CN1284259C - Method for preparing manganese-zinc ferrite granules and mixed carbonate by using waste dry batteries - Google Patents
Method for preparing manganese-zinc ferrite granules and mixed carbonate by using waste dry batteries Download PDFInfo
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Abstract
The method comprises the steps of leaching crushed waste dry batteries by using waste sulfuric acid or industrial sulfuric acid of a titanium white sulfate method, concentrating mercury in the form of mercuric sulfide in leached filter residues through vulcanization, treating the mercuric sulfide, purifying filtrate through oxidation heating, replacement and hydrolysis procedures, neutralizing the filtrate by using a carbonate solution, washing and drying precipitates to obtain mixed carbonate for preparing manganese-zinc ferrite, and concentrating and crystallizing the neutralized mother liquor to produce ammonium sulfate. Supplementing a certain amount of iron and manganese elements in the process, and pre-sintering and granulating the obtained mixed carbonate to obtain a manganese-zinc ferrite granular product; the added iron agent can also be iron sheet magnetically selected from waste dry batteries, and the waste dry batteries with the iron sheet separated are used for producing mixed carbonate. The method treats waste by waste, is simple and effective in mercury removal, can effectively utilize each valuable element, has high added value of products, and does not generate new 'three wastes' pollution in the whole process, thereby having very high economic benefit and social benefit.
Description
Technical Field
The invention relates to a method for producing manganese zinc ferrite granules and mixed carbonate by using waste dry batteries. The invention belongs to the technical field of resource regeneration.
Background
China is a big country for producing and consuming dry batteries, the annual output is nearly 200 hundred million, and the dry batteries are the first in the world. The waste dry batteries contain heavy metals such as mercury, cadmium, zinc, lead and the like listed in the national hazardous waste list, so that the waste dry batteries can seriously pollute the environment and damage the health of human bodies if being discarded without being processed. In terms of resources, the dry cell battery contains 15 ten thousand tons of zinc, 22 ten thousand tons of manganese dioxide, 15 ten thousand tons of iron, 2000 tons of copper, 4.3 ten thousand tons of carbon rods and the like calculated by 100 hundred million waste dry cells, and the resource value is considerable. In particular, the provision of the technical policy for preventing and treating the pollution of the waste batteries implemented in China is as follows: and the alkaline zinc-manganese battery with the mercury content of more than 0.0001 percent stops being produced from 1 month and 1 day in 2005. Gradually increasing the proportion of the alkaline zinc-manganese dioxide battery with the mercury content of less than 0.0001 percent in the primary battery; the production and sales volume of the paste battery are gradually reduced, and finally the elimination of the paste battery is realized. Therefore, dry batteries are developed to be mercury-free alkaline batteries, which is more beneficial to recycling of waste dry batteries.
At present, although China has researched and proposed various process flows for recycling waste dry batteries, a process which is put into practical application still does not exist. Such as roasting-electrodeposition, duplex metal electrolysis, zinc oxide and manganese dioxide production, zinc sulfate and lithopone production, feed-grade zinc sulfate and manganese carbonate production, zinc manganese trace fertilizer production, mineral separation for waste dry batteries, fire ferromanganese production, vacuum metallurgical separation, etc. Most of the processes separate and recover iron, zinc and manganese, and the common processes are complex, long in flow, low in metal recovery rate, low in product value and poor in economic benefit. Most processes cannot effectively treat mercury at low cost, and some processes do not treat mercury; some mercury is dispersed in the separation process, so that the difficulty and the cost of mercury treatment are increased; some pretreatment adopts low-temperature reduction roasting to evaporate mercury, so that the crushing strength is high, the energy consumption is high, the equipment investment is large due to the general use of a rotary kiln, the investment waste is caused after the dry battery is free of mercury, and the plastic is roasted under the low-temperature oxygen-deficient state to generate a large amount of dioxin and other toxic substances to generate new pollution. The TDK corporation of japan studied the production of magnetic materials by baking waste dry batteries to form oxides of manganese, zinc and iron. The method simplifies the separation process, greatly reduces the cost, but the product obtained by the method has high impurity content and can only be used as a low-grade product.
