CN111484081B - 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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- C01—INORGANIC CHEMISTRY
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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- 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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- 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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- Y02P10/20—Recycling
Abstract
The invention discloses a method for preparing manganese carbonate, ammonium sulfate and dry powder building coating by using electrolytic manganese leaching residues 4+ 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 all leaching residues of the electrolytic manganese and no emission, has high comprehensive benefit, and has very important significance for energy conservation and 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 characterized by using rabdosia mine or pyrolusite (roasting powder) → acid leaching (sulfuric acid) → adding aqueous ammonia to remove iron → adding a vulcanizing agent to remove heavy metalsBelongs to → static calcium and magnesium removal → qualified manganese sulfate liquid → electrolytic tank → metal manganese sheet. 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 solution 2+ Oxidation to Fe 3+ Hydrolyzing the precipitate, adding a proper amount of vulcanizing agent when the pH value is 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, namely the electrolytic manganese metal leaching residue. Because 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 lower thunder town of Daxin county in Guangxi Chong left city and lake wetting town of Bai-color Jingxi city share more than ten household manganese metal electrolysis production enterprises, the yield of electrolytic manganese metal is more than twenty thousand tons every year, and at least 2000 million tons of electrolytic manganese metal leaching residues are discharged every year. The chemical components of the leaching residues are mainly as follows: 30% of water and dihydrate Gypsum, caSO 4 .2H 2 O 60～70%、Al 2 O 3 7～8%、Fe 2 O 3 9～11%、SiO 2 25～30%、MnO 2 5～6%、(NH 4 ) 2 SO 4 7 to 8 percent; 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 simply, blow the leaching slag by wind and rain, and dissolve out soluble ions and heavy metal elements in the leaching slag under the long-term weathering leaching action, so that the surrounding soil, the ground 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 superfine active white carbon black by using manganese leaching residue and electrolytic manganese waste acid, firstly washing the manganese leaching residue 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 then decoloring the filtrate with amino-terminated hyperbranched polyester and polyacrylamide with the number average molecular weight of 1000000g/mol or more 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, thereby being 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 residue and electrolytic manganese waste acid, wherein the manganese carbonate leaching residue is 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, thereby being 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 a method for preparing infrared radiation base material by using electrolytic manganese slag, which is to calcine the electrolytic manganese slag and then mix the electrolytic manganese slag with Fe 2 O 3 、MnO 2 、CuO、Co 2 O 3 And/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 1.0-3.0, and then 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, adding water to ensure that the mass ratio of water to the electrolytic manganese slag is 4-6; and filter residues are solidified electrolytic manganese residues, filtrate is kept stand at room temperature for 24-48 h 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 rates 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 can generate manganese carbonate to 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 also makes a great deal of research on recycling of waste residues produced in manganese industry, and earlier research results are patented. Patent CN 104480314B discloses a method for recycling waste residues from manganese production, which comprises the following specific processes: (1) filter residue pretreatment; (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; and (6) preparing a nitrogen-phosphorus compound fertilizer base material. The invention can recover and obtain iron oxide red mineral powder and manganese carbonate from leached filter-pressing residueThe process of the concentrate and the nitrogen-phosphorus compound fertilizer base material is simple, the industrialization is easy to realize, simultaneously, the content of heavy metal components completely accords with the relevant national standard, harmful components such as heavy metal and the like are not contained in the waste water and the waste residue after the secondary treatment, the environmental pressure is reduced, and the method has great popularization value. The method for recycling the leaching filter-pressing residue in the production of electrolytic manganese metal and manganese dioxide in patent CN 104480315B comprises the following specific processes: (1) filter residue pretreatment; (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; and (7) 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 residues 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-nickel precious metal ore powder; (4) recovering gypsum powder; (5) preparing high-purity manganese carbonate ore powder; and (6) preparing the magnesium ammonium phosphate slow-release compound fertilizer. The invention can effectively recover resources such as iron and manganese in the leaching slag, and can systematically recover 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, and Mn which is discharged along with slag water content from the leaching slag for producing the electrolytic manganese metal 2+ And NH 4+ And valuable substances are obtained, so that the effects of comprehensive recycling 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.
Although the components of the leached residues of the electrolytic manganese are complex, the effects of complete comprehensive recycling and no emission are realized in the earlier research of the applicant, the earlier research mainly comprises recycling manganese carbonate and iron powder and preparing a nitrogen-phosphorus slow-release compound fertilizer, the price of the nitrogen-phosphorus slow-release compound fertilizer is low, so that the benefits of the comprehensive recycling of the leached residues of the electrolytic manganese are not high, the consumption of the nitrogen-phosphorus slow-release compound fertilizer is low, and products are easy to accumulate, therefore, the earlier method is difficult to industrially treat the leached residues of the electrolytic manganese in a large scale, the comprehensive recycling amount of the leached residues of the electrolytic manganese is limited, the leached residues of the electrolytic manganese produced by enterprises for producing electrolytic manganese metal is difficult to completely treat, and in conclusion, more methods capable of comprehensively recycling the leached 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.
(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:
Al 2 O 3 +3H 2 SO 4 =Al 2 (SO 4 ) 3 +3H 2 O；
Fe 2 O 3 +3H 2 SO 4 =Fe 2 (SO 4 ) 3 +3H 2 O；
2MnO 2 +2H 2 SO 4 (concentrated) =2MnSO 4 +O 2 ↑+2H 2 O。
(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:
MnSO 4 +2NH 4 HCO 3 =MnCO 3 ↓+(NH4) 2 SO 4 +CO 2 ↑+H 2 O；
Al 2 (SO 4 ) 3 +6NH 4 HCO 3 =2Al(OH) 3 ↓+6CO 2 ↑+3(NH 4 ) 2 SO 4 ；
Fe 2 (SO 4 ) 3 +6NH 4 HCO 3 =2Fe(OH) 3 ↓+6CO 2 ↑+3(NH 4 ) 2 SO 4 。
(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 (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.
(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:
(NH 4 ) 2 SO 4 +CaO=CaSO 4 ↓+H 2 O+2NH 3 ↑；
absorbing ammonia gas with dilute sulfuric acid:
2NH 3 +H 2 SO 4 =(NH4) 2 SO 4 。
(7) Injecting the ammonium sulfate solution in the ammonia gas collecting tower into an ammonium sulfate dissolution crystallizing tank, adding a methanol solution with the same volume as the ammonium sulfate solution while stirring to crystallize and separate out ammonium sulfate, stirring for 30min, then carrying out solid-liquid separation on an ammonium sulfate suspension, injecting filtrate into a distilling machine to recover methanol for recycling, 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 1h.
CaO+SiO 2 =CaSiO 3 。
(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 by using a 800-mesh sieve, then putting the powder into an aging bin, aging at normal temperature for over 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 to 2.0 percent of 1.6 modulus dry powder water glass; white cement 8-10%; 8 to 10 percent of re-dispersible latex powder; 0.2 to 0.5 percent of methyl cellulose ether; 0.3 to 0.4 percent of defoaming agent; 0.3 to 1.0 percent of lignocellulose; 0.1 to 0.3 percent 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 beneficial effects of the invention are:
the chemical components of the leaching residue of the electrolytic manganese are mainly as follows: 30% of water and CaSO 4 ．2H 2 O 60～70%、Al 2 O 3 7～8%、Fe 2 O 3 9～11%、SiO 2 25～30%、MnO 2 5～6%、(NH 4 ) 2 SO 4 7-8%, the invention is realized by forward leachingAdding concentrated sulfuric acid into the slag, performing solid-liquid separation, adding ammonium bicarbonate into the filtrate to precipitate Al, fe, mn and other ions, performing solid-liquid separation to obtain a product containing manganese carbonate as a main component, and recovering metal components such as Al, fe, mn and the like in the leached slag. Adding quicklime into the solid obtained by 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 residues 4+ And preparation of NH in ammonium bicarbonate added to manganese carbonate product 4+ . 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 SiO 2 、Al 2 O 3 、FeO、Fe 2 O 3 、CaO、TiO 2 And the like. The addition of fly ash in 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 outstanding bonding strength, endows the paint 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 paint. 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 white powder is a white pigment with strong tinting strength and excellent covering powerAnd color 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 slag 4+ 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 NH 4+ 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 are produced by using the leaching residue of the electrolytic manganese, the industrialized production can be realized, the consumption of the leaching residue of the electrolytic manganese is large, the product value is high, in addition, the cost of the ammonium bicarbonate, the quicklime and the additive added in the whole recovery process is low, the raw materials are more, the recovery and utilization method has good overall comprehensive benefits 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, and crushing to prepare 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) And pumping the slurry into a No. 1 filter press to be pressed into filter cakes for later use, injecting 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 (5) putting the filter cake in the step (3) and the filtrate in the step (4) into a No. 2 smashing and pulp mixing machine according to the liquid-solid ratio of 3.
