CN113234941B - High-value utilization method of electrolytic manganese anode slime - Google Patents
High-value utilization method of electrolytic manganese anode slime Download PDFInfo
- Publication number
- CN113234941B CN113234941B CN202110537032.5A CN202110537032A CN113234941B CN 113234941 B CN113234941 B CN 113234941B CN 202110537032 A CN202110537032 A CN 202110537032A CN 113234941 B CN113234941 B CN 113234941B
- Authority
- CN
- China
- Prior art keywords
- washing
- electrolytic manganese
- manganese anode
- anode slime
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a high-value utilization method of electrolytic manganese anode slime, relates to the technical field of manganese slag recycling, and solves the technical problem that in the recycling process of the electrolytic manganese anode slime, the high-value utilization of the electrolytic manganese anode slime is limited because impurities such as Ca, Mg, sulfate and the like are not deeply purified in the prior art. According to the high-value utilization method of the electrolytic manganese anode slime, impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime are efficiently removed by sequentially adopting a water washing method, an alkali washing method and an acid leaching method, then the anode slime after impurity removal is leached by adopting hydrogen peroxide and sulfuric acid, the obtained leachate is a high-purity manganese sulfate solution, and the leaching slag is lead concentrate. Compared with the prior art, the method can realize deep purification of impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime, and enrichment of Pb, and in addition, the obtained manganese sulfate solution can be used as a raw material for preparing high-purity manganese sulfate, electrolytic metal manganese and electrolytic manganese dioxide products.
Description
Technical Field
The invention relates to the technical field of manganese slag recycling, in particular to a high-value utilization method of electrolytic manganese anode slime.
Background
Electrolytic manganese metal is an important basic substance in national economy and one of important strategic resources of the country. China is a big country for producing, consuming and exporting electrolytic manganese, and the yield of electrolytic manganese metal in China in 2020 is 150.1 ten thousand tons, which accounts for 96.5 percent of the total global yield. When metal manganese is produced by electrolysis, the anode area generates electrolytic manganese anode mud waste residues, so that the electrolytic manganese industry is rapidly developed and faces huge resource and environmental pressure, and particularly, the disposal of the electrolytic manganese anode mud becomes one of the important concerns of electrolytic manganese enterprises. The electrolytic manganese anode mud is a black brown sediment generated by anode side reaction in the production process of electrolytic manganese metal, and the main components of the electrolytic manganese anode mud comprise Mn (40-50%), Pb (6-9%), Sn, Fe, Ni and other heavy metals. At present, electrolytic manganese anode slime is generally subjected to direct stockpiling treatment, which causes great pressure on the environment.
At present, the research on resource utilization of electrolytic manganese anode slime mainly focuses on how to realize efficient leaching of manganese. The conventional leaching process is to reduce high-valence manganese in the electrolytic manganese anode slime into Mn by adopting a reducing agent under an acidic condition2+And then the qualified manganese sulfate solution is prepared through the procedures of solid-liquid separation, impurity removal and the like. The reducing agents commonly used at present mainly comprise ammonium acetate, iron powder, ammonium sulfite and FeS2、SO2Sulfur-containing compounds, glucose, orange peel, wood chips, and the like. These reducing agents can realize manganese leaching, but because of complex process, high leaching cost, large consumption of reducing agents, low manganese leaching rate, residual organic matters in leaching solution and the like, the reducing agents are difficult to realize industrial application. The applicant also finds that during the manganese extraction process of the electrolytic manganese anode slime, impurities such as Ca, Mg, sulfate and the like carried in the electrolytic manganese anode slime easily enter a solution, so that a leachate contains a large amount of impurities such as Ca, Mg, sulfate and the like, and the impurities directly influence the purity of the leachate for preparing products such as high-purity manganese sulfate, electrolytic manganese metal, electrolytic manganese dioxide and the like. Therefore, how to efficiently remove impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime is a key for realizing high-value utilization of the electrolytic manganese anode slime.