China is also a big country for titanium dioxide production, wherein most enterprises are titanium dioxide produced by a sulfuric acid process, each 1 ton of titanium dioxide produced by the process can generate about 15-20% of waste sulfuric acid of 8-10 tons, and the waste acid contains about 180-250 g/l of sulfuric acid and about Fe 2+ 30～40g/l、 Ti 4+ 2～4g/l、Mn 2+ 0.5～5g/l、Mg 2+ 0.2～5g/l、Ca 2+ 0.1～0.4g/l、Al 3+ 0.1～1g/l、V 3+0.1-0.3 g/l, etc., at present, no good treatment method for the waste acid exists, such as rust removal for steel, iron oxide red production, 50% concentration production of sulfuric acid, lime cream neutralization, etc. The method for producing the aluminum-vanadium-containing alloy is characterized in that ammonia is used for neutralization, the pH value is controlled, hydroxides of aluminum, titanium and vanadium are precipitated, a proper amount of ammonia or ammonium sulfate is added, and the mixture is cooled to below 20 ℃ to precipitate ammonium alum.
The manganese-zinc ferrite particles can be divided into manganese-zinc power ferrite materials, manganese-zinc high-permeability ferrite materials and magnesium-manganese-zinc ferrite materials for deflection coils, and the production methods mainly comprise two types: oxide method (dry method) and coprecipitation method (wet method). The oxide method is a main method, and takes iron oxide, manganese oxide or manganese carbonate, zinc oxide or zinc carbonate as raw materials, and manganese-zinc ferrite granules are obtained by mixing, presintering, drying and granulating; the co-precipitation method is generally used for producing high-grade high-magnetic-permeability products, and is characterized by that the metal iron, manganese and zinc are dissolved in sulfuric acid, then the ammonium carbonate is added to make neutralization to make iron, manganese and zinc be co-precipitated, then the above-mentioned materials are presintered, dried and granulated to obtain the invented manganese-zinc ferrite granules with fine grain size, high activity, good uniformity and high cost. The annual output of manganese zinc ferrite granular materials in China is about 10 ten thousand tons, wherein the high magnetic conductivity output is about 2 to 3 ten thousand tons, and the annual output of manganese zinc ferrite granular materials produced by adopting a coprecipitation method is about 1 ten thousand tons. The manganese-zinc ferrite particles have high added value, the used raw materials also need high purity, each element raw material used by the manganese-zinc ferrite particles needs to be thoroughly separated from other elements (including useful elements of the manganese-zinc ferrite particles), and complicated separation processes are needed, so that the manganese-zinc ferrite particles have long process flow and low recovery rate and high cost.
Disclosure of Invention
The invention aims to provide a method for preparing manganese-zinc ferrite granules and mixed carbonate by using waste dry batteries and waste sulfuric acid or industrial sulfuric acid obtained by a titanium white sulfate method as raw materials.
The invention is realized by the following technical scheme:
a method for preparing manganese zinc ferrite granules and mixed carbonate by using waste dry batteries is characterized by comprising the following steps: the method comprises the steps of crushing waste dry batteries, leaching the crushed waste dry batteries by using waste sulfuric acid or industrial sulfuric acid of a titanium white sulfate method, forming mercury sulfide precipitate by vulcanizing, screening out large particles, filtering, washing filter residues, then recovering mercury and heat by safe landfill or high-temperature incineration treatment, magnetically separating oversize products, returning separated iron to acid leaching, washing the rest, then physically sorting or high-temperature incineration, purifying filtrate through oxidation heating, replacement and hydrolysis processes, washing purified residues, recovering valuable elements, neutralizing purified liquid by using carbonate solution, washing and drying precipitates to obtain mixed carbonate, and concentrating and crystallizing the neutralized mother liquor to produce ammonium sulfate. The process flow is shown in figure 1, and the specific steps are as follows:
(1) Crushing: crushing the waste dry batteries, but not crushing the carbon rods and the plastic into powder;
(2) Acid leaching: the leaching agent is waste sulfuric acid or industrial sulfuric acid obtained by a titanium sulfate white process, and is used for leaching crushed waste dry batteries to leach manganese ions and zinc ions; the leaching agent contains 180-250 g/l of sulfuric acid, the solid-liquid ratio of the waste dry battery to the leaching agent is 1: 4-8, the leaching temperature is 60-85 ℃, and the leaching time is 3-6 hours;
(3) And (3) vulcanizing: precipitating mercury by using an ammonium sulfide solution, wherein the using amount of ammonium sulfide (containing 8 percent of ammonium sulfide) is not more than 0.4 percent of the volume of an acid leaching solution, the reaction temperature is 50-80 ℃, the reaction time is 1-2 hours, and the pH value during vulcanization is 1-2 by controlling the solid-liquid ratio of the acid leaching reaction or adding a small amount of scrap iron for replacement; for mercury-free batteries, the sulfidation process can be performed before the reduction hydrolysis process;
(4) Screening and filtering: screening the pickle liquor to separate large particles, filtering, washing filter residues, safely burying or burning the filter residues to collect mercury and heat, magnetically separating iron from the screened filter residues, washing, physically separating copper rods, carbon rods and plastics or sending the materials to a burning furnace for treatment, and returning the iron to acid leaching. For the mercury-free battery, the carbon residue after filtration can be used for recovering carbon powder and returning to the production of a dry battery;
(5) And (3) incineration: burning in a closed manner, fully stirring and oxidizing to completely burn the carbon powder and the plastic, wherein the temperature of the burning furnace is more than or equal to 1200 ℃, the slag is used for recovering copper, and the flue gas is used for reducing the temperature, collecting dust and removing mercury;
(6) Oxidation heating and filtering: the oxidant adopted by the oxidation heating is hydrogen peroxide or Fe 2 (SO 4 ) 3 Solution in an amount corresponding to Ti in the solution 3+ 、K + 、Na + The ion content is determined, the heating reaction temperature is 70-95 ℃, the reaction time is 3-6 hours, the reaction pH value is 1-2, and a small amount of jarosite crystal seeds are added to accelerate the precipitation of the jarosite. Washing the filter residue and recovering TiO 2 Iron vitriol;
(7) Replacement: during the replacement, iron powder or zinc powder is added quantitatively, the reaction temperature is 50-80 ℃, the reaction time is 1-3 hours, and the reaction pH value is 2-5. The dosage of the iron powder and the zinc powder is determined according to the components of the solution and the requirements of the product;
(8) Hydrolysis: during hydrolysis, manganese carbonate or ammonia water is added quantitatively, the reaction temperature is 50-80 ℃, the reaction time is 1-3 hours, the reaction pH value is 2-5, and the dosage of the manganese carbonate is determined according to the solution components and the product requirements. In the case of industrial sulfuric acid production, a small amount of Fe can be added during hydrolysis because of less hydrolyzable matter 2 (SO 4 ) 3 Solution to produce Fe (OH) 3 Precipitating to adsorb purified silicon, etc. in an amount of less than 2% of the total metal content in the solution;
(9) And (3) filtering: filtering after the hydrolysis is finished, washing filter residues, recovering valuable elements, and neutralizing filtrate;
(10) Neutralizing: neutralizing the purified solution with carbonate solution, washing the precipitate, filtering, and concentrating and crystallizing the neutralized mother solution to produce ammonium sulfate;
(11) Drying: drying the filter residue at 110-120 ℃ to obtain a mixed carbonate raw material for producing manganese-zinc ferrite granules;
as shown in a dotted line box in fig. 1, iron and manganese elements are added in the acid leaching process, the obtained mixed carbonate is subjected to presintering and granulation to obtain a manganese-zinc ferrite granular material product, the adding mode of the iron and manganese elements is shown in a dotted line in fig. 1, the required mixed sulfate solution can be added into the purified solution, the iron sheet can be added into the acid leaching process to be leached together with the waste dry battery, and a certain amount of manganese sulfate and the byproduct of the titanyl sulfate method, namely, copperas, can be added into the filtrate before the oxidation heating process.
As shown in fig. 2, magnetic separation is performed on one part of the crushed waste dry batteries, the iron sheet magnetically separated is added into the other part of the waste dry batteries which are not magnetically separated, the proportion of the magnetic separation and the non-magnetic separation of the waste dry batteries is determined according to the proportion of iron, manganese and zinc in the waste dry batteries and the components of manganese-zinc ferrite particles to be produced, then the materials after magnetic separation are performed according to the process mode of producing mixed carbonate, the waste dry batteries added with the iron sheet are performed according to the method for preparing the manganese-zinc ferrite particles, and the manganese-zinc ferrite particles and the mixed carbonate are co-produced.
