CN103560240A - Preparation method of special electrolytic manganese dioxide for mercury-free alkaline battery - Google Patents
Preparation method of special electrolytic manganese dioxide for mercury-free alkaline battery Download PDFInfo
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Abstract
The invention belongs to the field of battery material processing, and particularly relates to a preparation method of electrolytic manganese dioxide special for a mercury-free alkaline battery. The preparation method comprises the steps of manganese sulfate leaching, neutralization deferrization, heavy metal impurity removal, electrolysis and post-treatment, wherein manganese oxide ore powder, pyrite ore powder and industrial sulfuric acid exist in SO2Soaking under the condition of (1) to prepare a crude manganese sulfate solution, then removing iron by using a calcium carbonate and calcium bicarbonate solution, removing heavy metals by using a vulcanized mixture, periodically electrolyzing to obtain a manganese dioxide semi-finished product at the anode, and finally obtaining the electrolytic manganese dioxide special for the mercury-free alkaline battery after post-treatment. The invention simplifies the production flow, improves the production process efficiency, and obtains the product with low impurity content and excellent product quality.
Description
Technical Field
The invention belongs to the field of battery material processing, and particularly relates to a preparation method of electrolytic manganese dioxide special for a mercury-free alkaline battery.
Background
Electrolytic Manganese Dioxide (EMD), which is a positive active material of batteries, directly participates in a discharge reaction of the batteries, and its appearance and development are closely connected to the battery industry. Since the advent of zinc-manganese batteries, a great deal of research work has been conducted on manganese dioxide in order to find manganese dioxide suitable for the fabrication of battery positive electrode active materials, thereby promoting the development and development of the industrial industry of artificial manganese dioxide, particularly electrolytic manganese dioxide. The application of the electrolytic manganese dioxide in the zinc-manganese battery greatly improves the discharge capacity of the battery, and greatly expands the application of the battery. With the progress of technology, various portable electric appliances are developed towards miniaturization and intellectualization, higher requirements are put on power supplies, and alkaline zinc-manganese batteries with high discharge capacity and suitable for large-current discharge appear. At present, the alkaline zinc-manganese battery becomes the most significant product in dry batteries due to the superior performance of the alkaline zinc-manganese battery, and is also the main development direction for upgrading and updating batteries in China. However, with the heavy use of batteries, especially mercury batteries, serious harm is brought to environmental protection, the mercury-free battery is imperative, and the mercury-free battery is basically realized in foreign developed industrial countries. In the end of 1997, the united release of the regulations on limiting the mercury content in battery products by nine ministers such as the institute of light industry in china and the national trade and commission required that alkaline zinc-manganese batteries with mercury content of more than 0.0001% be prohibited from being produced since 2005. On the other hand, the mercury-free battery is also a problem which needs to be solved urgently when the alkaline zinc-manganese battery product in China moves to the international market.
The mercury-free battery puts more and more strict requirements on electrolytic manganese dioxide, and only high-quality electrolytic manganese dioxide can meet the production requirements of alkaline zinc-manganese batteries. The improvement of the preparation method of alkaline zinc-manganese electrolytic manganese dioxide is also a hotspot of current research, but in order to meet the requirement of high-quality mercury-free manganese dioxide, the innovation and the improvement of the preparation method are imperative for alkaline zinc-manganese batteries with mercury content less than 0.0001 percent, even mercury-free electrolytic manganese dioxide. The production process route of the EMD special for the mercury-free alkaline zinc-manganese dioxide battery at present comprises the following steps: feeding, leaching, potassium removing, iron removing, filtering, molybdenum removing by catalysis, heavy metal removing, calcium and magnesium removing by precipitation flow method, aging, electrolysis, washing and conditioningAdjusting pH value, drying, grinding, grading particle size, homogenizing and packaging. The technical process is complicated, the standard reaching removal of Fe is difficult to realize in the later drying and impurity removing process, the mercury-free alkaline zinc-manganese battery is extremely sensitive to heavy metal impurities contained in electrolytic manganese dioxide in the manufacturing and storage processes due to the lack of the shielding effect of amalgamation on harmful elements, micro batteries can be formed by trace harmful impurities in the electrolytic manganese dioxide in the battery, the self-discharge, the gas expansion and the leakage in the battery are caused, the discharge capacity and the storage performance of the battery are reduced, and therefore the high-quality electrolytic manganese dioxide has extremely high requirements on the impurities in the battery<100×10 - 6 ppm。
Disclosure of Invention
The invention aims to solve the problems of complexity, long preparation process time, difficult standard impurity content, poor method specificity, poor performance of obtained products and the like of the conventional preparation process of the special electrolytic manganese dioxide for the mercury-free alkaline battery, and provides the preparation method of the special electrolytic manganese dioxide for the mercury-free alkaline battery.
