) chemically and mechanically polishing the demanganized cathode plate by adopting polishing solution, and then flushing.
Preferably, the polishing solution is prepared from abrasive particles, oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide.
In the invention, the preparation raw materials of the polishing solution preferably comprise abrasive particles, oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide, so that the surface of the cathode plate is brighter, electrolytic manganese can be more easily stripped from the cathode plate, the residual manganese amount is reduced, and meanwhile, the introduction of impurities into a manganese product is avoided.
Preferably, the polishing solution comprises the following preparation raw materials in percentage by mass: 6-8% of abrasive particles, 0.1-0.5% of oxalic acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.2% of hydrogen peroxide and the balance of water.
In the invention, the mass percentage of the raw materials for preparing the polishing solution is preferably controlled within a specific range, so that the stripping effect of electrolytic manganese from a cathode plate can be further improved, and the residual manganese amount is reduced.
In the present invention, the water used in the polishing solution is typically deionized water.
The abrasive particles comprise 6%, 6.2%, 6.5%, 6.8%, 7%, 7.2%, 7.5%, 7.8% or 8% by mass, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable; the oxalic acid content is 0.1-0.5% by mass, for example, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the water-soluble benzotriazole may be 0.3-0.5% by mass, for example, 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, 0.48% or 0.5%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the imidazole content is 0.2-0.3% by mass, for example, 0.2%, 0.22%, 0.24%, 0.26%, 0.28% or 0.3%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the hydrogen peroxide may be present in an amount of 0.1 to 0.2% by mass, for example, 0.1%, 0.12%, 0.15%, 0.18% or 0.2%, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure. Preferably, the abrasive particles comprise silica abrasive particles.
The abrasive particles preferably have an average particle size of 3 to 50 μm, and may be, for example, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the pH of the polishing solution in step (2) is 4-6, and may be, for example, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8 or 6, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the flow rate of the polishing solution is 40-60mL/min, for example, 40mL/min, 42mL/min, 44mL/min, 46mL/min, 48mL/min, 50mL/min, 52mL/min, 54mL/min, 56mL/min, 58mL/min or 60mL/min, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the chemical mechanical polishing time is 1-3min, for example, 1min, 2min or 3min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the chemical mechanical polishing pressure is 2-3kg, and may be, for example, 2kg, 2.2kg, 2.4kg, 2.6kg, 2.8kg or 3kg, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the polishing time and pressure are preferably controlled within a specific range, so that the polishing effect on the cathode plate can be further improved.
As a preferred technical scheme of the present invention, the treatment method comprises the following steps:
(1) Soaking the stripped cathode plate for 3-5min by adopting an acidic solution with the pH value of 0.1-2, and then flushing to obtain a demanganized cathode plate; the acidic solution comprises anolyte obtained by an electrolytic manganese process;
(2) If the surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is less than or equal to 1.6 mu m, soaking the demanganizing cathode plate for 40-60s by adopting corrosion inhibition passivation solution, and then flushing to obtain a treated cathode plate;
the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 3-5% of nitric acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.3% of hydrogen peroxide and the balance of water, wherein the purity of nitric acid used by the corrosion inhibition passivation solution is electronic grade, and the purities of imidazole, water-soluble benzotriazole and hydrogen peroxide used by the corrosion inhibition passivation solution are all analytically pure;
if the surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is more than 1.6 mu m, chemically and mechanically polishing the demanganizing cathode plate for 1-3min under the condition that the pressure is 2-3kg by adopting polishing solution, and then flushing to obtain a treated cathode plate;
the polishing solution comprises the following preparation raw materials in percentage by mass: 6-8% of abrasive particles, 0.1-0.5% of oxalic acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.2% of hydrogen peroxide and the balance of water, wherein the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure, the abrasive particles comprise silicon dioxide abrasive particles, the average particle size of the abrasive particles is 3-50 mu m, the pH value of the polishing solution is 4-6, and the flow rate of the polishing solution is 40-60mL/min.