The beneficial effects of the invention are: the manganese-zinc ferrite particle material and the mixed carbonate are prepared by using the waste dry batteries and the waste sulfuric acid or industrial sulfuric acid obtained by a titanium white sulfate method as raw materials, and meanwhile, the wet mercury removal method is simple, effective and free of new pollution, low in equipment investment, capable of being used for removing mercury-free batteries and high in economic benefit.
Drawings
The invention is described in further detail below with reference to the figures and examples.
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a process flow diagram for co-producing manganese zinc ferrite particles and mixed carbonate.
Detailed Description
Example 1
Taking two parts of 4 kg of crushed waste dry batteries, washing twice by softened water, separating washing water after sedimentation, adding one part into a titanium dioxide factory25 liters of waste sulfuric acid (containing 180g/l of sulfuric acid) and 25 liters of industrial sulfuric acid (containing 180g/l of sulfuric acid) are added into the other part, and then the mixture is heated and leached, wherein the leaching temperature is 80-85 ℃, and the leaching time is 4 hours. After the reaction is completed, the pH value of the solution is about 1, 60 ml of 8% ammonium sulfide solution is added dropwise and stirred for 2 hours, then large particles are sieved out and filtered, and the filtrate is about 22L and contains less than 0.05 mg/L of mercury. Fe containing 100 g of Fe is added into the filtrate 2 (SO 4 ) 3 Heating the solution to a reaction temperature of 90-95 ℃ for 3 hours, cooling and filtering. Adding 30 g of iron powder into the filtrate for replacement, adding 15 g of zinc powder for replacement after the reaction is completed, adding ammonia water after the reaction is completed to adjust the pH value to be 5 so as to complete the hydrolysis reaction, and adding 10 g of Fe during the hydrolysis in the part using industrial sulfuric acid as a leaching agent 2 (SO 4 ) 3 Solution to produce Fe (OH) 3 And (4) precipitating. Filtering after complete hydrolysis, neutralizing the filtrate with a mixed solution of ammonium bicarbonate and ammonia water with the same volume, keeping the reaction temperature at 45 ℃, keeping the end point pH value at 7.5, precipitating for 1 hour, washing the precipitate with pure water, filtering and drying to obtain the mixed carbonate raw material containing iron, zinc and manganese (the analysis result of the impurity components of the carbonate is shown in Table 1).
Example 2
4 kg of crushed waste dry batteries are washed twice by softened water, washing water is separated after sedimentation, 52 liters of industrial sulfuric acid (containing 180g/l of sulfuric acid) is added, 2.8 kg of iron sheet magnetically selected from the waste dry batteries is added, and then the waste dry batteries are heated and extracted, wherein the leaching temperature is 80-85 ℃, and the leaching time is 4 hours. After the reaction is completed, the solution has a pH value of about 1, 60 ml of 8% ammonium sulfide solution is added dropwise and stirred for 2 hours, then large particles are sieved out and filtered, and the filtrate is about 50L and contains less than 0.05 mg/L of mercury. Fe containing 100 g of Fe is added into the filtrate 2 (SO 4 ) 3 Heating the solution to the reaction temperature of 90-95 ℃ for 3 hours, then cooling and filtering. Adding 30 g of iron powder into the filtrate for replacement, and adding 15 g of iron powder after the reaction is completedZinc powder replacement, adding manganese carbonate slurry containing 75 g of manganese and ammonia water after the reaction is completed to adjust the pH value to 5 so as to complete the hydrolysis reaction, then filtering, neutralizing the filtrate by using mixed solution of ammonium bicarbonate and ammonia water with equal volume, wherein the reaction temperature is 45 ℃, the end-point pH value is 7.5,and (3) preserving heat and precipitating for 1 hour, then washing the precipitate with pure water, filtering and drying, then presintering at 950 ℃, and then performing sand milling, drying and granulating to obtain the manganese-zinc ferrite granular material product (the performance analysis result of the manganese-zinc ferrite granular material is shown in table 2).
Table 1: analysis result (ppm) of impurity component of carbonate
| Become into Is divided into | Cu | Ni | Cd | K 2 O | Na 2 O | CaO | MgO | Ti | Al | V | Nb | SiO 2 |
| 1 # | 2 | 660 | 27 | 31 | 91 | 39 | 6 | - | - | - | - | 95 |
| 2 # | 1 | 177 | 47.4 | 57 | 114 | 17.3 | 885 | 11 | 143 | 27 | 18 | 114 |
Table 2: results of Performance analysis of manganese Zinc ferrite particles
| Sintering conditions | 1420 deg.C, cooling in nitrogen | Sample type | T18×8×5 | |
| Test conditions | WK4225 instrument, 1KHz,1TS,0.25V, phi 0.5mm 25℃， | |||
| Analysis results | ||||
| Item | As a result, the | Frequency spectrum (1601 watch) | ||
| Inductor (L) | 6.94 | Frequency of | Inductance | |
| Quality factor (Q)(10KHz) | 19 | 1KHz | 6.72 | |
| Density (p) | 4.87 | 10KHz | 6.51 | |
| Curie temperature (Tc) | 110℃ | 50KHz | 5.91 | |
| Scale of reduction | 1.176 | 100KHz | 5.48 | |
| 150KHz | 5.12 | |||
| Note: the product is high magnetic permeability material with initial magnetic permeability of 8300 | ||||
Claims (3)
1. A method for preparing manganese zinc ferrite granules and mixed carbonate by using waste dry batteries is characterized by comprising the following steps: the method comprises the following steps of crushing waste dry batteries, leaching the crushed waste dry batteries by using waste sulfuric acid or industrial sulfuric acid of a titanium white sulfate method, forming mercury sulfide precipitate by using mercury through vulcanization, filtering after screening out large particulate matters, washing filter residues, recovering mercury and heat by safe landfill or high-temperature incineration treatment, magnetically separating oversize products, returning separated iron to acid leaching, physically sorting or high-temperature incineration after washing the rest, purifying filtrate through oxidation heating, replacement and hydrolysis processes, recovering valuable elements after washing purified residues, neutralizing purified liquid with a carbonate solution, washing and drying the precipitate to obtain mixed carbonate, and concentrating and crystallizing the neutralized mother liquor to produce ammonium sulfate, wherein the method specifically comprises the following steps:
(1) Crushing: crushing the waste dry batteries, but not crushing the carbon rods and the plastic into powder;
(2) Acid leaching: the leaching agent is waste sulfuric acid or industrial sulfuric acid obtained by a titanium sulfate white method, the crushed waste dry batteries are leached, the content of the sulfuric acid in the leaching agent is 180-250 g/l, the solid-liquid ratio of the waste dry batteries to the leaching agent is 1: 4-8, the leaching temperature is 60-85 ℃, and the leaching time is 3-6 hours;
(3) And (3) vulcanization: precipitating mercury by using an ammonium sulfide solution, wherein the use amount of the ammonium sulfide solution with the concentration of 8 percent does not exceed 0.4 percent of the volume of the acid leaching solution, the reaction temperature is 50-80 ℃, the reaction time is 1-2 hours, and the pH value during vulcanization is 1-2 by controlling the solid-to-liquid ratio of the acid leaching reaction or adding a small amount of scrap iron for replacement; for mercury-free batteries, the sulfurization process is carried out before the replacement hydrolysis process;
(4) Screening and filtering: screening the acid leaching solution to separate large-particle substances, filtering, washing filter residues, then safely burying or sending the filter residues to an incinerator for incineration treatment to recover mercury and heat, carrying out magnetic separation on oversize substances, washing the oversize substances, separating iron, physically separating copper rods, carbon rods and plastics or sending the copper rods, carbon rods and plastics to the incinerator for treatment, returning the iron to acid leaching, and for mercury-free batteries, recovering carbon powder from filtered carbon residues and returning the carbon powder to the production of dry batteries;
(5) And (3) incineration: burning in a closed manner, fully stirring and oxidizing to completely burn the carbon powder and the plastic, wherein the temperature of the burning furnace is more than or equal to 1200 ℃, the slag is used for recovering copper, and the flue gas is used for reducing the temperature, collecting dust and removing mercury;