(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 1h.
(10) And (3) putting the calcined dry powder into a dry powder mixer, and adding the additive and mixing uniformly.
(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% 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 modulus dry powder water glass 1.8%; 10% of fly ash; white cement 9%; 9 percent 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, chong, left city, guangxi, weighing 1000g of the leaching residues, putting the weighed leaching residues into a No. 1 crushing pulp mixer, adding 3000mL of tap water, and crushing the mixture to prepare slurry.
(2) And (3) injecting the slag slurry into a 5000mL stirring reaction tank, slowly adding concentrated sulfuric acid with the concentration of 98% while stirring, measuring the 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 is increased 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 (3) putting the filter cake in the step (3) and the filtrate in the step (4) into a No. 2 smashing and pulp mixing machine according to the liquid-solid ratio of 3.
(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 a No. 2 crushing and slurry mixing machine for recycling, and drying the filter cake into dry powder at 105 ℃ in a flash 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 1h.
(10) 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 42.5R, 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 x width x thickness of 200mmx100mmx10mm for standby.
2) Preparing the water-based paint: weighing 700mL of clean water, placing the clean water in a 5000mL stirrer, starting the stirrer, stirring at a constant speed of 300 revolutions per minute, weighing 2kg of dry powder building coating while stirring, slowly placing the dry powder building coating in the stirrer, weighing 300mL of clean water after the dry powder is added, continuously stirring for 15 minutes, standing for defoaming, coating the dry powder building coating on a cement test board by using a soft brush, wherein the thickness of the coating is about 0.2mm, and performing dry powder coating performance detection 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 (3)
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-preparing machine according to a liquid-solid ratio of 3;
(2) 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 continuously 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 a liquid-solid ratio of 3;
(6) Injecting the slurry obtained in the step (5) into a stirring reaction tank with a negative pressure pipeline 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 1h;
(10) Placing the calcined dry powder into a fine grinding machine for grinding modification, sieving with a 800-mesh sieve, then placing into an aging bin, performing aging treatment at normal temperature for more than 72h, and finally packaging to obtain the dry powder building coating;
and (10) putting the calcined dry powder into a dry powder mixer, adding an additive, uniformly mixing, putting the uniformly mixed powder into a fine grinding machine for grinding modification, sieving with a 800-mesh sieve, putting into an aging bin, performing aging treatment at normal temperature for over 72 hours, 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 as claimed in claim 1, wherein the additive comprises the following raw materials in percentage by weight: 1.5 to 2.0 percent of 1.6 modulus dry powder water glass; white cement 8-10%; 8 to 10 percent of re-dispersible latex powder; 0.2 to 0.5 percent of methyl cellulose ether; 0.3 to 0.4 percent of defoaming agent; 0.3 to 1.0 percent of lignocellulose; 0.1 to 0.3 percent of sodium tripolyphosphate; 2.5 percent of polyvinyl alcohol; 10 percent of titanium dioxide.
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 further comprises the following raw materials in percentage by weight: 10 percent of fly ash.
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