CN105624727A - Method for simultaneously producing electrolytic manganese metal and electrolytic manganese dioxide in one electrolysis bath - Google Patents
Method for simultaneously producing electrolytic manganese metal and electrolytic manganese dioxide in one electrolysis bath Download PDFInfo
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
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Abstract
The invention relates to a method for simultaneously producing electrolytic manganese metal and electrolytic manganese dioxide in one electrolysis bath. The method comprises the following steps: adding one or more of Bi2O3, BiCl3, BiOCl, Bi(OH)3 and Bi(OH)3.BiOSO4 into an electrolyte, and carrying out electrolysis by a widely used electrolytic manganese production device by using an industrial cloth filter as a diaphragm, thereby efficiently obtaining electrolytic manganese at the cathode and obtaining electrolytic manganese dioxide at the anode, wherein the cathode is a stainless steel plate, and the current density is controlled at 180-300 A/m<2>; the anode is a titanium plate, titanium manganese alloy or MnO2-coated titanium plate, and the anode current density is 50-100 A/m<2>; and the additive content in the electrolyte is controlled at 1-10 mg/L. The method can fully utilize the existing production device to simultaneously obtain the two products on one production line, thereby lowering the energy consumption.
Description
Technical field
The invention belongs to technical field of chemistry, it relates to one, in same electrolyzer, obtains electrolytic manganese dioxide in anode production, and negative electrode obtains the method for electrolytic metal Mn.
Background technology
Along with the acceleration of world industry process, energy consumption increases increasingly, CO2Quantity discharged increase severely. Big country is discharged as carbon, China's planning obviously reduces the carbon quantity discharged of per GDP within the coming years, the electric power energy more than 70% of current China derives from thermoelectricity, therefore eliminates or cuts down high energy consumption technique, and the new cleanproduction process that development is saved energy and reduce the cost is the important channel of carbon emission reduction. Manganese metal is important industrial chemicals and strategic resource, and Manganse Dioxide is important basic material at lithium cell and alkaline cell industry, both indispensable in Economic development. Metal current manganese and Manganse Dioxide are all that the mode by aqueous electrolysis obtains, wherein electrolytic manganese be by weakly alkaline ammonium sulfate and manganese sulfate solution in negative plate deposition, every ton of electrolytic manganese power consumption about about 6,000 degree; And electrolysis MnO2It is manganous sulfate electrolysis under sour environment, positive plate deposits, every ton of electrolysis MnO2Power consumption is about 3-4 about thousand degree. In electrolytic manganese production process, anode generates O2, and at electrolysis MnO2In production process, negative electrode generates H2, both generate useless gas at anode or negative electrode, it does not have be used, if electrolytic manganese and electrolytic manganese dioxide process are combined, in same electrolytic process, negative electrode generates electrolytic manganese, and anode generates electrolysis MnO2, then can make full use of the electrolytic reaction on each electrode, greatly fall low power consumption, reach the object of cleaner production.
Although at Mn-MnO2The research of electrolysis simultaneously relatively early receives concern, but wants to meet with difficulty greatly in practical application, and difficulty is metal M n and electrolysis MnO2Working condition difference huge, it is at high current density (300��400A/m that industry separately produces electrolytic metal Mn2), low temperature (40 DEG C), generates under neutral alkali on the weak side (pH=7-8) condition, and industry electrolysis MnO separately2It is at low current density (50��80A/m2), high temperature (95 DEG C), generates under strong acidic condition, and the bath composition of independent electrolytic process is different, and electrolytic metal Mn uses MnSO4-(NH4)2SO4Solution, electrolysis MnO2It is use MnSO4-H2SO4Solution. For above-mentioned difference, most research is at design electrolysis production Mn and MnO simultaneously2Following scheme is adopted during process:
(1) electrolyzer is two separate space separated in cathode can and anode slot, catholyte and anolyte realize repeats itself separately, the mass transfer of electrolytic solution is not had to flow between anode and cathode, just ensure conducting to form current circuit between anode and cathode by porousness dividing plate, this kind of mode makes its industrialization design of electrolysis cells, apply very loaded down with trivial details, cost of investment height, it is not suitable for tens and even the application (Liu Rongyi in parallel to electrolyzer up to a hundred, Mei Guanggui, Zhong Zhuqian. manganese-Manganse Dioxide simultaneous electrolysis novel process research. nation manganese industry, 1996, 14 (3) :) 40-43, Chen An, Zhu Yaohua, Zhang Qixin. produce the method [J] of electrolytic metal Mn and fibrous electrolytical manganese dioxide simultaneously. Fujian Normal University's journal (natural science edition), 1988,4 (3): 54-62,
(2) temperature contrast required due to negative electrode and positive column is very big, and catholyte Mn district to be maintained the temperature of about 40 DEG C, generally to be used coil pipe cooling in this region, and at anode electrolysis MnO2District needs to be heated to more than 90 DEG C. The research of above-mentioned Liu Rong justice, Chen An etc., likely can accomplish for laboratory to be maintained the short period of time such temperature head, but industrial production is all uninterruptedly carry out for 24 hours, due to the thermal conduction between anode and cathode, even if increasing cooling water flow, the extremely difficult low temperature maintaining cathodic area of long-time electrolysis, brings very big obstacle to industrial applications;
In addition, research is also had to use MnCl2As the method for electrolytic solution main component, as Chen An, Zhang Qixin etc. adopt MnCl2Solution is electrolyte system, adopts acidproof, alkaline-resisting, porousness or microporosity plastics to be dividing plate, obtains electrolytic metal Mn at negative electrode, and anode obtains fibrous electrolytical manganese dioxide; Chen Haiyan also adopts MnCl2Electrolyte system, it was demonstrated that adopt MnCl2Electrolytic solution MnCl2Electrolytic solution is than using MnSO4Required bath voltage is low. But the method generates MnO at anode2While can produce chlorine, production process bring pollution and potential safety hazard.
Du Jie uses ion-exchange membrane to separate negative electrode and anode, and negative electrode uses MnSO4-(NH4)2SO4Solution, and anode uses MnSO4-H2SO4Solution, electrolysis simultaneously generates electrolysis Mn and electrolysis MnO2, ion-exchange membrane then plays the effect separating catholyte and anolyte, ensures the electroconductibility between negative electrode and anode simultaneously. Adopt the advantage of ion-exchange membrane to be to ensure that the electrolytic solution composition of cathodic area and positive column can not be mixed mutually by barrier film, also avoid the mn ion of anode in a large number to cathodic migration, reduce the manganese ion concentration of positive column.
Li Weishan etc. (" utilizing paired electrolysis method synthesis electrocatalytic manganese dioxide and electrolytic manganese ", South China Normal University's journal (natural science edition), 1990,52-55) add Ag in positive column+, by anodic oxidation Ag+For Ag2+, Ag2+It is oxidized Mn again2+Generate MnO2, cathodic area electrolysis generates metal M n, and at 40 DEG C, anode efficiency reaches 91%, and at anode, this is a kind of electrocatalytic reaction, although anode high-level efficiency obtains MnO2, but following three shortcomings make it be difficult to practical application: the Ag that (1) to be used price high+, these Ag+Although not consuming in electrolytic process, but can be precipitated by sulfide cleaner in the process of leaching ore deposit, being carried under one's arms and loss by slag; (2) to be used special, anionic membrane of good performance to intercept Ag+Under the electric field to cathode motion, once there be minute quantity Ag+Enter negative electrode, preferential will deposit on negative electrode, and cause negative electrode to go up the extensive molten plate of metal M n of plate; (3) due to MnO2It is utilize Ag2+Strong oxidizing property, by oxidation Mn2+Chemical reaction obtains, and is a kind of loose, and the throw out being suspended in anolyte, its tap density is much smaller than electrolysis MnO2, and this kind obtained by chemical reaction be chemistry MnO2, its brilliant type is not �� type, and only has �� type MnO2Required for being only battery industry.
Simultaneous electrolysis is produced and is realized electrolysis MnO2It is the greatest differences of the best electrolysis temperature of two electrode processes with the maximum difficult point of metal M n application, and anode electrolysis MnO2Current efficiency temperature is very responsive, when temperature of anode is brought up to more than 50 DEG C, its current efficiency will obviously promote, and use traditional additive to carry out electrolysis Mn at such a temperature and produce and be there will be Mn and do not go up plate, flake on a large scale, molten plate, can not get electrolytic manganese, therefore technique is wanted electrolysis simultaneously and is obtained two kinds of products with high current efficiency and be difficult to accomplish at present, must improve by anticathode electrolytic process, improve the temperature range that it is suitable for, make the effect that negative electrode and anode can reach satisfied, it is that cost is lower that additive to wherein development of new improves the Applicable temperature of cathodic process, simple scheme, the independent electrolysis Mn process of major part is all use SeO at present2For additive, this substance is normal below 42 DEG C to be used, current efficiency is 68��70%, sharply decline higher than this temperature current efficiency, after mainly temperature raises, its adsorptive power on negative electrode reduces, and therefore the hydrogen gas evolution overpotential of cathode surface Mn reduces, occur that Mn not easily deposits, or molten plate. Select novel additive can promote the Applicable temperature of catholyte, such that it is able to while ensureing that negative electrode normal electrical solution obtains metal M n, obtain electrolysis MnO at anode with good current efficiency2. So just can use existing electrolysis Mn large-scale production device, it is achieved the simultaneous electrolysis MnO of production electrolysis simultaneously2With metal M n.
Summary of the invention:
The present invention relates to and use a kind of novel additive, this additive joins in electrolytic solution so that (50��65 DEG C) can electrolysis production metal M n and electrolysis MnO at relatively high temperatures2, negative electrode and anode all reach comparatively satisfied current efficiency, it is important that the method can carry out in the electrolyzer of now widely used production electrolytic manganese, greatly facilitate electrolytic manganese factory then produce two kinds of products simultaneously, save fixed assets investment. In electrolytic process, negative electrode and positive column solution are circulations, and two regions do not have temperature head yet, it is not necessary to solution negative electrode and anode region conduct heat mutually, and negative electrode and anode use common industrial filter cloth as barrier film.
For reaching above-mentioned technique effect, the technical solution used in the present invention is as follows:
Producing a method for electrolytic metal Mn and electrolytic manganese dioxide in same electrolyzer simultaneously, add additive in the electrolytic solution, additive comprises the compound containing Bi.
Further improvement, additive content in the electrolytic solution is 1-10mg/L.
Further improvement, described additive comprises at least one in the sulfuric acid oxidation thing of the oxide compound of Bi element, the muriate of Bi element, the oxychloride of Bi element, the oxyhydroxide of Bi element and Bi element.
Further improvement, the oxide compound of described Bi element is Bi2O3; The muriate of Bi element is BiCl3; The oxychloride of Bi element is BiOCl; The oxyhydroxide of Bi element is Bi (OH)3; The sulfuric acid oxidation thing of Bi element is Bi (OH)3��BiOSO4��
Further improvement, described additive comprises Bi (OH)3��BiOSO4And Bi2O3, Bi (OH)3��BiOSO4With Bi2O3Mass ratio be 1:1; Additive content in the electrolytic solution is 5mg/L.
Further improvement, described electrolyzer uses industrial filter cloth as the barrier film in cathodic area and positive column; Add liquid to add from cathodic area, overflow liquid and overflow from positive column; Negative electrode is stainless steel plate; Workshop section added by electrolytic solution, and in electrolyzer, the Fe content of electrolytic solution is 32-38g/L, ammonium sulfate content be 80-110g/L, pH is 6.5-6.8; Electrolysis workshop section: in electrolyzer, the Fe content of electrolytic solution is 18-20g/L, ammonium sulfate content be 90-110g/L, pH is 7.5-8.0; Electrolysis temperature is 50 DEG C-65 DEG C; The current density of negative electrode is 180��300A/m2, negative electrode changes plate in every 24 hours; Anode is titanium plate, titanium Mn alloy plate or MnO2Coated titanium plate; Anodic current density is 60��80A/m2, the sulfuric acid content of positive column is 30��40gH2SO4/ L, electrolysing period is 7-14 days.
Further improvement, described industrial filter cloth is terylene filter cloth, polypropylene fibre filter cloth or polyester cloth.
Can at high temperature electrolysis production metal M n and electrolysis MnO in the present invention2Additive be the oxide compound containing Bi, muriate, oxychloride, oxyhydroxide, sulfuric acid oxidation thing etc., specifically comprise following material: Bi2O3, BiCl3, BiOCl, Bi (OH)3, Bi (OH)3��BiOSO4, additive can be the one in above-mentioned substance, or two kinds and above combine, the content of additive in the electrolytic solution that electrolytic manganese production is used controls at 1-10mg/L.
The additive of application the present invention, directly can apply on existing electrolytic manganese production equipment, the manufacturing condition of the present invention is used to add workshop section for (1) electrolytic solution: qualifying liquid requirement Fe content is that 32-38g/L, ammonium sulfate content control at 6.5-6.8 at 80-110g/L, pH, add liquid to add from cathodic area, overflow liquid positive column and flow out. (2) electrolysis workshop section: negative electrode uses stainless steel, the Fe content that electrolyzer inner cathode requires is that 18-20g/L, ammonium sulfate content control at 7.5-8.0 at 90-110g/L, pH. Groove temperature control is between 50-65 DEG C, and the cathodic area catholyte cycle is 24 hours, and current density controls at 180��300A/m2; Anode uses titanium plate, titanium manganese alloy or MnO2Coated titanium plate, anodic current density is 60��80A/m2, anolyte acidity controls at 30��40gH2SO4/ L, electrolysing period is 7-14 days.
Described additive content in the electrolytic solution controls at 1-10mg/L, directly adds in electrolytic solution according to required additive amount.
The useful effect of the present invention:
Compared with prior art, the technical scheme of the present invention has the following advantages:
(1) the present invention uses above-mentioned additive to join in electrolytic solution, at relatively high temperatures (50��65 DEG C), can obtain electrolysis Mn at negative electrode, and anode obtains electrolysis MnO2, cathode efficiency reaches 65-70%, suitable with the current efficiency of independent electrolysis production metal M n, and is 48��60% in anodic current efficiency, and this kind of method compares independent electrolysis production metal M n, is equivalent to save production electrolysis MnO2The electricity consumption of part;
(2) existing method is compared, the method can carry out in the electrolyzer of now widely used production electrolytic manganese, the electrolyzer being separated with anode without the need to making the negative electrode of complex structure in addition, greatly facilitate electrolytic manganese factory then produce two kinds of products simultaneously, save fixed assets investment. In electrolytic process, negative electrode and positive column solution are circulations, and two regions do not have temperature head yet, it is not necessary to solution negative electrode and anode region conduct heat mutually.
Embodiment
Below in conjunction with specific embodiment, the technical scheme of the present invention is described in further details.
Following examples, electrolyzer uses industrial filter cloth to be separated in the cathodic area of electrolyzer and positive column; Industrial filter cloth can be terylene filter cloth, polypropylene fibre filter cloth or polyester cloth.
Embodiment 1
Get BiOCl as additive, this additive in the electrolytic solution content be 3mg/L.
Use and existing electrolytic manganese production equipment carries out electrolysis, it may also be useful to the manufacturing condition of the present invention adds workshop section for (1) electrolytic solution: qualifying liquid requires that Fe content is that 32-38g/L, ammonium sulfate content control at 6.5-6.8 at 100-110g/L, pH. (2) electrolysis workshop section: require in electrolyzer that Fe content is that 18-20g/L, ammonium sulfate content control at 7.5-8.0 at 100-110g/L, pH. Whole groove temperature control is at 50 DEG C; Cathode current density 300A/m2, negative electrode changes plate, anodic current density 80A/m in every 24 hours2, positive column sulfuric acid content is about 40g/L, and anode changes plate in every 7 days-14 days. Electrolysis result: cathode plate surface light, substantially without manganese knot, current efficiency 71%, the fine and close black electrolysis MnO of anode surface attachment2, scraping and all weigh, calculating current efficiency is 48%, and product meets electrolysis MnO after measured2National standard.
Embodiment 2
Get Bi2O3As additive, this additive in the electrolytic solution content be 4mg/L.
Use and existing electrolytic manganese production equipment carries out electrolysis, it may also be useful to the manufacturing condition of the present invention adds workshop section for (1) electrolytic solution: qualifying liquid requires that Fe content is that 32-38g/L, ammonium sulfate content control at 6.5-6.8 at 100-110g/L, pH. (2) electrolysis workshop section: require in electrolyzer that Fe content is that 18-20g/L, ammonium sulfate content control at 7.5-8.0 at 90g/L, pH. Whole groove temperature control is at 55 DEG C; Cathode current density 250A/m2, negative electrode changes plate, anodic current density 80A/m in every 24 hours2, positive column sulfuric acid content is about 40g/L, and anode changes plate in every 7 days. Electrolysis result: cathode plate surface light, substantially without manganese knot, current efficiency 67%, the fine and close black electrolysis MnO of anode surface attachment2, scraping and all weigh, calculating current efficiency is 54%, and product meets electrolysis MnO after measured2National standard.
Embodiment 3
Get Bi (OH)3��BiOSO4As additive, this additive in the electrolytic solution content be 2mg/L.
Use and existing electrolytic manganese production equipment carries out electrolysis, it may also be useful to the manufacturing condition of the present invention adds workshop section for (1) electrolytic solution: qualifying liquid requires that Fe content is that 32-38g/L, ammonium sulfate content control at 6.5-6.8 at 100-110g/L, pH. (2) electrolysis workshop section: require in electrolyzer that Fe content is that 18-20g/L, ammonium sulfate content control at 7.5-8.0 at 90g/L, pH. Whole groove temperature control is at 60 DEG C; Cathode current density 200A/m2, negative electrode changes plate, anodic current density 70A/m in every 24 hours2, positive column sulfuric acid content is about 40g/L, and anode changes plate in every 7 days. Electrolysis result: cathode plate surface light, substantially without manganese knot, current efficiency 62%, the fine and close black electrolysis MnO of anode surface attachment2, scraping and all weigh, calculating current efficiency is 59%, and product meets electrolysis MnO after measured2National standard.
Embodiment 4
Get Bi (OH)3��BiOSO4And Bi2O3By 1:1 weight ratio as mixed additive, this mixed additive in the electrolytic solution content be 5mg/L.
Use and existing electrolytic manganese production equipment carries out electrolysis, it may also be useful to the manufacturing condition of the present invention adds workshop section for (1) electrolytic solution: qualifying liquid requires that Fe content is that 32-38g/L, ammonium sulfate content control at 6.5-6.8 at 80��90g/L, pH. (2) electrolysis workshop section: require in electrolyzer that Fe content is that 18-20g/L, ammonium sulfate content control at 7.5-8.0 at 90g/L, pH. Whole groove temperature control is at 65 DEG C; Cathode current density 180A/m2, negative electrode changes plate, anodic current density 60A/m in every 24 hours2, positive column sulfuric acid content is about 30��40g/L, and anode changes plate in every 7 days. Electrolysis result: cathode plate surface light, substantially without manganese knot, current efficiency 66%, the fine and close black electrolysis MnO of anode surface attachment2, scraping and all weigh, calculating current efficiency is 60%, and product meets electrolysis MnO after measured2National standard.
The above; it is only the present invention's preferably embodiment; protection scope of the present invention is not limited to this; any being familiar with those skilled in the art in the technical scope of present disclosure, the simple change of the technical scheme that can obtain apparently or equivalence are replaced and are all fallen within the scope of protection of the present invention.
Claims (7)
1. a same electrolyzer is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterised in that, add additive in the electrolytic solution, additive comprises the compound containing Bi.
2. same electrolyzer as claimed in claim 1 is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterised in that, additive content in the electrolytic solution is 1-10mg/L.
3. same electrolyzer as claimed in claim 1 is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterized in that, described additive comprises at least one in the sulfuric acid oxidation thing of the oxide compound of Bi element, the muriate of Bi element, the oxychloride of Bi element, the oxyhydroxide of Bi element and Bi element.
4. same electrolyzer as claimed in claim 3 is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterised in that, the oxide compound of described Bi element is Bi2O3; The muriate of Bi element is BiCl3; The oxychloride of Bi element is BiOCl; The oxyhydroxide of Bi element is Bi (OH)3; The sulfuric acid oxidation thing of Bi element is Bi (OH)3��BiOSO4��
5. same electrolyzer as claimed in claim 4 is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterised in that, described additive comprises Bi (OH)3��BiOSO4And Bi2O3, Bi (OH)3��BiOSO4With Bi2O3Mass ratio be 1:1; Additive content in the electrolytic solution is 5mg/L.
6. same electrolyzer as claimed in claim 1 is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterised in that, described electrolyzer uses industrial filter cloth as the barrier film in cathodic area and positive column; Add liquid to add from cathodic area, overflow liquid and overflow from positive column; Negative electrode is stainless steel plate; Workshop section added by electrolytic solution, and in electrolyzer, the Fe content of electrolytic solution is 32-38g/L, ammonium sulfate content be 80-110g/L, pH is 6.5-6.8; Electrolysis workshop section: in electrolyzer, the Fe content of electrolytic solution is 18-20g/L, ammonium sulfate content be 90-110g/L, pH is 7.5-8.0; Electrolysis temperature is 50 DEG C-65 DEG C; The current density of negative electrode is 180��300A/m2, negative electrode changes plate in every 24 hours; Anode is titanium plate, titanium Mn alloy plate or MnO2Coated titanium plate; Anodic current density is 60��80A/m2, the sulfuric acid content of positive column is 30��40gH2SO4/ L, electrolysing period is 7-14 days.
7. same electrolyzer as claimed in claim 6 is produced the method for electrolytic metal Mn and electrolytic manganese dioxide simultaneously, it is characterised in that, described industrial filter cloth is terylene filter cloth, polypropylene fibre filter cloth or polyester cloth.
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Cited By (3)
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| CN109112569A (en) * | 2018-09-19 | 2019-01-01 | 兰州交通大学 | A kind of ion-exchange film method prepares the production method of manganese metal and manganese dioxide simultaneously |
| CN113373461A (en) * | 2021-04-27 | 2021-09-10 | 宁夏天元锰材料研究院(有限公司) | Process and equipment for producing battery-grade manganese dioxide by same-bath electrolysis |
| CN114534738A (en) * | 2020-11-27 | 2022-05-27 | 王益成 | Metal manganese or manganese alloy catalyst and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112569A (en) * | 2018-09-19 | 2019-01-01 | 兰州交通大学 | A kind of ion-exchange film method prepares the production method of manganese metal and manganese dioxide simultaneously |
| CN109112569B (en) * | 2018-09-19 | 2023-07-25 | 兰州交通大学 | Production method for simultaneously preparing manganese metal and manganese dioxide by ion exchange membrane electrolysis method |
| CN114534738A (en) * | 2020-11-27 | 2022-05-27 | 王益成 | Metal manganese or manganese alloy catalyst and preparation method thereof |
| CN114534738B (en) * | 2020-11-27 | 2024-05-24 | 王益成 | Metal manganese or manganese alloy catalyst and manufacturing method thereof |
| CN113373461A (en) * | 2021-04-27 | 2021-09-10 | 宁夏天元锰材料研究院(有限公司) | Process and equipment for producing battery-grade manganese dioxide by same-bath electrolysis |
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