(6) Oxidation heating and filtering: the oxidant adopted by the oxidation heating is hydrogen peroxide or Fe 2 (SO 4 ) 3 Solution in an amount corresponding to Ti in the solution 3+ 、K + 、Na + The ion content is determined, the heating reaction temperature is 70-95 ℃, the reaction time is 3-6 hours, the reaction pH value is 1-2, a small amount of jarosite crystal seeds or jarosite crystal seeds are added to accelerate the precipitation of the jarosite, and the filter residue is washed to recover TiO 2 Iron vitriol;
(7) Replacement: during replacement, quantitatively adding iron powder or zinc powder, wherein the dosage of the iron powder and the zinc powder is determined according to the solution components and the product requirements;
(8) Hydrolysis: during hydrolysis, manganese carbonate or ammonia water is quantitatively added, the pH value is adjusted to 2-5, the use level of manganese carbonate is determined according to the solution components and the product requirements, and during production by using industrial sulfuric acid, because the hydrolysate is less, a small amount of Fe is added during hydrolysis 2 (SO 4 ) 3 Solution to produce Fe (OH) 3 Precipitating to adsorb purified silicon, wherein the usage amount of the purified silicon is less than 2% of the total amount of metals in the solution;
(9) And (3) filtering: filtering after the hydrolysis is finished, washing filter residues, recovering valuable elements, and neutralizing filtrate;
(10) Neutralizing: neutralizing the purified solution with carbonate solution, washing the precipitate, filtering, and concentrating and crystallizing the neutralized mother solution to produce ammonium sulfate;
(11) And (3) drying: and drying the filter residue to obtain a mixed carbonate product for producing manganese-zinc ferrite.
2. The method as claimed in claim 1, wherein a certain amount of iron and manganese elements are added according to the components of the manganese-zinc ferrite granular material to be produced, the obtained mixed carbonate is presintered and granulated to obtain the manganese-zinc ferrite granular material, the iron and manganese elements are added in a mode of adding the required iron and manganese sulfate solution into the purified solution, or the iron sheet is added into the acid leaching process to be leached together with the waste dry battery, or a certain amount of manganese sulfate and the byproduct of the titanyl sulfate method are added into the filtrate before the oxidation heating process.
3. The method as claimed in claim 1, wherein a part of the crushed waste dry batteries is magnetically separated, the magnetically separated iron sheet is added to another part of the waste dry batteries which are not magnetically separated, the ratio of the magnetic separation and the non-magnetic separation of the waste dry batteries is determined according to the ratio of iron, manganese and zinc in the waste dry batteries and the components of the manganese-zinc ferrite particles to be produced, the magnetically separated materials are processed according to the process for producing the mixed carbonate, and the waste dry batteries added with the iron sheet are processed according to the method for producing the manganese-zinc ferrite particles to co-produce the manganese-zinc ferrite and the mixed carbonate.
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| CN101736167B (en) * | 2008-11-05 | 2011-11-16 | 广西银亿科技矿冶有限公司 | Method for leaching nickel-containing eluvial ore |
| CN103545538A (en) * | 2013-11-06 | 2014-01-29 | 安徽工业大学 | A method of using waste zinc-manganese dry batteries to prepare raw materials for manganese-based ferroalloys |
| CN104779403B (en) * | 2015-04-24 | 2017-05-31 | 桂林理工大学 | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology |
| WO2019150005A1 (en) * | 2018-02-05 | 2019-08-08 | Tracegrow Oy | Processes for production of micronutrients from spent alkaline batteries |
| CN110661052A (en) * | 2018-07-01 | 2020-01-07 | 临沂春光磁业有限公司 | Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder |
| CN109896849A (en) * | 2019-04-22 | 2019-06-18 | 南通冠优达磁业有限公司 | A kind of method that manganese-zinc ferrite grinding waste material prepares manganese-zinc ferrite |
| CN116875827B (en) * | 2023-07-12 | 2024-03-15 | 重庆上甲电子股份有限公司 | Method for preparing soft magnetic manganese zinc ferrite composite material by utilizing manganese-containing waste residues and zinc-containing waste residues generated in production of perillaldehyde |
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