In fact, impurities such as Ca, Mg and the like in the electrolytic manganese anode mud usually exist in the form of sulfate, double salt and the like, and the content is generally 1-5%. At present, the patents related to the resource utilization of the electrolytic manganese anode slime rarely relate to the removal of impurities such as Ca, Mg, sulfate and the like. For example, in patent No. cn202011072257.x, electrolytic manganese anode slime is carbonated first, and then lead is volatilized by high-temperature reduction, so that lead oxide smoke dust used as a raw material for lead smelting and manganese slag used for leaching manganese ore are obtained, the desulfurization rate of the anode slime treated by the method is over 90%, the volatilization rate of Pb is over 96%, but the energy consumption in the high-temperature reduction process is high, and impurities such as Ca, Mg, sulfate and the like are not removed. And treating the electrolytic manganese anode slime by using waste honey or industrial-grade glucose as a reducing agent as in the patent No. CN105039703.A, and removing impurities to obtain manganese carbonate and lead sulfate concentrate, wherein the leaching rate of manganese is 96.33%, the lead recovery rate is 90.63%, and the leachate obtained by the method still contains impurities such as Ca, Mg, sulfate and the like. And for example, in patent No. CN202010880509.5, sodium acetate is adopted to leach lead in the electrolytic manganese anode slime, the lead concentration can be increased to more than 30g/L after the lead leachate is evaporated and concentrated, but the obtained leachate still contains impurities such as Ca, Mg, sulfate and the like.
At present, a great deal of researchers mainly concentrate on how to separate/remove Mn and Pb in the electrolytic manganese anode slime, and do not consider deep purification of impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime, so that high-value utilization of the electrolytic manganese anode slime is limited.
Disclosure of Invention
The invention aims to provide a high-value utilization method of electrolytic manganese anode slime, which solves the technical problem that in the prior art, in the recycling process of the electrolytic manganese anode slime, the high-value utilization of the electrolytic manganese anode slime is limited because impurities such as Ca, Mg, sulfate and the like are not deeply purified. The various technical effects that can be produced by the preferred technical solution of the present invention are described in detail below.
In order to realize the purpose, the invention provides the following technical scheme:
the electrolytic manganese anode mud high-value utilization method adopts water washing, alkali washing and acidAfter Ca, Mg and sulfate in the electrolytic manganese anode slime are removed by a leaching method, H is adopted2O2And H2SO4The leaching obtains a manganese sulphate solution and a lead concentrate, and the method comprises the following steps:
s1: drying and crushing the electrolytic manganese anode mud, and sieving for later use;
s2: mixing the sieved electrolytic manganese anode mud with water, then washing for the first time, carrying out solid-liquid separation after the first washing to obtain a 1# material and a 2# washing liquid, and transferring the 2# washing liquid to a wastewater treatment workshop for centralized treatment;
s3: mixing the material 1 obtained in the step S2 with water, adding an alkaline material to adjust the pH of the system to be alkaline, adding carbonate to wash, performing solid-liquid separation after washing to obtain a material 3 and a washing liquid 4, and transferring the washing liquid 4 to a wastewater treatment workshop for centralized treatment;
s4: mixing the 3# material obtained in the step S3 with water, adding hydrochloric acid for acid washing, performing solid-liquid separation after acid washing to obtain a 5# material and a 6# washing liquid, and transferring the 6# washing liquid to a wastewater treatment workshop for centralized treatment;
s5: mixing the 5# material obtained in the step S4 with water, then carrying out secondary water washing, carrying out solid-liquid separation after the secondary water washing to obtain a 7# material and an 8# washing liquid, and transferring the 8# washing liquid to a wastewater treatment workshop for centralized treatment;
s6: mixing the material 7# obtained in the step S5 with water, and adding H2O2And H2SO4And after full reaction, carrying out solid-liquid separation to obtain a 9# material and a 10# washing solution, wherein the 9# material is lead concentrate, and the 10# washing solution is a manganese sulfate solution.
According to a preferred embodiment, in the step S1, the temperature for drying the electrolytic manganese anode slime is 40-80 ℃, and the drying time is 5-48 h; and crushing the dried electrolytic manganese anode mud, and sieving the crushed electrolytic manganese anode mud by using a sieve of 80-200 meshes.
According to a preferred embodiment, in the step S2, the sieved electrolytic manganese anode slime is mixed with water according to a solid-liquid mass ratio of 1: 2-1: 6, the temperature of primary water washing is 20-40 ℃, and the time of the primary water washing is 0.5-3 h.
According to a preferred embodiment, in the step S3, the material No. 1 and water are mixed according to the solid-liquid mass ratio of 1: 3-1: 5, carbonate is added to wash at the temperature of 20-40 ℃ for 2-5 h.
