CN111484081A - Method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues - Google Patents
Method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues Download PDFInfo
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- C01G45/00—Compounds of manganese
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
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- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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- 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
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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Abstract
The invention discloses a method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using leaching residues of electrolytic manganeseThe method comprises the steps of firstly pre-treating and recovering metal components such as Al, Fe, Mn and the like from electrolytic manganese leaching residues to prepare a manganese carbonate product and recover NH4+Preparing ammonium sulfate, calcining the rest solid, adding additive, mixing, grinding, and modifying to obtain dry powder coating. The preparation method is simple and low in cost, and the obtained product has good purity, excellent quality and high utilization rate, can achieve the effects of comprehensive recycling of the leaching residues of the electrolytic manganese and no emission, has high comprehensive benefit, and has very important significance for energy conservation, emission reduction and environmental pollution control in the electrolytic manganese metal industry.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of industrial waste slag, in particular to a method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using leaching residues of electrolytic manganese.
Background
The production process of electrolytic manganese metal is mainly implemented by using rabdosia mine or pyrolusite (baking powder) → acid leaching (sulfuric acid) → adding aqueous ammonia for iron removal → adding a vulcanizing agent for heavy metal removal → standing for calcium and magnesium removal → qualified manganese sulfate liquid → electrolytic bath → metal manganese tablets. In the electrolytic process, sulfuric acid reacts with metal carbonates such as manganese, iron, nickel, cobalt and the like in manganese ores to obtain electrolyte containing metal ions such as manganese, iron and the like, ammonia water is used for adjusting the pH value of the electrolyte to 3.5-4.0, and a proper amount of manganese dioxide mineral powder is added as an oxidant to enable Fe in the solution2+Oxidation to Fe3+Hydrolyzing the precipitate, adding a proper amount of vulcanizing agent when the pH value reaches 6.5-7.0 to precipitate other impurities, then performing filter pressing and solid-liquid separation by a filter press, feeding the filtrate into an electrolytic cell for electrolysis, and discharging filter cakes to obtain the electrolytic manganese metal leaching residue. As the grade of manganese ore is lower and lower, 8-10 tons of electrolytic manganese leaching slag are generated when 1 ton of metal manganese is produced. The production enterprises of metal manganese electrolysis of more than ten electrical appliances are shared by the lower thunder town of Daxin county in Chongxi city in Guangxi and the lake wetting town of Bai-color Jingxi city, the capacity of electrolyzing metal manganese is more than twenty thousand tons every year, and at least 2000 million tons of leaching residues of the electrolyzed metal manganese are discharged every year. The chemical components of the leaching residues are mainly as follows: 30% of water and dihydrate Gypsum, CaSO4.2H2O 60～70%、Al2O37～8%、Fe2O39～11%、SiO225～30%、MnO25～6%、(NH4)2SO47-8%; and also a small amount of heavy metal salts. The current method for treating the leaching slag of the electrolytic manganese metal is to simply transport the leaching slag to a slag warehouse, stack the leaching slag in the open air, blow the leaching slag with wind and rain and weather for a long timeUnder the leaching action, soluble ions and heavy metal elements in the slag are dissolved out, so that surrounding soil, earth surface and underground water are polluted, and the local environment and drinking water of residents are seriously polluted. And simultaneously wastes a large amount of manganese ions and ammonium sulfate. Therefore, the comprehensive recycling of the leaching residues of the electrolytic manganese metal is very necessary.