Compared with the prior art, the invention has the following beneficial effects:
the treatment method provided by the invention can enable the cathode plate to be easier to strip from the cathode plate in the subsequent electrolytic manganese preparation, greatly improves the stripping efficiency, effectively reduces the residual manganese on the cathode plate, and is beneficial to improving the purity of manganese products, and the treatment method can enable the residual manganese to be below 9.0%, to be below 7.6% under the optimal condition, and to enable the purity of manganese products to be above 99.9991%.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps:
(1) Soaking the stripped cathode plate for 4min by adopting an anolyte (mainly containing manganese sulfate, ammonium sulfate and sulfuric acid, and having the pH value of 0.15) obtained by adopting an electrolytic manganese process, and then flushing with deionized water to obtain a demanganized cathode plate;
(2) The surface roughness Ra of the demanganized cathode plate obtained in the step (1) is 1.2 mu m, the demanganized cathode plate is soaked for 50s by adopting corrosion inhibition passivation solution, and then deionized water is used for washing, so that a treated cathode plate is obtained;
the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 4% of nitric acid, 0.4% of water-soluble benzotriazole, 0.25% of imidazole, 0.2% of hydrogen peroxide and the balance of water, wherein the purity of nitric acid used in the corrosion inhibition passivation solution is electronic grade, and the purity of imidazole, water-soluble benzotriazole and hydrogen peroxide used in the corrosion inhibition passivation solution are all analytically pure.
Example 2
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps:
(1) Soaking the stripped cathode plate for 3min by adopting an anolyte (mainly containing manganese sulfate, ammonium sulfate and sulfuric acid, and having the pH value of 0.15) obtained by adopting an electrolytic manganese process, and then flushing with deionized water to obtain a demanganized cathode plate;
(2) The surface roughness Ra of the demanganized cathode plate obtained in the step (1) is 0.8 mu m, the demanganized cathode plate is soaked for 60 seconds by adopting corrosion inhibition passivation solution, and then deionized water is used for washing, so that a treated cathode plate is obtained;
the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 3% of nitric acid, 0.5% of water-soluble benzotriazole, 0.2% of imidazole, 0.3% of hydrogen peroxide and the balance of water, wherein the purity of nitric acid used in the corrosion inhibition passivation solution is electronic grade, and the purities of imidazole, water-soluble benzotriazole and hydrogen peroxide are all analytically pure.
Example 3
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps:
(1) Soaking the stripped cathode plate for 5min by adopting an anolyte (mainly containing manganese sulfate, ammonium sulfate and sulfuric acid, and having the pH value of 0.3) obtained by adopting an electrolytic manganese process, and then flushing with deionized water to obtain a demanganized cathode plate;
(2) The surface roughness Ra of the demanganized cathode plate obtained in the step (1) is 1.5 mu m, the demanganized cathode plate is soaked for 40 seconds by adopting corrosion inhibition passivation solution, and then deionized water is used for washing, so that a treated cathode plate is obtained;
the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 5% of nitric acid, 0.3% of water-soluble benzotriazole, 0.3% of imidazole, 0.1% of hydrogen peroxide and the balance of water, wherein the purity of nitric acid used in the corrosion inhibition passivation solution is electronic grade, and the purity of imidazole, water-soluble benzotriazole and hydrogen peroxide used in the corrosion inhibition passivation solution are all analytically pure.
Example 4
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps:
(1) Soaking the stripped cathode plate for 4min by adopting an anolyte (mainly containing manganese sulfate, ammonium sulfate and sulfuric acid, and having the pH value of 0.1) obtained by adopting an electrolytic manganese process, and then flushing with deionized water to obtain a demanganized cathode plate;
(2) The surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is 1.8 mu m, the demanganizing cathode plate is subjected to chemical mechanical polishing for 2min under the condition that the pressure is 2.5kg by adopting polishing solution, and then the demanganizing cathode plate is rinsed by deionized water, so that a treated cathode plate is obtained;
the polishing solution comprises the following preparation raw materials in percentage by mass: the polishing solution comprises 7% of abrasive particles, 0.3% of oxalic acid, 0.4% of water-soluble benzotriazole, 0.25% of imidazole, 0.15% of hydrogen peroxide and the balance of water, wherein the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure, the abrasive particles are silica abrasive particles, the average particle size is 20 mu m, the pH of the polishing solution is 4.2, and the flow rate of the polishing solution is 50mL/min.
Example 5
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps:
(1) Soaking the stripped cathode plate for 3min by adopting an anolyte (mainly containing manganese sulfate, ammonium sulfate and sulfuric acid, and having the pH value of 0.15) obtained by adopting an electrolytic manganese process, and then flushing with deionized water to obtain a demanganized cathode plate;
(2) The surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is 1.9 mu m, chemical mechanical polishing is carried out on the demanganizing cathode plate for 1min under the condition that the pressure is 3kg by adopting polishing solution, and then deionized water is used for washing, so that the treated cathode plate is obtained;
the polishing solution comprises the following preparation raw materials in percentage by mass: the polishing solution comprises 6% of abrasive particles, 0.5% of oxalic acid, 0.3% of water-soluble benzotriazole, 0.3% of imidazole, 0.1% of hydrogen peroxide and the balance of water, wherein the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure, the abrasive particles are silica abrasive particles, the average particle size is 45 mu m, the pH of the polishing solution is 5, and the flow rate of the polishing solution is 40mL/min.