According to a preferred embodiment, in step S3, the alkaline material is ammonia water and/or NaOH, and the pH of the system is adjusted to 7.0 to 9.0 by adding ammonia water and/or NaOH.
According to a preferred embodiment, in step S3, the carbonate is (NH)4)2CO3、NH4HCO3、Na2CO3And the mass ratio of the carbonate to the 1# material is 0.5: 100-5: 100.
According to a preferred embodiment, in the step S4, the material 3# is mixed with water according to the solid-liquid mass ratio of 1: 2-1: 5; the concentration of the hydrochloric acid is 0.6-0.8 g/L, the temperature for acid washing by adding the hydrochloric acid is 20-40 ℃, and the washing time is 1-5 h.
According to a preferred embodiment, in the step S5, the 5# material and water are mixed according to the solid-liquid mass ratio of 1: 4-1: 6, the temperature of the secondary water washing is 20-40 ℃, and the time of the secondary water washing is 0.5-3 h.
According to a preferred embodiment, in step S6, the material No. 7 is mixed with water according to a solid-liquid mass ratio of 1: 4-1: 6, and the material No. 7 is mixed with H2O2And H2SO4The reaction temperature of (2) is 30-60 ℃, and the reaction time is 10-120 min.
According to a preferred embodiment, in step S6, material # 7 is mixed with H2O2The mass ratio of (A) to (B) is 1: 0.5-1: 1.2; 7# Material and H2SO4The mass ratio of (A) to (B) is 1: 0.6-1: 1.2.
The high-value utilization method of the electrolytic manganese anode slime provided by the invention at least has the following beneficial technical effects:
according to the high-value utilization method of the electrolytic manganese anode slime, on the basis of occurrence forms of impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime, firstly, the impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime are efficiently removed by sequentially adopting methods of water washing, alkali washing and acid leaching, and then, the anode slime after impurity removal is leached by adopting hydrogen peroxide and sulfuric acid. Compared with the prior art, the method can realize deep purification of impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode mud, meanwhile, the content of Pb in the slag obtained after leaching hydrogen peroxide and sulfuric acid can be increased to 50-55% from 6-7% of the original electrolytic manganese anode mud, enrichment and resource utilization of Pb are realized, the obtained manganese sulfate solution can be used as a raw material for preparing high-purity manganese sulfate, electrolytic manganese metal and electrolytic manganese dioxide products, and a new idea is provided for high-value utilization of the electrolytic manganese anode mud.
According to the high-value utilization method of the electrolytic manganese anode slime, after impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime are removed efficiently, the purity of lead concentrate and manganese sulfate solution obtained after the electrolytic manganese anode slime is leached is high, specifically, the content of lead in the lead concentrate is more than 50%, the leaching rate of manganese is more than 98%, and leachate contains extremely low Ca and Mg, so that the utilization value is higher, the high-value utilization of the electrolytic manganese anode slime can be realized, and the technical problem that the high-value utilization of the electrolytic manganese anode slime is limited because the impurities such as Ca, Mg, sulfate and the like are not deeply purified in the recycling process of the electrolytic manganese anode slime in the prior art is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow chart of the high-value utilization method of electrolytic manganese anode slime.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without making any creative effort, shall fall within the protection scope of the present invention.
The method for high-value utilization of electrolytic manganese anode slime according to the invention is described in detail below with reference to the accompanying drawing 1 and examples 1 to 3.
The high-value utilization method of the electrolytic manganese anode slime adopts methods of water washing, alkali washing and acid leaching to remove Ca, Mg and sulfate in the electrolytic manganese anode slime, and then adopts H2O2And H2SO4The leaching yields a manganese sulphate solution and lead concentrate, as shown in figure 1. Compared with the prior art, the high-value utilization method of the electrolytic manganese anode slime can realize deep purification of impurities such as Ca, Mg, sulfate and the like in the electrolytic manganese anode slime, simultaneously improve the Pb content in the slag obtained after leaching hydrogen peroxide and sulfuric acid to 50-55% from 6-7% of the original electrolytic manganese anode slime, realize Pb enrichment and resource utilization, and obtain a manganese sulfate solution which can be used as a raw material for preparing high-purity manganese sulfate, electrolytic manganese metal and electrolytic manganese dioxide products.