The following patent documents are searched for the recycling of the leaching residue of the electrolytic manganese metal:
patent CN102225768A discloses a method for preparing ultrafine active white carbon black by using manganese leaching slag and electrolytic manganese waste acid, washing the manganese leaching slag with dilute acid and alkaline aqueous solution to be neutral, reacting and filtering the obtained filter residue with strong alkaline solution to obtain filtrate, and decoloring the filtrate with amino-terminated hyperbranched polyester and polyacrylamide with the number average molecular weight of more than 1000000g/mol to obtain decolored silicate aqueous solution; adding a particle active agent, then dropwise adding the electrolytic manganese waste acid solution subjected to decoloration treatment, heating, reacting, filtering, washing and drying to obtain the white carbon black. The method effectively utilizes the waste residues and waste liquids generated by manganese ore enterprises to produce the white carbon black with high added value, and is beneficial to environmental protection and comprehensive utilization of resources; and has the advantages of simple process, low cost, high added value, suitability for industrial production and the like. Patent CN 105197941A discloses a method for preparing high-activity white carbon black by using manganese carbonate leaching residues and electrolytic manganese waste acid, wherein the manganese carbonate leaching residues are directly washed to be neutral by tap water and then dried, and the dried solid powder is treated by microwave for 1-5 minutes; reacting the obtained activated manganese waste residue with a strong alkali solution, filtering to obtain a filtrate, and decolorizing the filtrate with a dithiocarbamate of high molecular weight polyacrylamide to obtain a silicate aqueous solution; and slowly dripping the electrolytic manganese waste acid solution subjected to the decoloring treatment, and then heating, reacting, filtering, washing and drying to obtain the white carbon black. The method effectively utilizes the waste residues and waste liquids generated by manganese ore enterprises to produce the white carbon black with high added value, and is beneficial to environmental protection and comprehensive utilization of resources; and has the advantages of simple process, low cost, high added value, suitability for industrial production and the like.
Patent CN 103073312A discloses aThe method for preparing the infrared radiation base material by utilizing the electrolytic manganese slag comprises the steps of calcining and pretreating the electrolytic manganese slag and Fe2O3、MnO2、CuO、Co2O3And/or CoO is ground, mixed, uniformly sintered to prepare the infrared radiation base material, thereby providing a clean production technology with high added value.
Patent CN 103320621B discloses a method for solidifying heavy metals in electrolytic manganese slag and co-producing sulfur, which comprises the following basic steps: uniformly mixing a raw material containing calcium sulfite and/or calcium sulfate and a carbon-based reducing agent in a molar ratio of 1: 2.0-3.0, and roasting at 800-1000 ℃ for 1.5-2 h to obtain calcine containing calcium sulfide, wherein the yield of the calcium sulfide is over 90%; uniformly mixing electrolytic manganese slag sieved by a 50-400-mesh sieve and calcine containing calcium sulfide according to a dry basis mass ratio of 3-8: 1, adding water to enable the mass ratio of water to the electrolytic manganese slag to be 4-6: 1, stirring and reacting for 2-4 hours at room temperature, and filtering to obtain filtrate and filter residue; and filter residues are solidified electrolytic manganese residues, filtrate is kept stand at room temperature for 24-48 hours to separate out sulfur, the sulfur and the filtrate are filtered and separated again, the yield of the sulfur is 30-45 kg/t of manganese residues, and the filtrate is recycled as water. The solidification rate of cadmium, cobalt, copper, nickel, iron, manganese and zinc in the electrolytic manganese slag can reach more than 93 percent, and the leaching toxicity of the electrolytic manganese slag after the heavy metal is solidified meets the relevant national standard.
Patent CN 105039718B discloses a comprehensive recovery processing method of electrolytic manganese anolyte, comprising the following steps: 1) introducing ammonia gas into the electrolytic manganese anolyte, continuously stirring and adjusting the pH value of the anolyte to 6-7, then adding a manganese precipitation additive to carry out manganese precipitation reaction, and carrying out solid-liquid separation on slurry after the reaction is finished to obtain filtrate and manganese-containing filter residues; 2) adding a magnesium precipitation additive into the filtrate obtained in the step 1), continuously stirring, and blowing off the filtrate by air blowing; 3) and (3) carrying out solid-liquid separation on the slurry subjected to the air stripping in the step 2) to obtain magnesium-containing filter residue and filtrate, and recycling the filtrate. In the process of the invention, manganese in the electrolytic manganese anolyte generates manganese carbonate which can replace the prior double-flying powder; the gas blown off contains ammonia gas which can be used for neutralizing the next batch of electrolytic manganese anolyte to be treated, or directly introduced into water to recover ammonia, and the recovered ammonia can be used for leaching a workshop or an electrolysis workshop, so that the ammonium in the anolyte is recycled.