The scheme of the invention is realized by the following steps: a preparation method of special electrolytic manganese dioxide for mercury-free alkaline batteries is characterized by comprising the following steps:
a. leaching manganese sulfate: manganese oxide ore powder with the granularity of more than or equal to 200 meshes, pyrite powder and industrial sulfuric acid are mixed according to the weight ratio of 10000g:800 to 1500g:1500 to 2200g of the mixture is put into an leaching reaction tank, the mixture reacts for 1.5 to 2 hours under the conditions that the stirring speed is 50 to 65rpm and the temperature is 90 to 95 ℃, then the stirring speed is adjusted to 20 to 50rpm and the temperature is 90 to 95 ℃, and sulfur dioxide SO is introduced into the reaction tank 2 Gas, manganese oxide ore powder and sulfur dioxide SO 2 The proportion of the gas introduction amount is 10000g:0.5-1.5mol, the reaction time is 1.0-1.5 hours, and crude manganese sulfate solution is obtained by leaching. In the invention, the Mn content in the manganese oxide ore powder is 16-20%, and the S content in the pyrite powder is 20-30%.
b. Neutralizing and deironing: under the condition of normal temperature, the crude manganese sulfate solution obtained in the step aIn which calcium carbonate CaCO is added 3 And calcium bicarbonate CaHCO 3 The mixture is neutralized for residual H in solution 2 SO 4 The pH value of the solution is adjusted to 4.5, and the addition of calcium carbonate CaCO is stopped 3 And calcium bicarbonate CaHCO 3 Mixture, concentration of ferrous ion in detection solution is less than or equal to 10 -5 The product is qualified when the mol/L is higher than 10 -5 Adding manganese oxide ore powder with the granularity of more than or equal to 300 meshes into the mixture by mol/L until the content of ferrous ions in the mixed solution is qualified, and continuously adding calcium carbonate CaCO after the content of the ferrous ions is qualified 3 And calcium bicarbonate CaHCO 3 Adjusting the pH value of the mixture to 6.5, and detecting the concentration of ferric ions in the mixed solution to be less than or equal to 10 -5 The product is qualified when the mol/L is higher than 10 -5 Adding calcium carbonate CaCO continuously at mol/L 3 And calcium bicarbonate CaHCO 3 And (4) mixing the mixture until the content of ferric ions in the mixed solution is qualified, and filtering to remove ore pulp slag to obtain a crude manganese sulfate solution.
c. Removing impurities from heavy metals: heating the crude manganese sulfate solution obtained in the step b to 85-90 ℃, and slowly adding barium sulfide BaS and sodium sulfide Na 2 S, a vulcanization mixture, wherein the adding speed of the vulcanization mixture is 2-5g/L/min, the concentration of Cu, pb, ni, co, V, as, sb and Mo is detected every 30min, when Cu is less than or equal to 0.5ppm, pb is less than or equal to 3ppm, ni is less than or equal to 2ppm, co is less than or equal to 2ppm, V is less than or equal to 3ppm, as is less than or equal to 0.5ppm, sb is less than or equal to 0.5ppm, mo is less than or equal to 0.5ppm, the addition of the vulcanization mixture is stopped, manganese oxide ore powder with the granularity of more than or equal to 300 meshes is added, and the concentration of element Mo is less than or equal to 0.003ppm according to the reaction solution: filter aid =100L: adding filter aid in a proportion of 20-25g, stirring for 20-30min, filtering to remove precipitate to obtain filtrate, adding high molecular polyelectrolyte into the filtrate, wherein the proportion of the added high molecular polyelectrolyte to the filtrate is 2-5g:100L, standing for 3-5 days after the addition is finished, and obtaining the manganese sulfate solution after impurity removal.
d. Electrolysis and post-treatment: and c, transferring the manganese sulfate solution subjected to impurity removal obtained in the step c into an electrolytic cell for electrolysis, wherein the electrolysis conditions are as follows: the electrolysis temperature is 95-98 ℃, and the anode current density is 100-120A/m 2 Sulfuric acid H as electrolyte 2 SO 4 The concentration is 0.4-0.5mol/L, the concentration of feed liquid manganese sulfate is 1.0-1.2mol/L, and the electrolysis period isAnd (3) obtaining a semi-finished product of electrolytic manganese dioxide at the anode for 7-9 days, rinsing and crushing the semi-finished product of manganese dioxide, conveying the semi-finished product of manganese dioxide to a gravity blending bin in a dense phase pneumatic conveying mode for blending, wherein the blending time is 18-22 hours, and obtaining the special electrolytic manganese dioxide product for the mercury-free alkaline battery.
As a further limitation of the invention, said calcium carbonate CaCO 3 And calcium bicarbonate CaHCO 3 Calcium carbonate CaCO in a mixture 3 And calcium bicarbonate CaHCO 3 The weight ratio of (1 g).
As a further limitation of the invention, the sulfidizing mixture is 20% to 30% sodium sulfide Na 2 The volume ratio of the S solution to the 20-30% barium sulfide BaS solution is 0.1-0.2L: 0.8 to 0.9L.
The filter aid is any one of diatomite, perlite, cellulose, asbestos, graphite powder and sawdust.
In a further limitation of the present invention, the polymer polyelectrolyte is any one of polyacrylamide, polyethyleneimine, cationic starch, and polyamide.
The water washing is to use NaOH alkali liquor with the concentration of 20 to 30 percent for acid neutralization until the pH is 7.5 to 8.0, then use H with the concentration of 3 to 4 mol percent 2 SO 4 Alkali washing is carried out on the solution to remove impurities until the pH value is 7.0 neutral, and the processing temperature is kept at 80-95 ℃ in the rinsing process.
As a further limitation of the invention, the manganese dioxide product is pulverized into manganese dioxide particles with a passing rate of 95-97% of manganese dioxide particles on a 200-mesh sieve and 70-90% of manganese dioxide particles on a 325-mesh sieve.
The invention has the following good effects:
(1) The invention introduces SO by improving the traditional electrolytic manganese dioxide 'two-ore acid-adding method' production process 2 Catalysis, calcium carbonate and calcium bicarbonate mixture neutralization deferrization, not only accelerate the reaction but also lighten the treatment pressure on impurities in the product in the later period, and finally realize that the electrolytic manganese dioxide product of the automobile power battery meets the following requirements: (1) manganese dioxide not less than 92.50%, mercury contentThe content of impurities such As Fe, cu, pb, ni, co, V, as, sb, mo, K, na, ca, mg and the like is less than 0.0001 percent, the contents of the indexes such As Cu, pb, ni, co, V, as, mg and the like are low, cu is less than or equal to 0.5ppm, pb is less than or equal to 3ppm, ni is less than or equal to 2ppm, co is less than or equal to 2ppm, V is less than or equal to 3ppm, as is less than or equal to 0.5ppm, sb is less than or equal to 0.5ppm, mo is less than or equal to 0.5ppm, hg is less than or equal to 0.5ppm, particularly Fe reaches the required concentration and is controlled below 60ppm, the impurity K is less than or equal to 0.03 percent, the content of Na is reduced to the minimum, and the content of hydrochloric acid is less than or equal to 0.01 percent; (2) the specific surface area is controlled to be 30m 2 /g-35m 2 (ii)/g; (3) reasonable neutralizing agent is selected in the rinsing production process, so that the contents of impurities K and Na are reduced to the minimum; (4) the particle size distribution range of the finished product is concentrated.
(2) The preparation method can rapidly produce the special electrolytic manganese dioxide for the mercury-free alkaline battery, simplifies the production flow, improves the production process efficiency by introducing the catalyst and effective reaction conditions, and finally reduces the production cost, and the obtained product has high performance.
Detailed Description
The following description of the method for preparing electrolytic manganese dioxide for mercury-free alkaline batteries according to the present invention is provided in conjunction with the following examples, which are not intended to limit the present invention in any way.
Example 1
a. Leaching manganese sulfate: manganese oxide ore powder with the granularity of more than or equal to 200 meshes, pyrite ore powder and industrial sulfuric acid are mixed according to the weight ratio of 10000g:1500g of: 1500g of the mixture is put into a leaching reaction tank and reacted for 1.5 hours under the conditions that the stirring speed is 50rpm and the temperature is 90 ℃, then the stirring speed is adjusted to be 20rpm and the temperature is 90 ℃, and simultaneously sulfur dioxide SO is introduced 2 Gas, manganese oxide ore powder and sulfur dioxide SO 2 The gas introduction amount ratio is 10000g:1.0mol, the reaction time is 1.0 hour, and crude manganese sulfate solution is obtained by leaching. In the invention, the Mn content in the manganese oxide ore powder is 20%, and the S content in the pyrite powder is 25%.
b. Neutralizing and deironing: adding calcium carbonate CaCO into the crude manganese sulfate solution obtained in the step a under the normal temperature condition 3 And calcium bicarbonate CaHCO 3 Mixture of calcium carbonate CaCO 3 And calcium bicarbonate CaHCO 3 1g of (a) neutralizing H remaining in the solution 2 SO 4 The pH value of the solution is adjusted to 4.5, and the addition of calcium carbonate CaCO is stopped 3 And calcium bicarbonate CaHCO 3 Mixture, concentration of ferrous ion in detection solution is less than or equal to 10 -5 The product is qualified when the mol/L is higher than 10 -5 Adding manganese oxide ore powder with the granularity of more than or equal to 300 meshes into the mixture by mol/L until the content of ferrous ions in the mixed solution is qualified, and continuously adding calcium carbonate CaCO after the content of the ferrous ions is qualified 3 And calcium bicarbonate CaHCO 3 Adjusting the pH value of the mixture to 6.5, and detecting the concentration of ferric ions in the mixed solution to be less than or equal to 10 -5 The product is qualified when the mol/L is higher than 10 -5 Adding calcium carbonate CaCO continuously at mol/L 3 And calcium bicarbonate CaHCO 3 And (4) mixing until the content of ferric ions in the mixed solution is qualified, and filtering to remove the ore pulp slag to obtain a crude manganese sulfate solution.
c. Removing impurities from heavy metals: c, heating the crude manganese sulfate solution obtained in the step b to 90 ℃, and slowly adding barium sulfide BaS and sodium sulfide Na 2 Sulfurized mixture of S, 30% sodium sulfide Na 2 The volume ratio of the S solution to the 30% barium sulfide BaS solution is 0.1L:0.9L of the mixture is mixed, the adding speed of the vulcanized mixture is 5g/L/min, the concentrations of Cu, pb, ni, co, V, as, sb and Mo are detected every 30min, when the Cu is less than or equal to 0.5ppm, the Pb is less than or equal to 3ppm, the Ni is less than or equal to 2ppm, the Co is less than or equal to 2ppm, the V is less than or equal to 3ppm, the As is less than or equal to 0.5ppm, the Sb is less than or equal to 0.5ppm, the vulcanized mixture is stopped adding, manganese oxide ore powder with the granularity of more than or equal to 300 meshes is added, the concentration of element Mo is less than or equal to 0.003ppm, according to the reaction solution: filter aid =100L: adding 25g of diatomite filter aid, stirring for 20-30min, filtering to remove precipitates to obtain filtrate, adding polyacrylamide polymer polyelectrolyte into the filtrate, wherein the ratio of the added polymer polyelectrolyte to the filtrate is 5g:100L, standing for 1 day after the addition is finished, and obtaining the manganese sulfate solution after impurity removal.
d. Electrolysis and post-treatment: and c, transferring the manganese sulfate solution subjected to impurity removal obtained in the step c into an electrolytic cell for electrolysis, wherein the electrolysis conditions are as follows: the electrolysis temperature is 96 ℃, the anode current density is 120A/m 2 Sulfuric acid H as electrolyte 2 SO 4 The concentration is 0.40mol/L, the concentration of manganese sulfate in the feed liquid is 1.0mol/L, the electrolysis period is 7 days, a semi-finished product of electrolytic manganese dioxide is obtained at the anode, the semi-finished product of manganese dioxide is rinsed and crushed to obtain a finished product of electrolytic manganese dioxide, rinsing is carried out by using 30 percent NaOH alkaline solution to wash and neutralize until the pH value is 7.5, and then using 3 percent H solution to wash and neutralize 2 SO 4 Alkali washing is carried out on the solution to remove impurities until the pH value is 7.0 neutral, and the treatment temperature is kept at 80 ℃ in the rinsing process. The passing rate of the manganese dioxide particles in a 200-mesh sieve is 97 percent, and the passing rate of a 325-mesh sieve is 80 percent. And conveying the crushed electrolytic manganese dioxide to a gravity blending bin for blending in a dense-phase pneumatic conveying mode for 18 hours to obtain the special electrolytic manganese dioxide product for the mercury-free alkaline battery.
The product obtained in the embodiment has 93.50% of manganese dioxide, less than 0.0001% of mercury, low contents of impurities such As Fe, cu, pb, ni, co, V, as, sb, mo, K, na, ca, mg and the like, less than or equal to 0.5ppm of Cu, less than or equal to 3ppm of Pb, less than or equal to 2ppm of Ni, less than or equal to 2ppm of Co, less than or equal to 3ppm of V, less than or equal to 0.5ppm of As, less than or equal to 0.5ppm of Sb, less than or equal to 0.5ppm of Mo, less than or equal to 0.5ppm of Hg, particularly, the required concentration of Fe is controlled below 60ppm, so that the impurities such As K is less than or equal to 0.03%, the Na content is reduced to the minimum, less than or equal to 0.01% of hydrochloric acid insoluble matter, and the specific surface area is controlled to 30m 2 /g-35m 2 /g。
Example 2
a. Leaching manganese sulfate: manganese oxide ore powder with the granularity of more than or equal to 200 meshes, pyrite ore powder and industrial sulfuric acid are mixed according to the weight ratio of 10000g:800g:2200g of the mixture is put into a leaching reaction tank and reacts for 2 hours under the conditions that the stirring speed is 65rpm and the temperature is 95 ℃, then the stirring speed is adjusted to be 50rpm and the temperature is 95 ℃, and simultaneously sulfur dioxide SO is introduced 2 Gas, manganese oxide ore powder and sulfur dioxide SO 2 The gas introduction amount ratio is 10000g:0.5mol, the reaction time is 1.0 hour, and crude manganese sulfate solution is obtained by leaching. In the invention, the Mn content in the manganese oxide ore powder is 18 percent, and the S content in the pyrite powder is 20 percent.
b. Neutralizing and deironing: c, adding calcium carbonate CaCO into the crude manganese sulfate solution obtained in the step a under the normal temperature condition 3 And calcium bicarbonate CaHCO 3 The mixture is mixed with a solvent to form a mixture,calcium carbonate CaCO 3 And calcium bicarbonate CaHCO 3 The weight ratio of (1) is 1 g.
c. Removing impurities from heavy metals: b, heating the crude manganese sulfate solution obtained in the step b to 85 ℃, and slowly adding barium sulfide BaS and sodium sulfide Na 2 Sulfurized mixture of S, 20% sodium sulfide Na 2 The volume ratio of the S solution to the 30% barium sulfide BaS solution is 0.15L:0.85L of the mixture, the adding speed of the vulcanizing mixture is 2.5g/L/min, the concentration of Cu, pb, ni, co, V, as, sb and Mo is detected every 30min, when the concentration of Cu is less than or equal to 0.5ppm, the concentration of Pb is less than or equal to 3ppm, the concentration of Ni is less than or equal to 2ppm, the concentration of Co is less than or equal to 2ppm, the concentration of V is less than or equal to 3ppm, the concentration of As is less than or equal to 0.5ppm, the concentration of Sb is less than or equal to 0.5ppm and the concentration of Mo is less than or equal to 300 meshes, manganese oxide ore powder is added to ensure that the concentration of Mo is less than or equal to 0.003ppm according to the reaction solution: filter aid =100L: adding a perlite filter aid in a ratio of 20g, stirring for 20min, filtering to remove precipitates to obtain a filtrate, adding a polyethyleneimine polymeric polyelectrolyte into the filtrate, wherein the ratio of the added polymeric polyelectrolyte to the filtrate is 2g:100L, standing for 1 day after the addition is finished, and obtaining the manganese sulfate solution after impurity removal.
d. Electrolysis and post-treatment: and c, transferring the manganese sulfate solution subjected to impurity removal obtained in the step c into an electrolytic cell for electrolysis, wherein the electrolysis conditions are as follows: the electrolysis temperature is 95 ℃, the anode current density is 100A/m 2 Sulfuric acid H as electrolyte 2 SO 4 The concentration is 0.50mol/L, the concentration of feed liquid manganese sulfate is 1.0mol/L, the electrolysis cycle is 9 days, a semi-finished product of electrolytic manganese dioxide is obtained at the anode, the semi-finished product of manganese dioxide is rinsed and crushed to obtain a finished product of electrolytic manganese dioxide, the rinsing is to use 25 percent NaOH alkaline solution to wash acid and neutralize the acid until the pH value is 8.0, and then H with the concentration of 3.5 percent is used 2 SO 4 Alkali washing is carried out on the solution to remove impurities until the pH value is 7.0 neutral, and the treatment temperature is kept at 95 ℃ in the rinsing process. The passing rate of manganese dioxide particles in a 200-mesh sieve is 95%, and the passing rate of a 325-mesh sieve is 85%. And conveying the crushed electrolytic manganese dioxide to a gravity blending bin for blending in a dense-phase pneumatic conveying mode for 22 hours to obtain the special electrolytic manganese dioxide product for the mercury-free alkaline battery.