Preferably, the method for high-value utilization of electrolytic manganese anode slime comprises the following steps:
s1: drying and crushing the electrolytic manganese anode mud, and sieving for later use. Preferably, the temperature for drying the electrolytic manganese anode mud is 40-80 ℃, and the drying time is 5-48 h; and crushing the dried electrolytic manganese anode mud, and sieving the crushed electrolytic manganese anode mud by using a sieve of 80-200 meshes. The electrolytic manganese anode slime is dried, crushed and sieved, so that the removal effect of Ca, Mg and sulfate impurities in the electrolytic manganese anode slime is improved.
S2: and mixing the sieved electrolytic manganese anode mud with water, then carrying out primary water washing, carrying out solid-liquid separation after the primary water washing to obtain a 1# material and a 2# washing liquid, and transferring the 2# washing liquid to a wastewater treatment workshop for centralized treatment. Preferably, the sieved electrolytic manganese anode mud and water are mixed according to the solid-liquid mass ratio of 1: 2-1: 6, the temperature of primary washing is 20-40 ℃, and the time of the primary washing is 0.5-3 h. The screened electrolytic manganese anode mud is mixed with water to be washed for one time, and then the electricity can be removedSoluble Ca entrained in manganese-dissolving anode slime2+、Mg2+Ammonium sulfate, manganese sulfate and the like. Specifically, the 2# washing liquid obtained by primary washing mainly contains sulfate such as calcium sulfate, magnesium sulfate, ammonium sulfate, manganese sulfate and the like, and the 2# washing liquid can be treated by a triple-effect multistage evaporation concentration method after being transferred to a wastewater treatment workshop. Part of sulfate such as manganese sulfate, magnesium sulfate and the like is carried in the material 1 obtained by the primary water washing.
S3: and (4) mixing the material 1 obtained in the step (S2) with water, adding an alkaline material to adjust the pH value of the system to be alkaline, adding carbonate to wash, carrying out solid-liquid separation after washing to obtain a material 3 and a washing solution 4, and transferring the washing solution 4 to a wastewater treatment workshop for centralized treatment. Preferably, the No. 1 material and water are mixed according to the solid-liquid mass ratio of 1: 3-1: 5, the temperature for washing by adding carbonate is 20-40 ℃, and the washing time is 2-5 hours. Preferably, the alkaline material is ammonia water and/or NaOH, and the pH value of the system is adjusted to 7.0-9.0 by adding the ammonia water and/or NaOH. Preferably, the carbonate is (NH)4)2CO3、NH4HCO3、Na2CO3And the mass ratio of the carbonate to the 1# material is 0.5: 100-5: 100. According to the invention, the carbonate is added to wash the material 1# obtained in the step S2, so that the manganese sulfate and magnesium sulfate carried by the material and the insoluble calcium sulfate can be converted into manganese carbonate, magnesium carbonate and calcium carbonate. Specifically, the 3# material obtained by washing the material with carbonate mainly contains MnCO3、SiO2、PbSO4And CaCO3、MgCO3Etc.; the resulting 4# wash solution contained predominantly (NH)4)2SO4、(NH4)2CO3、Na2CO3、Na2CO3And the like.
S4: and (4) mixing the 3# material obtained in the step (S3) with water, adding hydrochloric acid for acid washing, performing solid-liquid separation after acid washing to obtain a 5# material and a 6# washing liquid, and transferring the 6# washing liquid to a wastewater treatment workshop for centralized treatment. Preferably, in the step S4, the 3# material is mixed with water according to the solid-liquid mass ratio of 1: 2-1: 5; the concentration of the hydrochloric acid is 0.6 g/L-0.8 g/L,the temperature for acid washing by adding hydrochloric acid is 20-40 ℃, and the washing time is 1-5 h. According to the invention, the manganese carbonate, the magnesium carbonate and the calcium carbonate precipitate can be dissolved by adding hydrochloric acid to wash the 3# material obtained in the step S3. Specifically, the 5# material obtained by pickling with hydrochloric acid mainly contains MnO2、SiO2、PbSO4Etc.; the obtained No. 6 lotion mainly contains CaCl2、MgCl2、NH4Cl, and the like.