The above patent documents for recycling manganese slag all have problems of insufficient utilization, single product obtained, high cost and the like. The inventor of the application, Zhaoyang minister, also makes a great deal of research on recycling of waste residues produced in the manganese industry, and the earlier research results also carry out patent application. Patent CN 104480314B discloses a method for recycling waste residues in manganese industry, which comprises the following specific processes: (1) pretreating filter residues; (2) adding acid for leaching; (3) filtering ore pulp and performing solid-liquid separation; (4) recovering iron oxide red mineral powder; (5) recovering manganese carbonate concentrate; (6) preparing nitrogen-phosphorus compound fertilizer base material. The method can recover and obtain the iron oxide red mineral powder, the manganese carbonate concentrate and the nitrogen-phosphorus compound fertilizer base material from the leached filter-pressing residues, has simple process, is easy to realize industrialization, simultaneously has the content of heavy metal components completely meeting the relevant national standard, does not contain harmful components such as heavy metal and the like in the waste water and waste residue after secondary treatment, reduces the environmental pressure, and has great popularization value. The method for recycling the leaching filter-pressing residue in the production of electrolytic manganese metal and manganese dioxide in the patent CN 104480315B comprises the following specific processes: (1) pretreating filter residues; (2) adding acid for leaching; (3) filtering ore pulp and performing solid-liquid separation; (4) recovering iron oxide red mineral powder; (5) recovering manganese carbonate concentrate; (6) preparing a nitrogen-phosphorus compound fertilizer base material; (7) and (3) preparing sodium fluosilicate. The method can recover and obtain iron oxide red mineral powder, manganese carbonate concentrate, sodium fluosilicate and nitrogen-phosphorus compound fertilizer base materials from the leached filter-pressing residues, has simple process, is easy to realize industrialization, simultaneously has the content of heavy metal components completely meeting the relevant national standard, does not contain harmful components such as heavy metal and the like in the waste water and waste residue after secondary treatment, reduces the environmental pressure, and has great popularization value. Patent CN 105152153B is a comprehensive recycling method of leaching residue in electrolytic manganese metal production, and the specific process comprises several parts: (1) preparing a compound fertilizer base material; (2) recovering iron phosphate powder; (3) recovering copper, cobalt and nickel precious metal mineral powder; (4) recovering gypsum powder; (5) preparing high-purity manganese carbonate ore powder; (6) and (3) preparing the magnesium ammonium phosphate slow-release compound fertilizer. The invention can effectively recover resources such as ferrum, manganese and the like in the leaching slag and can produce electrolytic goldBelongs to a comprehensive system in manganese leaching slag, recovers a certain amount of manganese carbonate ore and manganese dioxide ore which are not dissolved completely, precipitated iron hydroxide and precious metal sulfide ore of copper, cobalt and nickel in the leaching slag, and extracts Mn along with slag moisture2+And NH4+And the like, thereby achieving the effects of complete comprehensive recycling and no emission, and having very important significance for energy conservation and emission reduction and environmental pollution treatment in the electrolytic manganese metal industry.
The components of the leaching residues of the electrolytic manganese are complex, although the effects of complete comprehensive recycling and no emission are realized in the previous research of the applicant, the previous research mainly aims at recycling the manganese carbonate and the iron powder and preparing the nitrogen-phosphorus slow-release compound fertilizer, the price of the nitrogen-phosphorus slow-release compound fertilizer is low, the benefit of the comprehensive recycling of the leaching residues of the electrolytic manganese is low, the consumption of the nitrogen-phosphorus slow-release compound fertilizer is low, and the products are easy to accumulate, so that the previous method is difficult to industrially treat the leaching residues of the electrolytic manganese in a large scale, the comprehensive recycling amount of the leaching residues of the electrolytic manganese is limited, the electrolytic manganese leaching residues produced by an electrolytic manganese metal production enterprise are difficult to completely treat, and in conclusion, more methods capable of comprehensively recycling the leaching residues of the electrolytic manganese are required to be researched.
Disclosure of Invention
The invention aims to provide a method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using leached residues of electrolytic manganese, the preparation method is simple and low in cost, and the obtained product has good purity, excellent quality and high utilization rate, can achieve the effects of comprehensive recycling and non-emission of the leached residues of the electrolytic manganese, has high comprehensive benefit, and has very important significance for energy conservation, emission reduction and environmental pollution control in the electrolytic manganese metal industry.
A method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues comprises the following steps:
(1) adding the electrolytic manganese leaching residue and water into a crushing and pulp-blending machine according to the liquid-solid ratio of 3:1, and crushing to prepare residue slurry.
(2) And (3) injecting the slag slurry into a stirring reaction tank, slowly adding concentrated sulfuric acid with the concentration of 98% while stirring to fully dissolve the composite ammonium salt, stopping adding the concentrated sulfuric acid when the pH value is reduced to 4.0-4.5, and stopping stirring for 30 min.
Adding concentrated sulfuric acid into the slag slurry to perform partial chemical reaction:
Al2O3+3H2SO4=Al2(SO4)3+3H2O；
Fe2O3+3H2SO4=Fe2(SO4)3+3H2O；
2MnO2+2H2SO4(concentrated) =2MnSO4+O2↑+2H2O。
(3) And (3) carrying out solid-liquid separation on the turbid liquid, keeping the solid for later use, injecting the filtrate into a neutralization reaction tank, adding ammonium bicarbonate powder while stirring, stopping adding ammonium bicarbonate when the pH value in the solution is increased to 7.8-8.0, and continuously stirring for 30min to obtain the suspension emulsion.
Adding ammonium bicarbonate into filtrate of the neutralization reaction tank for chemical reaction:
MnSO4+2NH4HCO3=MnCO3↓+(NH4)2SO4+CO2↑+H2O；
Al2(SO4)3+6NH4HCO3=2Al(OH)3↓+6CO2↑+3(NH4)2SO4；
Fe2(SO4)3+6NH4HCO3=2Fe(OH)3↓+6CO2↑+3(NH4)2SO4。
(4) and (3) carrying out solid-liquid separation on the suspension emulsion, standing the filtrate, drying and packaging the solid to obtain the manganese carbonate product.
(5) And (4) putting the solid in the step (3) and the filtrate in the step (4) into a crushing pulp mixer according to the liquid-solid ratio of 3:1 for crushing and pulp mixing.
(6) And (3) injecting the slurry obtained in the step (5) into a stirring reaction tank with a negative pressure and an air exhaust pipeline, adding quicklime accounting for 6% of the weight of the electrolytic manganese leaching residue while stirring, starting an exhaust fan of an ammonia gas collecting tower to suck ammonia gas, reacting the ammonia gas with dilute sulfuric acid in the collecting tower to generate ammonium sulfate, and stopping stirring when no ammonia gas is generated in the stirring reaction tank.
Adding quicklime into the negative-pressure stirring reaction tank:
(NH4)2SO4+CaO=CaSO4↓+H2O+2NH3↑；
absorbing ammonia gas with dilute sulfuric acid:
2NH3+H2SO4=(NH4)2SO4。
(7) injecting the ammonium sulfate solution in the ammonia gas collecting tower into an ammonium sulfate dissolution crystallization tank, adding a methanol solution with the same volume as the ammonium sulfate solution while stirring, separating out ammonium sulfate crystals, stirring for 30min, performing solid-liquid separation on an ammonium sulfate suspension, injecting the filtrate into a distillation machine to recover methanol for recycling, and drying and packaging the solid to obtain an ammonium sulfate product.
(8) And (4) carrying out solid-liquid separation on the slurry in the stirring reaction tank in the step (6), returning the filtrate to the crushing and slurry-preparing machine in the step (5) for recycling, and drying the solid into dry powder.
(9) Calcining the dry powder at 120-180 ℃ for 1 h.
CaO+SiO2=CaSiO3。
(10) And (3) putting the calcined dry powder into a fine grinding machine for grinding modification, sieving by using a 800-mesh sieve, then putting into an aging bin, performing aging treatment at normal temperature for more than 72h, and finally packaging to obtain the dry powder building coating.
Further, in the step (10), the calcined dry powder can be put into a dry powder mixer, and the admixture is added to be mixed uniformly. And then putting the uniformly mixed powder into a fine grinding machine for grinding modification, sieving the powder by a 800-mesh sieve, then putting the powder into an aging bin, performing aging treatment at normal temperature for more than 72 hours, and finally packaging to obtain the dry powder building coating.
The additive comprises the following raw materials in percentage by weight: 1.5-2.0% of 1.6-modulus dry powder water glass; 8-10% of white cement; 8-10% of redispersible latex powder; 0.2-0.5% of methyl cellulose ether; 0.3-0.4% of defoaming agent; 0.3-1.0% of lignocellulose; 0.1-0.3% of sodium tripolyphosphate; 2.5 percent of polyvinyl alcohol; 10 percent of titanium dioxide.
The admixture can also comprise the following raw materials in percentage by weight: 10 percent of fly ash.