The manganese dioxide content of the product obtained in this example92.80 percent, less than 0.0001 percent of mercury, low contents of impurities such As Fe, cu, pb, ni, co, V, as, sb, mo, K, na, ca, mg and the like, less than or equal to 0.5ppm of Cu, less than or equal to 3ppm of Pb, less than or equal to 2ppm of Ni, less than or equal to 2ppm of Co, less than or equal to 3ppm of V, less than or equal to 0.5ppm of As, less than or equal to 0.5ppm of Sb, less than or equal to 0.5ppm of Mo, less than or equal to 0.5ppm of Hg, particularly, the required concentration of Fe is controlled below 60ppm, the impurities such As K, less than or equal to 0.03 percent, the Na content is reduced to the minimum limit, less than or equal to 0.01 percent of hydrochloric acid insoluble matter, and the specific surface area is controlled to 30m 2 /g-35m 2 /g。
Example 3
a. Leaching manganese sulfate: manganese oxide ore powder with the granularity of more than or equal to 200 meshes, pyrite powder and industrial sulfuric acid are mixed according to the weight ratio of 10000g:1200g: putting 1800g of the mixture into a leaching reaction tank, reacting for 1.5 hours under the conditions of stirring speed of 60rpm and temperature of 92 ℃, then adjusting the stirring speed to 40rpm and the temperature to 92 ℃, and simultaneously introducing sulfur dioxide SO 2 Gas, manganese oxide ore powder and sulfur dioxide SO 2 The gas introduction amount ratio is 10000g:1.5mol, the reaction time is 1.0 hour, and crude manganese sulfate solution is obtained by leaching. In the invention, the Mn content in the manganese oxide ore powder is 25%, and the S content in the pyrite powder is 30%.
b. Neutralizing and deironing: adding calcium carbonate CaCO into the crude manganese sulfate solution obtained in the step a under the normal temperature condition 3 And calcium bicarbonate CaHCO 3 Mixture of calcium carbonate CaCO 3 And calcium bicarbonate CaHCO 3 The weight ratio of (1 g).
c. Removing impurities from heavy metals: c, heating the crude manganese sulfate solution obtained in the step b to 85 ℃, and slowly adding barium sulfide BaS and sodium sulfide Na 2 Sulfurized mixture of S, 25% sodium sulfide Na 2 The volume ratio of the S solution to the 25% barium sulfide BaS solution is 0.2L:0.8L of mixing, the adding speed of the vulcanizing mixture is 3.5g/L/min, the concentration of Cu, pb, ni, co, V, as, sb and Mo is detected every 30min, when the concentration of Cu is less than or equal to 0.5ppm, the concentration of Pb is less than or equal to 3ppm, the concentration of Ni is less than or equal to 2ppm, the concentration of Co is less than or equal to 2ppm, the concentration of V is less than or equal to 3ppm, the concentration of As is less than or equal to 0.5ppm, the concentration of Sb is less than or equal to 0.5ppm and the concentration of Mo is less than or equal to 0.5ppm, manganese oxide ore powder with the granularity of more than or equal to 300 meshes is added to ensure that the concentration of Mo is less than or equal to 0.003ppm according to the reaction solution: filter aid =100L:22Adding sawdust filter aid in a ratio of g, stirring for 25min, filtering to remove precipitate to obtain filtrate, adding polyamide polymer polyelectrolyte into the filtrate, wherein the ratio of the added polymer polyelectrolyte to the filtrate is 3.5g:100L, standing for 1 day after the addition is finished, and obtaining the manganese sulfate solution after impurity removal.
d. Electrolysis and post-treatment: and c, transferring the manganese sulfate solution subjected to impurity removal obtained in the step c into an electrolytic cell for electrolysis, wherein the electrolysis conditions are as follows: the electrolysis temperature is 98 ℃, and the anode current density is 100A/m 2 Sulfuric acid H as electrolyte 2 SO 4 The concentration is 0.45mol/L, the concentration of manganese sulfate in the feed liquid is 1.1mol/L, the electrolysis period is 8 days, a semi-finished product of electrolytic manganese dioxide is obtained at the anode, the semi-finished product of manganese dioxide is rinsed and crushed to obtain a finished product of electrolytic manganese dioxide, the rinsing is to use NaOH alkali liquor with the concentration of 20 percent to wash and neutralize the acid until the pH value is 8.0, and then H with the concentration of 4 percent is used 2 SO 4 Alkali washing is carried out on the solution to remove impurities until the pH value is 7.0 neutral, and the treatment temperature is kept at 90 ℃ in the rinsing process. The passing rate of the manganese dioxide particles in a 200-mesh sieve is 96 percent, and the passing rate of a 325-mesh sieve is 75 percent. And conveying the crushed electrolytic manganese dioxide to a gravity blending bin in a dense phase pneumatic conveying mode for blending for 20 hours to obtain the special electrolytic manganese dioxide product for the mercury-free alkaline battery.
The product obtained in the embodiment has 93.00 percent of manganese dioxide, less than 0.0001 percent of mercury, low contents of indexes such As impurities Fe, cu, pb, ni, co, V, as, sb, mo, K, na, ca, mg and the like, less than or equal to 0.5ppm of Cu, less than or equal to 3ppm of Pb, less than or equal to 2ppm of Ni, less than or equal to 2ppm of Co, less than or equal to 3ppm of V, less than or equal to 0.5ppm of As, less than or equal to 0.5ppm of Sb, less than or equal to 0.5ppm of Mo, less than or equal to 0.5ppm of Hg, particularly the required concentration of Fe is controlled below 60ppm, so that the impurities K is less than or equal to 0.03 percent, the Na content is reduced to the minimum, less than or equal to 0.01 percent of hydrochloric acid insoluble matter, and the specific surface area is controlled to 30m 2 /g-35m 2 /g。
The above-described embodiments of the present invention are intended to be illustrative only and not limiting, and the scope of the invention is indicated in the claims, along with the full range of ingredients, ratios of ingredients, and process parameters of manufacture, and the above description is not intended to be exhaustive of the invention, and thus, any changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.
The invention is produced by accumulating long-term working experience of a plurality of researchers for electrolyzing manganese dioxide and creative labor, and finally realizes that the electrolytic manganese dioxide product of the automobile power battery meets the following requirements: (1) more than or equal to 93.50 percent of manganese dioxide, less than 0.0001 percent of mercury, low contents of impurities such As Fe, cu, pb, ni, co, V, as, sb, mo, K, na, ca, mg and the like, less than or equal to 0.5ppm of Cu, less than or equal to 3ppm of Pb, less than or equal to 2ppm of Ni, less than or equal to 2ppm of Co, less than or equal to 3ppm of V, less than or equal to 0.5ppm of As, less than or equal to 0.5ppm of Sb, less than or equal to 0.5ppm of Mo, less than or equal to 0.5ppm of Hg, particularly, the required concentration of Fe is controlled below 60ppm, so that the content of the impurities K is less than or equal to 0.03 percent, the content of Na is reduced to the minimum, and the content of hydrochloric acid is less than or equal to 0.01 percent; (2) the specific surface area is controlled to be 30m 2 /g-35m 2 (iv) g; (3) reasonable neutralizing agent is selected in the rinsing production process, so that the contents of impurities K and Na are reduced to the minimum; (4) the distribution range of the granularity of the finished product is concentrated. The invention simplifies the production flow, improves the production process efficiency, and obtains the product with low impurity content and excellent quality.
Claims (6)
1. A preparation method of electrolytic manganese dioxide special for mercury-free alkaline batteries is characterized by comprising the following steps:
a. leaching manganese sulfate: manganese oxide ore powder with the granularity of more than or equal to 200 meshes, pyrite powder and industrial sulfuric acid are mixed according to the weight ratio of 10000g:800 to 1500g: putting 1500-2200 g of the mixture into a leaching reaction tank, reacting for 1.5-2 hours under the conditions that the stirring speed is 50-65rpm and the temperature is 90-95 ℃, then regulating the stirring speed to be 20-50rpm and the temperature to be 90-95 ℃, and simultaneously introducing sulfur dioxide SO 2 Gas, manganese oxide ore powder and sulfur dioxide SO 2 The gas introduction amount ratio is 10000g:0.5-1.5mol, the reaction time is 1.0-1.5 hours, and crude manganese sulfate solution is obtained by leaching;
b. neutralizing and deironing: adding calcium carbonate CaCO into the crude manganese sulfate solution obtained in the step a under the normal temperature condition 3 And calcium bicarbonate CaHCO 3 The mixture is neutralized for residual H in solution 2 SO 4 To adjust the pH of the solutionAt 4.5, the addition of calcium carbonate CaCO was stopped 3 And calcium bicarbonate CaHCO 3 Mixture, concentration of bivalent iron ion in detecting solution is less than or equal to 10 -5 The product is qualified when the mol/L is higher than 10 -5 Adding manganese oxide ore powder with the granularity of more than or equal to 300 meshes into the mixture by mol/L until the content of ferrous ions in the mixed solution is qualified, and continuously adding calcium carbonate CaCO after the content of the ferrous ions is qualified 3 And calcium bicarbonate CaHCO 3 Adjusting the pH value of the mixture to 6.5, and detecting the concentration of ferric ions in the mixed solution to be less than or equal to 10 -5 The product is qualified when the mol/L is higher than 10 -5 Adding calcium carbonate CaCO continuously at mol/L 3 And calcium bicarbonate CaHCO 3 Mixing the mixture until the content of ferric ions in the mixed solution is qualified, and filtering to remove ore pulp slag to obtain a crude manganese sulfate solution;
c. removing impurities from heavy metals: heating the crude manganese sulfate solution obtained in the step b to 85-90 ℃, and slowly adding barium sulfide BaS and sodium sulfide Na 2 S, a vulcanization mixture, wherein the adding speed of the vulcanization mixture is 2-5g/L/min, the concentration of Cu, pb, ni, co, V, as, sb and Mo is detected every 30min, when Cu is less than or equal to 0.5ppm, pb is less than or equal to 3ppm, ni is less than or equal to 2ppm, co is less than or equal to 2ppm, V is less than or equal to 3ppm, as is less than or equal to 0.5ppm, sb is less than or equal to 0.5ppm, mo is less than or equal to 0.5ppm, the addition of the vulcanization mixture is stopped, manganese oxide ore powder with the granularity of more than or equal to 300 meshes is added, and the concentration of element Mo is less than or equal to 0.003ppm according to the reaction solution: filter aid =100L: adding filter aid in a proportion of 20-25g, stirring for 20-30min, filtering to remove precipitate to obtain filtrate, adding high molecular polyelectrolyte into the filtrate, wherein the proportion of the added high molecular polyelectrolyte to the filtrate is 2-5g:100L, standing for 1 day after the addition is finished to obtain a manganese sulfate solution after impurity removal;
d. electrolysis and post-treatment: d, transferring the manganese sulfate solution subjected to impurity removal obtained in the step c into an electrolytic cell for electrolysis, wherein the electrolysis conditions are as follows: the electrolysis temperature is 95-98 ℃, and the anode current density is 100-120A/m 2 Sulfuric acid H as electrolyte 2 SO 4 The concentration is 0.4-0.5mol/L, the concentration of manganese sulfate is 1.0-1.2mol/L, the electrolysis period is 7-9 days, the electrolytic manganese dioxide semi-finished product is obtained at the anode, the manganese dioxide semi-finished product is rinsed, crushed and conveyed to a gravity blending bin in a dense phase pneumatic conveying mode for blendingMixing for 18-22 hours to obtain the special electrolytic manganese dioxide product for the mercury-free alkaline battery.
2. The method for preparing electrolytic manganese dioxide specially used for mercury-free alkaline batteries according to claim 1, wherein the calcium carbonate CaCO 3 And calcium bicarbonate CaHCO 3 Calcium carbonate CaCO in a mixture 3 And calcium bicarbonate CaHCO 3 The weight ratio of (1 g).
3. The method for preparing electrolytic manganese dioxide specially used for mercury-free alkaline batteries according to any one of claims 1 or 2, characterized in that the sulfuration mixture is 20% -30% of sodium sulfide Na 2 The volume ratio of the S solution to the 20-30% barium sulfide BaS solution is 0.1-0.2L: 0.8 to 0.9L.
4. The method for preparing electrolytic manganese dioxide specially used for mercury-free alkaline batteries according to claim 3, wherein the filter aid is any one of diatomite, perlite, cellulose, asbestos, graphite powder and sawdust.
5. The method for preparing special electrolytic manganese dioxide for mercury-free alkaline batteries according to claim 4, wherein the polymer polyelectrolyte is any one of polyacrylamide, polyethyleneimine, cationic starch and polyamide.
6. The method for preparing the electrolytic manganese dioxide specially used for the mercury-free alkaline battery according to any one of claims 4 or 5, wherein the water washing is performed by washing with NaOH alkali liquor with a concentration of 20% -30% and acid neutralization until the pH value is 7.5-8.0, and then washing with H with a concentration of 3% -4% 2 SO 4 Alkali washing is carried out on the solution to remove impurities until the pH value is 7.0 neutral, and the processing temperature is kept at 80-95 ℃ in the rinsing process.
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| CN114525523A (en) * | 2021-12-31 | 2022-05-24 | 广西汇元锰业有限责任公司 | Deep impurity removal process for electrolytic manganese dioxide electrolyte |
| WO2022205535A1 (en) * | 2021-03-31 | 2022-10-06 | 广西桂柳化工有限责任公司 | Method for preparing electrolytic manganese dioxide for producing lithium manganate material |
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