S5: and (5) mixing the 5# material obtained in the step (S4) with water, then carrying out secondary water washing, carrying out solid-liquid separation after the secondary water washing to obtain a 7# material and an 8# washing liquid, and transferring the 8# washing liquid to a wastewater treatment workshop for centralized treatment. Preferably, the No. 5 material and water are mixed according to the solid-liquid mass ratio of 1: 4-1: 6, the temperature of secondary washing is 20-40 ℃, and the time of secondary washing is 0.5-3 h. The invention mixes the 5# material obtained in the step S4 with water and then carries out secondary water washing to remove residual chloride ions in the 5# material. After the treatment of the steps S1-S5, the content of impurities such as Ca, Mg and the like in the obtained 7# material is extremely low, and the 7# material mainly contains MnO2And PbSO4。
S6: mixing the material 7# obtained in the step S5 with water, and adding H2O2And H2SO4And after full reaction, carrying out solid-liquid separation to obtain a 9# material and a 10# washing solution, wherein the 9# material is lead concentrate, and the 10# washing solution is a manganese sulfate solution. Preferably, the 7# material is mixed with water according to the solid-liquid mass ratio of 1: 4-1: 6, and the 7# material is mixed with H2O2And H2SO4The reaction temperature is 30-60 ℃, and the reaction time is 10-120 min. Preferably, the 7# material is mixed with H2O2The mass ratio of (A) to (B) is 1: 0.5-1: 1.2; 7# Material and H2SO4The mass ratio of (A) to (B) is 1: 0.6-1: 1.2. By means of H2O2Has reducing property under acidic condition, thereby reducing and leaching manganese oxide H in electrolytic manganese anode mud2O2The manganese is decomposed into water and oxygen in the leaching process, so that the leaching rate of the manganese in the electrolytic manganese anode mud can be ensured, harmful byproducts can not be generated, and the environmental pollution is reduced.
Preferably, obtained in step S2After the 2# washing solution obtained in the step S3, the 4# washing solution obtained in the step S3, the 6# washing solution obtained in the step S4 and the 8# washing solution obtained in the step S5 are collectively transferred to a wastewater treatment plant, the wastewater is treated by a triple-effect multistage evaporation concentration method to obtain an evaporated liquid and a concentrated product. The main component of the evaporation liquid is water, and the evaporation liquid can be recycled; the concentrated product contains (NH) as main component4)2SO4、(NH4)2CO3、Na2CO3、MgCO3、NH4Cl and the like, and the concentrated product can be recycled.
The method for high-value utilization of electrolytic manganese anode slime of the present invention will be described in detail with reference to examples 1 to 3.
Example 1
Taking 5kg of electrolytic manganese anode mud which is dried, crushed and sieved by a sieve of 80 meshes, washing for 3h under the conditions that the mass ratio of clear water to electrolytic manganese anode mud solution is 2: 1 and the reaction temperature is 20 ℃, and filtering; mixing the dried filter residue with clear water according to the solid-liquid mass ratio of 1: 3, adjusting the pH of the system to 7.0 by adopting NaOH, and then adding 400g of NH4HCO3Controlling the reaction temperature of the system at 20 ℃, and filtering after 5 hours of reaction; mixing the dried filter residue with clear water according to the solid-liquid mass ratio of 1: 2, adding 0.6g/L hydrochloric acid for acid washing after mixing, controlling the reaction temperature of the system at 20 ℃, reacting for 5 hours, and filtering; washing the dried filter residue and clear water according to the solid-liquid mass ratio of 1: 4, washing at the temperature of 20 ℃, washing for 3 hours and then filtering; mixing the dried residue with clear water at a ratio of 1: 4, and adding 3.5L H2O2And 2L H2SO4And reacting for 1h at the reaction temperature of 30 ℃. In the example, the content of Mn in anode mud (i.e. material No. 7) obtained after impurity removal is 53.30%, the content of Pb is 6.82%, the content of Ca is 160Mg/kg, and the content of Mg is 54 Mg/kg; after impurities are leached by hydrogen peroxide, the leaching rate of manganese in the electrolytic manganese anode slime is 98.3%, the concentrations of Ca and Mg in the leaching solution (namely the 10# material) are respectively 16Mg/L and 15Mg/L, and the content of Pb in the leached slag (namely the 9# material) is 52.5%.