Example 6
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which comprises the following steps:
(1) Soaking the stripped cathode plate for 5min by adopting an anolyte (mainly containing manganese sulfate, ammonium sulfate and sulfuric acid, and having the pH of 0.15) obtained by adopting an electrolytic manganese process, and then flushing with deionized water to obtain a demanganized cathode plate;
(2) The surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is 2.1 mu m, chemical mechanical polishing is carried out on the demanganizing cathode plate for 3min under the condition that the pressure is 2kg by adopting polishing solution, and then deionized water is used for washing, so that the treated cathode plate is obtained;
the polishing solution comprises the following preparation raw materials in percentage by mass: 8% of abrasive particles, 0.1% of oxalic acid, 0.5% of water-soluble benzotriazole, 0.2% of imidazole, 0.2% of hydrogen peroxide and the balance of water, wherein the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure, the abrasive particles are silicon dioxide abrasive particles, the average particle size is 8 mu m, the pH of the polishing solution is 5.9, and the flow rate of the polishing solution is 60mL/min.
Example 7
This example provides a treatment method for preparing a cathode plate for high-purity manganese, which is different from example 1 only in that nitric acid is not added to the raw materials for preparing the corrosion inhibition passivation solution, and the addition amount of other raw materials is unchanged.
Example 8
The present example provides a treatment method for preparing a cathode plate for high-purity manganese, which is different from example 1 only in that imidazole is not added to the raw materials for preparing the corrosion inhibition passivation solution, and the addition amount of other raw materials is unchanged.
Example 9
The present example provides a treatment method for preparing a cathode plate for high-purity manganese, which is different from example 1 only in that water-soluble benzotriazole is not added to the raw materials for preparing the corrosion inhibition passivation solution, and the addition amount of other raw materials is unchanged.
Example 10
This example provides a treatment method for preparing a cathode plate for high-purity manganese, which is different from example 1 only in that hydrogen peroxide is not added to the raw materials for preparing the corrosion inhibition passivation solution, and the addition amount of other raw materials is unchanged.
Example 11
The embodiment provides a treatment method for preparing a cathode plate for high-purity manganese, which is different from embodiment 1 only in that the preparation raw materials of the corrosion inhibition passivation solution comprise the following components in percentage by mass: 4% of nitric acid, 0.1% of water-soluble benzotriazole, 0.25% of imidazole, 0.2% of hydrogen peroxide and the balance of water.
Example 12
This example provides a treatment method for preparing a cathode plate for high purity manganese, which differs from example 4 only in that oxalic acid is not added to the raw materials for preparing the polishing solution, and the addition amounts of other raw materials are unchanged.
Example 13
This example provides a treatment method for preparing a cathode plate for high purity manganese, which differs from example 4 only in that water-soluble benzotriazole is not added to the raw materials for preparing the polishing solution, and the addition amounts of the other raw materials are unchanged.
Example 14
This example provides a treatment method for preparing a cathode plate for high purity manganese, which differs from example 4 only in that imidazole is not added to the raw materials for preparing the polishing solution, and the addition amounts of other raw materials are unchanged.
Example 15
This example provides a treatment method for preparing a cathode plate for high purity manganese, which differs from example 4 only in that hydrogen peroxide is not added to the raw materials for preparing the polishing liquid, and the addition amounts of the other raw materials are unchanged.
Example 16
This example provides a treatment method for preparing a cathode plate for high purity manganese, which differs from example 4 only in that the preparation raw materials of the polishing solution include, by mass: 7% of abrasive particles, 0.05% of oxalic acid, 0.4% of water-soluble benzotriazole, 0.25% of imidazole, 0.15% of hydrogen peroxide and the balance of water.
Comparative example 1
This comparative example provides a treatment method for preparing a cathode plate for high-purity manganese, which differs from example 1 only in that the corrosion inhibition passivation solution is replaced with a mixed aqueous solution of nitric acid and potassium dichromate, wherein the mass percentage of nitric acid is 5%, the mass percentage of potassium dichromate is 4%, the purity of nitric acid is analytically pure, and the purity of potassium dichromate is superior pure.
Comparative example 2
This comparative example provides a method of treating a cathode plate which differs from example 1 only in that step (2) is not performed, and the treated cathode plate is the demanganized cathode plate obtained in step (1).