The invention has the beneficial effects that:
the chemical components of the leaching residue of the electrolytic manganese are mainly as follows: 30% of water and dihydrate Gypsum, CaSO4．2H2O 60～70%、Al2O37～8%、Fe2O39～11%、SiO225～30%、MnO25～6%、(NH4)2SO47-8%, adding concentrated sulfuric acid into the leaching slag, performing solid-liquid separation, adding ammonium bicarbonate into the filtrate, performing solid-liquid separation after precipitation of Al, Fe, Mn and other ions, obtaining a product with the main component of manganese carbonate, and recovering metal components of Al, Fe, Mn and the like in the leaching slag. Adding quick lime into the solid obtained after adding concentrated sulfuric acid into the leached residues to react to generate ammonia gas, absorbing the ammonia gas by using sulfuric acid through an ammonia gas collecting tower to prepare an ammonium sulfate product, and recovering NH in the leached residues4+And NH in ammonium bicarbonate added for preparing manganese carbonate product4+. The solid left after the separation in the two steps mainly contains gypsum and silicon dioxide, the silicon dioxide and quicklime are calcined to generate calcium silicate, and the gypsum and the calcium silicate are common raw materials in the field of buildings and can be used for preparing dry powder building coatings.
In the raw materials of the additive used in the invention, the silicic acid gel precipitated in the hardening of the water glass has strong adhesiveness, the silicic acid gel can block the capillary pores of the material and form a continuous closed film on the surface, and has the characteristic of increasing the strength of the skin by high-temperature drying, and does not react with acid substances, so that the additive has good bonding capability, weather resistance, impermeability, fire resistance, heat resistance and acid resistance, and the 1.6 modulus dry powder water glass is selected to be easily soluble in water and has high strength. The fly ash is the main solid waste discharged by coal-fired power plants, and the main oxide composition of the fly ash of the heat-engine plants in China is SiO2、Al2O3、FeO、Fe2O3、CaO、TiO2And the like. The addition of fly ash to the coating can save the use amount of cement and gypsum and increase the strength and durability of the coating. The main component of the white cement is calcium silicate, so that the white cement has higher whiteness and bright color. The re-dispersible latex powder has extremely outstanding bonding strength, endows the coating with excellent alkali resistance, and can improve the adhesive bonding property, the breaking strength, the water resistance, the plasticity, the wear resistance and the workability of the coating. The methyl cellulose ether has water retention and thickening properties, and can improve the leveling property of the coating. Sodium tripolyphosphate has dispersing and solubilizing functions, and is used as an emulsifier for the coating. The polyvinyl alcohol has good film-forming property and can be used as a film-forming agent in the coating. Titanium dioxide is a white pigment, has strong tinting strength and excellent covering power and tinting fastness. The dry powder architectural coating prepared by adding the additive and uniformly mixing the dry powder mainly containing gypsum and calcium silicate separated from the leaching residue of electrolytic manganese has good water resistance, chemical resistance, scrubbing resistance, freezing resistance and the like, and is good in strength and not easy to crack.
The method can effectively recover resources such as iron, aluminum, manganese, calcium, silicon and the like in the leaching slag and recover NH separated along with the leaching slag4+When valuable substances are obtained, simultaneously, the ammonium bicarbonate and the quicklime added in the recovery process are all converted into products, so that the effects of all comprehensive recovery and utilization and no emission are achieved, and the method has very important significance for energy conservation and emission reduction and environmental pollution treatment in the electrolytic manganese metal industry; at the same time, by reacting NH4+The ammonia gas is converted into ammonia gas and the ammonia gas is absorbed by sulfuric acid through an ammonia gas collecting tower to prepare an ammonium sulfate product, and the obtained ammonium sulfate product has high purity, wide application and great economic benefit. The preparation process of the invention has simple steps, easy operation and low production cost, and the produced dry powder building coating has wide application, large daily use amount and higher price, so the manganese carbonate, ammonium sulfate and dry powder building coating produced by leaching residues of electrolytic manganese can realize industrialized production, the consumption of the leaching residues of electrolytic manganese is large, the product value is high, and the added ammonium bicarbonate, quicklime and additives in the whole recovery process have low cost, and the original cost is lowThe recycling method has the advantages of multiple materials, good overall comprehensive benefit and very wide application prospect.
Drawings
FIG. 1 is a flow chart of preparing manganese carbonate, ammonium sulfate and dry powder building coating by using leaching residue of electrolytic manganese.
Detailed Description
In order to describe the present invention in more detail, the present invention will be further described with reference to the following examples.
Example 1
A method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues comprises the following steps:
(1) adding the cake-shaped electrolytic manganese leaching residue and water into a No. 1 crushing and pulp mixing machine according to the liquid-solid ratio of 3:1, crushing and preparing into residue pulp.
(2) And (3) injecting the slag slurry into a stirring reaction tank, slowly adding concentrated sulfuric acid with the concentration of 98% while stirring to fully dissolve the composite ammonium salt, stopping adding the concentrated sulfuric acid when the pH value is reduced to 4.0-4.5, and stopping stirring for 30 min.
(3) Pumping the slurry into a No. 1 filter press to press the slurry into a filter cake for later use, injecting the filtrate into a neutralization reaction tank, adding ammonium bicarbonate powder while stirring, stopping adding the ammonium bicarbonate when the pH value in the solution rises to 7.8-8.0, and continuously stirring for 30min to obtain the suspension emulsion.
(4) And (3) pumping the suspension emulsion into a No. 2 filter press for solid-liquid separation, standing the filtrate, drying the filter cake and packaging to obtain the manganese carbonate product.
(5) And (4) putting the filter cake in the step (3) and the filtrate in the step (4) into a No. 2 crushing pulp mixer according to the liquid-solid ratio of 3:1 for crushing and pulp mixing.
(6) And (3) injecting the slurry obtained in the step (5) into a stirring reaction tank with a negative pressure and an air exhaust pipeline, adding quicklime accounting for 6% of the weight of the electrolytic manganese leaching residue while stirring, starting an exhaust fan of an ammonia gas collecting tower to suck ammonia gas, reacting the ammonia gas with dilute sulfuric acid in the collecting tower to generate ammonium sulfate, and stopping stirring when no ammonia gas is generated in the stirring reaction tank.
(7) Injecting the ammonium sulfate solution in the ammonia gas collecting tower into an ammonium sulfate dissolution crystallization tank, adding a methanol solution with the same volume as the ammonium sulfate solution while stirring, separating out ammonium sulfate crystals, stirring for 30min, injecting the ammonium sulfate suspension into a suction filter for solid-liquid separation, injecting the filtrate into a distillation machine for recycling methanol, drying the filter residue in a drying machine, and packaging to obtain the ammonium sulfate product.
(8) And (4) pumping the slurry in the stirring reaction tank in the step (6) into a No. 3 filter press for solid-liquid separation, returning the filtrate to the No. 2 crushing and pulp-mixing machine for recycling, and drying the filter cake into dry powder in a flash evaporation dryer.
(9) And (3) putting the dry powder into a calcining machine for calcining, wherein the calcining temperature is 120-180 ℃, and the calcining time is 1 h.
(10) And (3) putting the calcined dry powder into a dry powder mixer, and simultaneously adding an additive to uniformly mix the mixture.
(11) And (3) putting the uniformly mixed powder into a fine grinding machine for grinding modification, sieving the powder by using a 800-mesh sieve, then putting the powder into an aging bin, performing aging treatment at normal temperature for more than 72 hours, and finally packaging to obtain the dry powder building coating.
Wherein the admixture can comprise the following raw materials in percentage by weight: 1.6 percent of modulus dry powder water glass 1.5 percent; 10% of fly ash; white cement 8 percent; 8 percent of redispersible latex powder; 0.2% of methyl cellulose ether; 0.3 percent of defoaming agent; 0.3 percent of lignocellulose; 0.1 percent of sodium tripolyphosphate; 2.5 percent of polyvinyl alcohol; 10 percent of titanium dioxide.
Or the additive can comprise the following raw materials in percentage by weight: 1.6 modulus dry powder water glass 2.0%; 10% of fly ash; white cement 10%; 10 percent of redispersible latex powder; 0.5% of methyl cellulose ether; 0.4 percent of defoaming agent; 1.0% of lignocellulose; 0.3 percent of sodium tripolyphosphate; 2.5 percent of polyvinyl alcohol; 10 percent of titanium dioxide.
The preferable additive can comprise the following raw materials in percentage by weight: 1.6 percent of modulus dry powder water glass 1.8 percent; 10% of fly ash; white cement 9 percent; 9% of redispersible latex powder; 0.35% of methyl cellulose ether; 0.35 percent of defoaming agent; 0.65% of lignocellulose; 0.2 percent of sodium tripolyphosphate; 2.5 percent of polyvinyl alcohol; 10 percent of titanium dioxide.
Application examples
A method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues comprises the following steps:
(1) collecting freshly discharged electrolytic manganese leaching residues from a manganese industry company in Daxin county, Chonggao, Guangxi, weighing 1000g of the leaching residues, putting the weighed leaching residues into a No. 1 crushing and pulp-blending machine, adding 3000m L of tap water, and crushing to prepare slurry.
(2) Pouring the slurry into a 5000m L stirring reaction tank, slowly adding 98% concentrated sulfuric acid while stirring, measuring pH value, stopping adding sulfuric acid when the pH value is reduced to 4.0, and stopping stirring for 30 min.
(3) Pumping the slurry into a No. 1 filter press to press the slurry into a filter cake for later use, injecting the filtrate into a neutralization reaction tank, adding ammonium bicarbonate powder while stirring, stopping adding the ammonium bicarbonate when the pH value in the solution rises to 7.8-8.0, and continuously stirring for 30min to obtain the suspension emulsion.
(4) And (3) pumping the suspension emulsion into a No. 2 filter press for solid-liquid separation, standing the filtrate, drying the filter cake and packaging to obtain the manganese carbonate product.
(5) And (4) putting the filter cake in the step (3) and the filtrate in the step (4) into a No. 2 crushing pulp mixer according to the liquid-solid ratio of 3:1 for crushing and pulp mixing.
(6) And (3) injecting the slurry obtained in the step (5) into a stirring reaction tank with a negative pressure and an air exhaust pipeline, adding 60g of quicklime while stirring, starting an exhaust fan of an ammonia gas collecting tower to suck ammonia gas, reacting the ammonia gas with dilute sulfuric acid in the collecting tower to generate ammonium sulfate, and stopping stirring when no ammonia gas is generated in the stirring reaction tank.
(7) Injecting the ammonium sulfate solution in the ammonia gas collecting tower into an ammonium sulfate dissolution crystallization tank, adding a methanol solution with the same volume as the ammonium sulfate solution while stirring, separating out ammonium sulfate crystals, stirring for 30min, injecting the ammonium sulfate suspension into a suction filter for solid-liquid separation, injecting the filtrate into a distillation machine for recycling methanol, drying the filter residue in a drying machine, and packaging to obtain the ammonium sulfate product.
(8) And (4) pumping the slurry in the stirring reaction tank in the step (6) into a No. 3 filter press for solid-liquid separation, returning the filtrate to the No. 2 crushing and pulp-mixing machine for recycling, and drying the filter cake into dry powder at 105 ℃ in a flash evaporation dryer.
(9) And (3) putting the dry powder into a muffle furnace calcining machine for calcining, wherein the calcining temperature is 170 ℃, and the calcining time is 1 h.
(10) And (3) putting the calcined dry powder into a dry powder mixer, and simultaneously adding 12g of 1.6-modulus dry powder water glass, 70g of conch cement P.O 42.5.5R, 56g of redispersible latex powder, 2g of methyl cellulose ether, 2g of antifoaming agent AGITNP803, 2g of wood fiber, 1g of sodium tripolyphosphate, 14g of polyvinyl alcohol, 70g of titanium dioxide and 2g of thixotropic lubricant OPTIBENT602, and uniformly mixing.
(11) And (3) putting the uniformly mixed powder into a fine grinding machine for grinding modification, sieving the powder by using a 800-mesh sieve, then putting the powder into an aging bin, performing aging treatment for 72 hours at normal temperature, and finally packaging to obtain the dry powder building coating.
In order to verify the performance of the dry powder architectural coating prepared by the invention, the applicant also uses the coating prepared by the application example to paint a cement board and then detects the formed coating, and the concrete steps are as follows:
1) manufacturing a cement test board: a proper amount of cement and fine sand are taken to prepare 30 cement test plates with the specification of length, width and thickness of 200mmx100mmx10mm for standby.