Example 2
Taking 5kg of electrolytic manganese anode mud which is dried, crushed and sieved by a 160-mesh sieve, mixing the electrolytic manganese anode mud with clear waterThe electrolytic manganese anode slime is washed for 2 hours at the reaction temperature of 30 ℃ and filtered, with the mass ratio of 4: 1; mixing the dried filter residue with clear water according to the solid-liquid mass ratio of 1: 4, adjusting the pH of the system to 8.0 by adopting NaOH, and then adding 350g of NH4HCO3Controlling the reaction temperature of the system at 30 ℃, reacting for 3 hours, and filtering; mixing the dried filter residue with clear water according to the solid-liquid mass ratio of 1: 3, adding 0.7g/L hydrochloric acid for acid washing after mixing, controlling the reaction temperature of the system at 30 ℃, reacting for 3 hours, and filtering; washing the dried filter residue and clear water according to the solid-liquid mass ratio of 1: 5, washing at the temperature of 30 ℃, washing for 1.5h, and filtering; mixing the dried residue with clear water at a ratio of 1: 5, adding 4L H2O2And 2.7L H2SO4And reacting for 2 hours at the reaction temperature of 30 ℃. In the example, the content of Mn in anode mud (i.e. 7# material) obtained after impurity removal is 53.70%, the content of Pb is 7.42%, the content of Ca is 174Mg/kg, and the content of Mg is 89 Mg/kg; after impurities are leached by hydrogen peroxide, the leaching rate of manganese in the electrolytic manganese anode slime is 98.5%, the concentrations of Ca and Mg in the leaching solution (namely the 10# material) are 23Mg/L and 17Mg/L respectively, and the content of Pb in the leached slag (namely the 9# material) is 51.2%.
Example 3
5kg of electrolytic manganese anode mud which is dried, crushed and sieved by a 200-mesh sieve is taken, washed for 0.5h under the conditions that the mass of clear water and the electrolytic manganese anode mud liquid is 6: 1 and the reaction temperature is 40 ℃, and filtered; mixing the dried filter residue with clear water according to the solid-liquid mass ratio of 1: 5, adjusting the pH of the system to 9.0 by adopting NaOH, and adding 300g of NH4HCO3Controlling the reaction temperature of the system at 40 ℃, reacting for 2 hours, and filtering; mixing the dried filter residue with clear water according to the solid-liquid mass ratio of 1: 5, adding 0.8g/L hydrochloric acid for acid washing after mixing, controlling the reaction temperature of the system at 40 ℃, reacting for 1 hour, and filtering; washing the dried filter residue and clear water according to the solid-liquid mass ratio of 1: 6, washing at the temperature of 40 ℃, washing for 0.5h, and filtering; mixing the dried residue with clear water at a ratio of 1: 6, adding 4.5L H2O2And 3L H2SO4And reacting for 2 hours at the reaction temperature of 30 ℃. In this example after removal of impuritiesThe obtained anode mud (namely the 7# material) has the Mn content of 52.80 percent, the Pb content of 6.92 percent, the Ca content of 160Mg/kg and the Mg content of 64 Mg/kg; after impurity removal by leaching with hydrogen peroxide, the leaching rate of manganese in the electrolytic manganese anode slime is 97.8%, the concentrations of Ca and Mg in the leachate (namely the 10# material) are respectively 26Mg/L and 18Mg/L, and the content of Pb in the leached slag (namely the 9# material) is 53.1%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A high-value utilization method of electrolytic manganese anode slime is characterized in that Ca, Mg and sulfate in the electrolytic manganese anode slime are removed by adopting methods of water washing, alkali washing and acid leaching, and then H is adopted2O2And H2SO4The leaching obtains a manganese sulphate solution and lead concentrate, and the method comprises the following steps:
s1: drying and crushing the electrolytic manganese anode mud, and sieving for later use;
s2: mixing the sieved electrolytic manganese anode mud with water, then washing for the first time, carrying out solid-liquid separation after the first washing to obtain a 1# material and a 2# washing liquid, and transferring the 2# washing liquid to a wastewater treatment workshop for centralized treatment;
s3: mixing the material 1 obtained in the step S2 with water, adding an alkaline material to adjust the pH of the system to be alkaline, adding carbonate to wash, performing solid-liquid separation after washing to obtain a material 3 and a washing liquid 4, and transferring the washing liquid 4 to a wastewater treatment workshop for centralized treatment; the alkaline material is ammonia water and/or NaOH, and the pH value of the system is adjusted to 7.0-9.0 by adding the ammonia water and/or NaOH; the carbonate is (NH)4)2CO3、NH4HCO3、Na2CO3One or more than one of the above, wherein the mass ratio of the carbonate to the No. 1 material is 0.5: 100-5: 100;