Comparative example 3
This comparative example provides a method of treating a cathode plate which differs from example 4 only in that step (2) is not performed, and the treated cathode plate is the demanganized cathode plate obtained in step (1).
Electrolytic manganese production was performed using the treated cathode plates obtained in examples 1 to 16 and comparative examples 1 to 3, then the electrolytic manganese on the cathode plate was stripped, and the amount of residual manganese on the stripped cathode plate was measured, and the residual manganese amount=1-the mass of manganese stripped/the mass of electrolytic manganese, the mass of electrolytic manganese=the mass of the out-tank cathode plate-the mass of the cathode plate before electrolysis, and the mass of the out-tank cathode plate, the mass of the cathode plate before electrolysis, and the mass of manganese stripped were all obtained by weighing, and the residual manganese amount results are shown in table 1.
The purity of the peeled manganese product was measured by GDMS, and the results are shown in Table 1.
TABLE 1
From the data in Table 1, the following points can be seen:
(1) From the data of examples 1-16, it can be seen that the treatment method provided by the invention can make the residual manganese content be less than 9.0%, under the preferred conditions, less than 7.6%, and the purity of the manganese product be more than 99.9991%.
(2) From a combination of the data of examples 1 and examples 7 to 10, it can be seen that examples 7 to 10 differ from example 1 only in that nitric acid, imidazole, water-soluble benzotriazole and hydrogen peroxide are not added, respectively, and that the amount of residual manganese in example 1 is significantly lower than that in examples 7 to 10, and that the purity of the manganese product in example 1 is significantly higher than that in examples 7 to 10, and that the synergistic effect of nitric acid, imidazole, water-soluble benzotriazole and hydrogen peroxide in the corrosion inhibition passivation solution is preferably controlled, so that the purity of the manganese product can be improved while the amount of residual manganese can be reduced.
(3) As can be seen from the data of comparative examples 1 and 11, the mass percentage of the water-soluble benzotriazole in the corrosion-inhibiting passivation solution used in example 1 is 0.4%, and the amount of residual manganese in example 1 is significantly lower than that in example 11, and the purity of the manganese product in example 1 is significantly higher than that in example 11, compared with 0.1% in example 11.
(4) From a combination of the data of examples 4 and examples 12 to 15, it can be seen that examples 12 to 15 differ from example 4 only in that oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide are not added, respectively, and that the amount of residual manganese in example 4 is significantly lower than that in examples 12 to 15, and that the purity of manganese product in example 4 is significantly higher than that in examples 12 to 15, whereby it can be seen that the present invention preferably controls the synergistic effect of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide in the polishing liquid, and can reduce the amount of residual manganese while improving the purity of manganese product.
(5) As can be seen from a combination of the data of example 4 and example 16, the mass percentage of oxalic acid in the polishing solution used in example 4 was 0.3%, while the mass percentage of oxalic acid in example 16 was 0.05%, the purity of the manganese product in example 4 was significantly higher than that in example 16, and the amount of residual manganese in example 4 was significantly lower than that in example 16, so that it was found that the present invention preferably controlled the mass percentage of each component in the polishing solution in a specific range, and the purity of the manganese product was improved while the amount of residual manganese was further reduced.
(6) As can be seen from the data of comparative example 1 and comparative example 1, the comparative example 1 is different from example 1 only in that the corrosion inhibition passivation solution is replaced by a mixed aqueous solution of nitric acid and potassium dichromate, the residual manganese content in example 1 is obviously lower than that in comparative example 1, and the purity of the manganese product in example 1 is obviously higher than that in comparative example 1, so that the corrosion inhibition passivation solution provided by the invention can achieve the effects of reducing the residual manganese content and improving the purity of the manganese product.
(7) As can be seen from the data of comparative examples 1 and 2 and examples 4 and 3, comparative example 2 differs from example 1 only in that no corrosion inhibition passivation treatment is performed, comparative example 3 differs from example 4 only in that no chemical mechanical polishing treatment is performed, the amount of residual manganese in example 1 is significantly lower than that in comparative example 2, and the amount of residual manganese in example 4 is significantly lower than that in comparative example 3, and thus it can be seen that the present invention can reduce the amount of residual manganese and enhance the peeling effect by the corrosion inhibition passivation treatment or chemical mechanical polishing treatment.
In summary, the treatment method provided by the invention can enable the cathode plate to be easier to strip from the cathode plate in the subsequent electrolytic manganese production, greatly improves the stripping efficiency, effectively reduces the residual manganese on the cathode plate, and is beneficial to improving the purity of manganese products.
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 process for preparing a cathode plate for high purity manganese, the process comprising the steps of:
(1) Carrying out demanganization on the stripped cathode plate to obtain a demanganization cathode plate;
(2) If the surface roughness Ra of the demanganized cathode plate obtained in the step (1) is less than or equal to 1.6 mu m, performing corrosion inhibition passivation treatment on the demanganized cathode plate to obtain a treated cathode plate;
and (3) if the surface roughness Ra of the demanganized cathode plate obtained in the step (1) is more than 1.6 mu m, performing chemical mechanical polishing treatment on the demanganized cathode plate to obtain a treated cathode plate.
2. The process of claim 1, wherein the demanganizing treatment of step (1) comprises: the stripped cathode plate is soaked by adopting acid solution and then washed.
3. The process according to claim 2, wherein the pH of the acidic solution is 0.1-2;
preferably, the acidic solution comprises an anolyte obtained by an electrolytic manganese process;
preferably, the time for soaking with the acidic solution is 3-5min.
4. A process according to any one of claims 1 to 3, wherein the corrosion inhibition passivation treatment of step (2) comprises: soaking the demanganizing cathode plate by adopting corrosion inhibition passivation solution, and then flushing.
5. The method according to claim 4, wherein the raw materials for preparing the corrosion inhibition passivation solution comprise nitric acid, imidazole, water-soluble benzotriazole and hydrogen peroxide;
preferably, the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 3-5% of nitric acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.3% of hydrogen peroxide and the balance of water;
preferably, the purity of the nitric acid used by the corrosion inhibition passivation solution is electronic grade;
preferably, the purities of imidazole, water-soluble benzotriazole and hydrogen peroxide used in the corrosion inhibition passivation solution are all analytically pure;
preferably, the time for soaking by adopting the corrosion inhibition passivation solution is 40-60s.
6. The method of any one of claims 1-5, wherein the chemical mechanical polishing process of step (2) comprises: and (3) chemically and mechanically polishing the demanganized cathode plate by adopting polishing solution, and then flushing.
7. The method according to claim 6, wherein the polishing liquid is prepared from abrasive grains, oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide;
preferably, the polishing solution comprises the following preparation raw materials in percentage by mass: 6-8% of abrasive particles, 0.1-0.5% of oxalic acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.2% of hydrogen peroxide and the balance of water;
preferably, the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure;
preferably, the abrasive particles comprise silica abrasive particles;
preferably, the abrasive particles have an average particle size of 3 to 50 μm.
8. The method according to claim 6 or 7, wherein the pH of the polishing liquid in step (2) is 4 to 6;
preferably, the flow rate of the polishing solution is 40-60mL/min.
9. The process of any one of claims 6 to 8, wherein the chemical mechanical polishing is for a period of 1 to 3 minutes;
preferably, the chemical mechanical polishing pressure is 2-3kg.
10. A process according to any one of claims 1 to 9, characterized in that it comprises the steps of:
(1) Soaking the stripped cathode plate for 3-5min by adopting an acidic solution with the pH value of 0.1-2, and then flushing to obtain a demanganized cathode plate; the acidic solution comprises anolyte obtained by an electrolytic manganese process;
(2) If the surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is less than or equal to 1.6 mu m, soaking the demanganizing cathode plate for 40-60s by adopting corrosion inhibition passivation solution, and then flushing to obtain a treated cathode plate;
the corrosion inhibition passivation solution is prepared from the following raw materials in percentage by mass: 3-5% of nitric acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.3% of hydrogen peroxide and the balance of water, wherein the purity of nitric acid used by the corrosion inhibition passivation solution is electronic grade, and the purities of imidazole, water-soluble benzotriazole and hydrogen peroxide used by the corrosion inhibition passivation solution are all analytically pure;
if the surface roughness Ra of the demanganizing cathode plate obtained in the step (1) is more than 1.6 mu m, chemically and mechanically polishing the demanganizing cathode plate for 1-3min under the condition that the pressure is 2-3kg by adopting polishing solution, and then flushing to obtain a treated cathode plate;
the polishing solution comprises the following preparation raw materials in percentage by mass: 6-8% of abrasive particles, 0.1-0.5% of oxalic acid, 0.3-0.5% of water-soluble benzotriazole, 0.2-0.3% of imidazole, 0.1-0.2% of hydrogen peroxide and the balance of water, wherein the purities of oxalic acid, water-soluble benzotriazole, imidazole and hydrogen peroxide used in the polishing solution are all analytically pure, the abrasive particles comprise silicon dioxide abrasive particles, the average particle size of the abrasive particles is 3-50 mu m, the pH value of the polishing solution is 4-6, and the flow rate of the polishing solution is 40-60mL/min.
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