2) Preparing the water-based paint, namely weighing 700m L clear water, putting the clear water into a 5000m L stirrer, starting the stirrer, uniformly stirring at a rotating speed of 300 revolutions per minute, weighing 2kg of dry powder building paint while stirring, slowly putting the dry powder building paint into the stirrer, weighing 300m L clear water after the dry powder is added, continuously stirring for 15 minutes, standing for defoaming, coating the dry powder building paint on a cement test board by using a soft brush, wherein the thickness of the coating is about 0.2mm, and performing performance detection on the dry powder paint after the test board is placed in a dry place for 7 days, wherein the results are as follows:
through the tests, the dry powder building coating prepared by the method of the invention by using the leaching residue of the electrolytic manganese metal can reach the national standard.
Claims (4)
1. A method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues is characterized by comprising the following steps:
(1) adding the electrolytic manganese leaching residue and water into a crushing and pulp-blending machine according to the liquid-solid ratio of 3:1, and crushing to prepare residue slurry;
(2) pouring the slag slurry into a stirring reaction tank, slowly adding concentrated sulfuric acid with the concentration of 98% while stirring to fully dissolve the composite ammonium salt, stopping adding the concentrated sulfuric acid when the pH value is reduced to 4.0-4.5, and stopping stirring for 30 min;
(3) carrying out solid-liquid separation on the turbid liquid, keeping the solid for later use, injecting the filtrate into a neutralization reaction tank, adding ammonium bicarbonate powder while stirring, stopping adding ammonium bicarbonate when the pH value in the solution is increased to 7.8-8.0, and continuously stirring for 30min to obtain a suspension emulsion;
(4) carrying out solid-liquid separation on the suspension emulsion, standing the filtrate, drying and packaging the solid to obtain a manganese carbonate product;
(5) putting the solid in the step (3) and the filtrate in the step (4) into a crushing pulp mixer according to the liquid-solid ratio of 3:1 for crushing and pulp mixing;
(6) injecting the slurry obtained in the step (5) into a stirring reaction tank with a negative pressure and an air exhaust pipeline, adding quicklime accounting for 6% of the weight of the electrolytic manganese leaching residue while stirring, starting an exhaust fan of an ammonia gas collecting tower to suck ammonia gas, reacting the ammonia gas with dilute sulfuric acid in the collecting tower to generate ammonium sulfate, and stopping stirring when no ammonia gas is generated in the stirring reaction tank;
(7) injecting the ammonium sulfate solution in the ammonia gas collecting tower into an ammonium sulfate dissolution crystallization tank, adding a methanol solution with the same volume as the ammonium sulfate solution while stirring, separating out ammonium sulfate crystals, stirring for 30min, performing solid-liquid separation on an ammonium sulfate suspension emulsion, injecting the filtrate into a distillation machine to recover methanol for recycling, and drying and packaging the solid to obtain an ammonium sulfate product;
(8) carrying out solid-liquid separation on the slurry in the stirring reaction tank in the step (6), returning the filtrate to the crushing and slurry-preparing machine in the step (5) for recycling, and drying the solid into dry powder;
(9) calcining the dry powder at 120-180 ℃ for 1 h;
(10) and (3) putting the calcined dry powder into a fine grinding machine for grinding modification, sieving by using a 800-mesh sieve, then putting into an aging bin, performing aging treatment at normal temperature for more than 72h, and finally packaging to obtain the dry powder building coating.
2. The method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leached residues according to claim 1, wherein the step (10) is further characterized in that the calcined dry powder is put into a dry powder mixer, and simultaneously, an additive is added to be mixed uniformly, the uniformly mixed powder is put into a fine grinding machine to be ground and modified, the powder is sieved by a 800-mesh sieve and then enters an aging bin, the aging treatment is carried out at normal temperature for more than 72h, and finally the dry powder building coating is obtained by packaging.
3. The method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leached residues as claimed in claim 2, wherein the additive comprises the following raw materials in percentage by weight: 1.5-2.0% of 1.6-modulus dry powder water glass; 8-10% of white cement; 8-10% of redispersible latex powder; 0.2-0.5% of methyl cellulose ether; 0.3-0.4% of defoaming agent; 0.3-1.0% of lignocellulose; 0.1-0.3% of sodium tripolyphosphate; 2.5 percent of polyvinyl alcohol; 10 percent of titanium dioxide.
4. The method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leached residues as claimed in claim 3, wherein the additive further comprises the following raw materials in percentage by weight: 10 percent of fly ash.
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