s4: mixing the 3# material obtained in the step S3 with water, adding hydrochloric acid for acid washing, performing solid-liquid separation after acid washing to obtain a 5# material and a 6# washing liquid, and transferring the 6# washing liquid to a wastewater treatment workshop for centralized treatment;
s5: mixing the 5# material obtained in the step S4 with water, then carrying out secondary washing, carrying out solid-liquid separation after the secondary washing to obtain a 7# material and an 8# washing liquid, and transferring the 8# washing liquid to a wastewater treatment workshop for centralized treatment;
s6: mixing the material 7# obtained in the step S5 with water, and adding H2O2And H2SO4Carrying out solid-liquid separation after full reaction to obtain a 9# material and a 10# washing solution, wherein the 9# material is lead concentrate, and the 10# washing solution is a manganese sulfate solution; mixing the 7# material with water according to the solid-liquid mass ratio of 1: 4-1: 6, and mixing the 7# material with H2O2And H2SO4The reaction temperature is 30-60 ℃, and the reaction time is 10-120 min; 7# Material and H2O2The mass ratio of (A) to (B) is 1: 0.5-1: 1.2; 7# Material and H2SO4The mass ratio of (A) to (B) is 1: 0.6-1: 1.2.
2. The method for high-value utilization of electrolytic manganese anode slime as claimed in claim 1, wherein in step S1, the temperature for drying the electrolytic manganese anode slime is 40-80 ℃, and the drying time is 5-48 h; and crushing the dried electrolytic manganese anode mud, and sieving the crushed electrolytic manganese anode mud by using a sieve of 80-200 meshes.
3. The method for high-valued utilization of electrolytic manganese anode slime as claimed in claim 1, wherein in step S2, the sieved electrolytic manganese anode slime is mixed with water according to a solid-liquid mass ratio of 1: 2-1: 6, the temperature of primary washing is 20-40 ℃, and the time of primary washing is 0.5-3 h.
4. The method for high-valued utilization of electrolytic manganese anode slime as claimed in claim 1, wherein in step S3, the material No. 1 is mixed with water according to a solid-liquid mass ratio of 1: 3-1: 5, the temperature for washing by adding carbonate is 20-40 ℃, and the washing time is 2-5 h.
5. The electrolytic manganese anode slime high-value utilization method according to claim 1, wherein in the step S4, the material No. 3 is mixed with water according to a solid-liquid mass ratio of 1: 2-1: 5; the concentration of the hydrochloric acid is 0.6-0.8 g/L, the temperature for acid washing by adding the hydrochloric acid is 20-40 ℃, and the washing time is 1-5 h.
6. The method for high-valued utilization of electrolytic manganese anode slime as claimed in claim 1, wherein in step S5, the 5# material and water are mixed according to a solid-liquid mass ratio of 1: 4-1: 6, the temperature of the secondary water washing is 20-40 ℃, and the time of the secondary water washing is 0.5-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110537032.5A CN113234941B (en) | 2021-05-18 | 2021-05-18 | High-value utilization method of electrolytic manganese anode slime |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110537032.5A CN113234941B (en) | 2021-05-18 | 2021-05-18 | High-value utilization method of electrolytic manganese anode slime |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113234941A CN113234941A (en) | 2021-08-10 |
| CN113234941B true CN113234941B (en) | 2022-07-19 |
Family
ID=77134983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110537032.5A Active CN113234941B (en) | 2021-05-18 | 2021-05-18 | High-value utilization method of electrolytic manganese anode slime |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234941B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789551A (en) * | 2014-02-18 | 2014-05-14 | 广西大学 | Method for preparing manganese sulfate electrolyte and recycling lead by using electrolytic manganese anode mud |
| JP2016180125A (en) * | 2015-03-23 | 2016-10-13 | 住友金属鉱山株式会社 | Recovery method of valuable metal from waste nickel hydrogen battery and recovery device of valuable metal from waste nickel hydrogen battery |
| CN112551591A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing high-purity manganese sulfate qualified liquid by electrolyzing metal manganese anode slime |
| CN112553468A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司 | Method for producing high-purity manganese sulfate by adopting metal manganese anode mud |
| CN112607782A (en) * | 2020-12-18 | 2021-04-06 | 中信大锰矿业有限责任公司 | Method for preparing battery-grade high-purity manganese sulfate by using metal manganese anode slime |
| CN112795773A (en) * | 2020-12-18 | 2021-05-14 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746108A (en) * | 2015-04-23 | 2015-07-01 | 重庆大学 | Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime |
-
2021
- 2021-05-18 CN CN202110537032.5A patent/CN113234941B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789551A (en) * | 2014-02-18 | 2014-05-14 | 广西大学 | Method for preparing manganese sulfate electrolyte and recycling lead by using electrolytic manganese anode mud |
| JP2016180125A (en) * | 2015-03-23 | 2016-10-13 | 住友金属鉱山株式会社 | Recovery method of valuable metal from waste nickel hydrogen battery and recovery device of valuable metal from waste nickel hydrogen battery |
| CN112551591A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing high-purity manganese sulfate qualified liquid by electrolyzing metal manganese anode slime |
| CN112553468A (en) * | 2020-12-18 | 2021-03-26 | 中信大锰矿业有限责任公司 | Method for producing high-purity manganese sulfate by adopting metal manganese anode mud |
| CN112607782A (en) * | 2020-12-18 | 2021-04-06 | 中信大锰矿业有限责任公司 | Method for preparing battery-grade high-purity manganese sulfate by using metal manganese anode slime |
| CN112795773A (en) * | 2020-12-18 | 2021-05-14 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
Non-Patent Citations (2)
| Title |
|---|
| Optimization of the synergy between reduction leaching of manganese anode slime and oxidation pretreatment of refractory gold ore by response surface methodology;Guo,P等;《CHEMICAL PAPERS》;20200531;全文 * |
| 电解金属锰阳极泥的综合回收利用研究;魏汉可等;《中国锰业》;20170427;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113234941A (en) | 2021-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108118157B (en) | Wiring board burns the recovery method of cigarette ash pretreatment and bromine | |
| CN105772486B (en) | A kind of method of cyanide in removal aluminum cell waste cathode carbon | |
| CN106048217B (en) | The comprehensive reutilization method of oxide powder and zinc | |
| CN102031381B (en) | Process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash | |
| CN108728634B (en) | Harmless treatment method for electrolytic manganese slag | |
| CN101899582A (en) | Method for extracting vanadium pentoxide from vanadium slag | |
| CN101838736A (en) | Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system | |
| CN110157913B (en) | Method for comprehensively treating copper slag | |
| CN101392332B (en) | Cleaning production technique for directly transforming rare earth sulfate bake ore to extract rare earth | |
| WO2022213678A1 (en) | Method for recycling aluminum in waste positive electrode sheet by using selective leaching and application thereof | |
| CN102766765A (en) | Zinc oxide powder recycling method | |
| CN109354071B (en) | Method for producing battery-grade manganese sulfate by using manganese tailings and waste sulfuric acid of titanium white | |
| CN103290221A (en) | Method for recovering copper, arsenium and antimony from black copper sludge | |
| CN111647754A (en) | Comprehensive utilization method of zinc-containing dust and sludge in steel plant | |
| CN114314661B (en) | Method for producing high-purity ammonium metavanadate by deep cobalt removal of vanadium raw material | |
| CN102275969B (en) | Comprehensive utilization method of titanium dioxide waste | |
| CN107673374A (en) | Steel mill sinters flue dust and desulfurization waste liquor method of comprehensive utilization | |
| CN105838904B (en) | The method for removing the copper arsenic in material containing zinc sulphur dioxide reduction leachate | |
| CN104762478A (en) | Method for production and recovery of precious metals on the basis of pickling sludge | |
| CN104745821A (en) | Method for recovering nickel and copper metals in acid pickling sludge | |
| CN113234941B (en) | High-value utilization method of electrolytic manganese anode slime | |
| CN103274449A (en) | Method for rapidly removing arsenic in high arsenic zinc oxide through zinc ash and sodium carbonate peroxide in iron and steel plants and producing zinc sulfate | |
| CN114058857A (en) | Method for recovering lead and manganese from electrolytic manganese anode slime | |
| CN103667695A (en) | Method for extracting arsenic from gold ore | |
| CN111424168A (en) | Water-washing dechlorination system and method for metallurgical precipitator dust |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |