CN101691633B - Method for innocent treatment and comprehensive utilization of manganese slag - Google Patents

Method for innocent treatment and comprehensive utilization of manganese slag Download PDF

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Publication number
CN101691633B
CN101691633B CN2009103081936A CN200910308193A CN101691633B CN 101691633 B CN101691633 B CN 101691633B CN 2009103081936 A CN2009103081936 A CN 2009103081936A CN 200910308193 A CN200910308193 A CN 200910308193A CN 101691633 B CN101691633 B CN 101691633B
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manganese
slag
ammonia
reaction
manganous
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CN2009103081936A
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CN101691633A (en
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周启云
夏纪勇
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湖南广义科技有限公司
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/242Slag reuse in metallurgical processes

Abstract

The invention provides a method for innocent-treatment and comprehensive utilization of manganese slag, which comprises the steps of: (1) washing and pressure-filtering the manganese slag, and separating manganese sulphate from ammonium sulphate which cause environmental pollution from leaching residue; (2) performing a reaction of slag washing water and a precipitator, ensuring that 5 to 10 percent of excessive precipitator is added, the reaction time is between 0.5 and 3 hours and the reaction temperature is between 30 and 100 DEG C, converting manganese ions in the slag washing water into manganese hydrate or manganese carbonate to precipitate the manganese ions, and then performing solid-liquid separation to realize the recovery of manganese; and (3) reacting a solution obtained by recovering the manganese and lime milk, wherein the reaction temperature is between 60 and 100 DEG C, reaction time is between 0.5 and 3 hours and reaction pressure is between 0 and 200mmHg, ensuring that the ammonium sulfate is converted into ammonia and calcium sulphate, absorbing the ammonia into ammonia water through an absorption device, filtering a solid-liquid mixture, separating out solid calcium sulphate, and recycling a filtrate in the slag washing process in the step (1). The method has the advantages of less equipment investment, low energy consumption and production cost, high recovery rate of valuable compositions and good comprehensive effect of innocent treatment of the manganese slag.

Description

A kind of manganese slag harmlessness is handled and comprehensive utilization method

Technical field

The present invention relates to a kind of manganese slag harmlessness and handle and comprehensive utilization method, especially relate to the harmless treatment and the comprehensive utilization method thereof of the discarded manganese slag that produces in the manganese goods hydrometallurgy process such as a kind of electrolytic metal Mn, electrolytic manganese dioxide and manganous sulfate.

Background technology

China is manganese production of articles big country, is example with the electrolytic metal Mn, and its yearly capacity has reached 2,000,000 tons, and actual annual production has reached 800,000 tons.Because the manganese ore grade is more and more lower, only manganese metal factory produces 6,800,000 tons of manganese filter residues every year at least.Containing the liquid weighted average after the press filtration in the manganese slag calculates by minimum 25%, take away manganese sulfate solution in the above-mentioned manganese slag and reach 1,700,000 tons, manganous sulfate content is on average pressed 110g/L (Mn40g/L) calculating in the solution, ammonium sulfate content is on average pressed 120g/L and is calculated, annual from these manganese slags the loss manganous sulfate reach 18.7 ten thousand tons of (amount to 6.8 ten thousand tons of manganese amounts of metal, be equivalent to 45.3 ten thousand tons of the manganese carbonate ores of Mn content 15%), ammonium sulfate and reach 20.4 ten thousand tons.Ammonium sulfate wouldn't directly reclaim, and can only reclaim liquefied ammonia, calculates about 52500 tons of recyclable liquefied ammonia to reclaim liquefied ammonia.

The contained manganous sulfate of these manganese slags, ammonium sulfate and other vitriol all are water miscible, can permeate the ground or flow into rivers,lakes and seas with water, cause serious environmental to pollute.Because also there are a lot of hidden danger in the existence of manganese and other element even these slags are used for producing building materials.Utilize general simple washery slag technology, understand the balance of destroying electrolytic solution because of entering of slag washing water and be restricted.

Owing to do not have suitable technique means and economic manganese slag treating method, environmental administration requires electrolytic manganese factory to adopt the stacking mode of building impermeable slag dam at present.Because slag dam is generally built the mountain valley in, rain-out, immersion can make soluble substance enter water system, polluted source.Especially, slag dam collapses, and slag enters rivers, and the serious accident of serious environment pollution also happens occasionally.

Therefore, how efficient, science, handle manganese ore leached mud in the manganese ore hydrometallurgical liquid process economically, make it innoxious, recycle wherein valuable manganese and ammonium simultaneously, be one and relate to environment protection and resource-effective vital task.

Notification number be CN1180100C patent disclosure a kind of " utilizing waste manganese mud to soak the method that the manganous sulfate in the slag is produced manganous carbonate ", recycle waste manganese mud and soak the manganous sulfate production manganous carbonate of carrying secretly in the slag, solve solubility manganous sulfate pollution on the environment and make full use of Mineral resources, its method is to be raw material with the useless slag that soaks of manganese ore powder after sulfuric acid to leach prepares sulphuric acid soln, water embathes waste manganese mud and soaks slag recovery manganese sulfate solution wherein, after removing impurity with soluble carbon hydrochlorate (for example bicarbonate of ammonia) solution reaction, produce manganous carbonate, prepare other corresponding manganese products by manganous carbonate again.Its shortcoming is: extracted manganese and but caused more serious ammonium polluted by nitrogen, because a large amount of ammonium salts exist, precipitated not really fully, the rate of recovery is lower, and cost recovery is higher.

Publication number is that the patent application of CN101306425A discloses a kind of " a kind of technology of electrolytic manganese residues comprehensive utilization ", by washing repeatedly, filtering recyclable materials in the electrolytic manganese residues is reclaimed.The shortcoming of this scheme is, repeatedly repetitive scrubbing just can make strength of solution increase gradually, and washing flow is long, and occupied ground is big; Its evaporation concentration must consume big energy, expense height; Concentrate and still can make the total amount of liquid increase after back electrolytic solution enters electrolyzer, destroy electrolyte balance.

Publication number is that the patent application of CN101348273A discloses " a kind of neutralizing agent and application thereof that reduces manganese content in the manganese slag ", and this neutralizing agent is that a kind of BET value is less than 5m 2The unslaked lime of/g, its median size are 10~50 μ m.Use the present invention's neutralizing agent that sulfuric acid leaching manganese feed liquid is neutralized, neutral temperature 80-90 ℃, in and time 0.5-3Hr, the concentration of soluble manganese in the manganese slag can be reduced to below the 2ppm from thousands of ppm, thereby needn't build the manganese slag separately specially and handle the field, after only need doing simple pH adjustment to water seepage, can externally discharge with sulfuric acid; Also solved nuisance to phreatic osmosis pollution problem and rainy season the manganese slag the sliming problem, make the manganese slag become environmentally friendly refuse.The technical problem of its solution is to add which kind of neutralizing agent to make the pH of manganese slag reach emission standard, and the valuable constituent of how extracting is not wherein provided technical scheme.

Summary of the invention

The object of the present invention is to provide a kind of facility investment few, energy consumption and production cost are low, and the manganese slag harmlessness that the valuable constituent rate of recovery is high is handled and method of comprehensive utilization.

The objective of the invention is to be achieved through the following technical solutions, it may further comprise the steps: (1) to the manganese slag wash, press filtration, separate from leached mud causing the manganous sulfate and the ammonium sulfate of environmental pollution, to realize the harmless treatment to the manganese slag, washing and filter pressing gained manganese slag later can be used for brickmaking or makes other purposes; (2) with slag washing water and precipitation agent reaction, the excessive 5-10% of precipitation agent that adds, reaction times 0.5-3 hour, temperature of reaction is different and different according to the precipitation agent of selecting for use, generally can in 30-100 ℃ of scope, select, manganese is changed into manganous hydroxide or manganous carbonate is precipitated out, carry out solid-liquid separation then, realize recovery manganese; (3) will reclaim the reaction of later solution of manganese and milk of lime, temperature of reaction 60-100 ℃, reaction times 0.5-3 hour, reaction pressure 0 was to-200mmHg, and reaction formula is: (NH 4) 2SO 4+ Ca (OH) 2=CaSO 4↓+2NH 3↑+2H 2O), make the ammonium sulfate in the solution be converted into ammonia and calcium sulfate, ammonia absorbs into ammoniacal liquor by absorption unit, can make neutralizing agent and use; Solidliquid mixture (suspension) is filtered, and isolated solid calcium sulphate can make to prepare raw material or other purposes of cement, and filtrate is returned the recycle of step (1) washery slag operation.

Described step (1) has prior art available.

Precipitation agent in the described step (2) can be alkaline material or other soluble carbon hydrochlorates such as ammoniacal liquor, volatile salt, bicarbonate of ammonia, calcium hydroxide:

(1) when precipitation agent is ammoniacal liquor, its reaction formula is:

MnSO 4+2NH 4OH=Mn(OH) 2↓+(NH 4) 2SO 4

After the manganous hydroxide precipitation reclaimed, alternative part ammonia entered system liquid workshop section, regulates the pH value; Behind step (3) recovery ammonium, ammonia volume can reduce than existing technology.

(2) when precipitation agent is volatile salt, its reaction formula is:

MnSO 4+(NH 4) 2CO 3=MnCO 3↓+(NH 4) 2SO 4

After manganous carbonate being precipitated recovery and ammonia recovery, ammonia volume can reduce than existing technology.

(3) when precipitation agent is bicarbonate of ammonia, its reaction formula is:

MnSO 4+2NH 4HCO 3=MnCO 3↓+(NH 4) 2SO 4+CO 2↑+H 2O

After manganous carbonate precipitation reclaims can in and part of sulfuric acid, after ammonium reclaimed by step (3), ammonia volume can be than existing technology minimizing.

(4) when adding lime, when precipitation agent was calcium hydroxide, its reaction formula was:

MnSO 4+Ca(OH) 2=Mn(OH) 2↓+CaSO 4

(NH 4) 2SO 4+Ca(OH) 2=CaSO 4↓+2NH 3↑+2H 2O

Described step (2), (3) as required, can merge and carry out, and for example, select for use calcium hydroxide to make precipitation agent, can precipitate manganese and ammonia still process simultaneously.At this moment, because above-mentioned two reactions are carried out simultaneously, when reclaiming ammonium acquisition ammoniacal liquor, obtained the mixture of manganous hydroxide and calcium sulfate.This mixture can substitute partial ammonia water in system liquid workshop section and regulate the pH value, though because entering of calcium sulfate can increase the quantity of slag, can improve strainability, simplifies flow process; Also can obtain manganese sulfate solution, wash heat be washed the gypsum (calcium sulfate) of back acquisition and do the building materials use by sulfuric acid to leach.

In the described step (3), can reclaim the speed and the rate of recovery so that improve ammonia in conjunction with stirring, intensification, negative pressure.

Adopting the present invention to handle the electrolytic manganese leached mud, to have a facility investment few, and energy consumption and production cost are low, valuable constituent rate of recovery height, and the manganese slag harmlessness is handled the good characteristics of net effect.

Embodiment

Below in conjunction with embodiment the present invention is described in further detail.

Embodiment 1

Get 300 tons of electrolytic manganese factory leached muds, liquid content 30% (weight) wherein, manganous sulfate content 110g/L (Mn40g/L) in the described solution, ammonium sulfate content 120g/L, treatment step is as follows:

(1) in leached mud, adds and be equivalent to slag and weigh 50% water, carry out the continuous countercurrent washing again by stirring pulping, make that manganese ion concentration is 22g/L in the slag washing water, ammonium sulfate 70g/L carries out solid-liquid separation then, manganous sulfate content 1.8g/kg in the slag, ammonium sulfate content 1.8g/kg, total yield 93%, filter residue send brickmaking, filtrate send preheater to be preheating to 80 ℃, send reactor then;

(2) in reactor, filtrate is heated to 90 ℃, generates calcium sulfate, ammonia and manganous hydroxide respectively with calcium hydroxide reaction, and in 3 hours reaction times, slightly negative pressure is (20mmHg) in the reaction vessel;

(3) ammonia of reaction generation enters the absorption tower, and ammonia is absorbed by water and becomes ammoniacal liquor in the absorption tower, is stored in then in the ammoniacal liquor storage tank, makes neutralizing agent and uses;

(4) calcium sulfate and the manganous hydroxide suspension of reaction generation, by the pressure filter press filtration, after carrying out solid-liquid separation, filtrate is returned the recycling of step (1) washing procedure, and filter residue send infusion fluid preparation vehicle intercropping neutralizing agent usefulness, but the manganous hydroxide replacing partial ammonia water in the filter residue, regulate the pH value, reach the purpose that reclaims manganese simultaneously, calcium sulfate does not then react, and helps the effect of filter.

By reclaim altogether 4893 kilograms of manganous hydroxides; 2100 kilograms of ammonia.Energy consumption: ton manganese power consumption 480 kilowatt-hours; 1.5 tons in ton ammonia consumption coal.Production cost: 1266 yuan of ton manganese cost recovery; 1899 yuan of ton ammonia cost recovery, manganese recovery ratio 90%, ammonia recovery 90%.

Embodiment 2

Get 300 tons of electrolytic manganese factory leached muds, liquid content 30% (weight) wherein, manganous sulfate content 110g/L (Mn40g/L) in the described solution, ammonium sulfate content 120g/L.Treatment step is as follows:

(1) in leached mud, adds and be equivalent to slag and weigh 80% water, cooperate pressure filter to carry out the washing of three stage countercurrents by stirring pulping, make that manganese ion concentration is at 15g/L in the slag washing water, ammonium sulfate carries out solid-liquid separation then at 45g/L, manganous sulfate content 1.5g/kg in the slag, ammonium sulfate content 1.5g/kg, total yield 95%, filter residue send brickmaking, filtrate send preheater to be preheating to 80 ℃, send reactor then;

(2) in reactor, filtrate is heated to 95 ℃, generates calcium sulfate, ammonia and manganous hydroxide respectively with calcium hydroxide reaction, and 2 hours reaction times was normal pressure in the reaction vessel;

(3) ammonia of reaction generation enters the absorption tower, and ammonia is absorbed by water and becomes ammoniacal liquor in the absorption tower, is stored in then in the ammoniacal liquor storage tank, makes neutralizing agent and uses;

(4) calcium sulfate and the manganous hydroxide suspension of reaction generation, by the pressure filter press filtration, after carrying out solid-liquid separation, filtrate is returned the recycling of step (1) washing procedure, and filter residue send infusion fluid preparation vehicle intercropping neutralizing agent usefulness, the manganous hydroxide replacing partial ammonia water in the filter residue, regulate the pH value, reach the purpose that reclaims manganese simultaneously, calcium sulfate does not then react, and helps the effect of filter.

By reclaim altogether 4890 kilograms of manganous hydroxides; 2050 kilograms of ammonia.Energy consumption: ton manganese power consumption 480 kilowatt-hours; 1.5 tons in ton ammonia consumption coal.Production cost: 1266 yuan of ton manganese cost recovery; 1945 yuan of ton ammonia cost recovery, manganese recovery ratio 90%, ammonia recovery 90%.

Embodiment 3

Get 300 tons of electrolytic manganese factory leached muds, liquid content 30% (weight) wherein, manganous sulfate content 110g/L (Mn40g/L) in the described solution, ammonium sulfate content 120g/L.Treatment step is as follows:

(1) in leached mud, adds and be equivalent to slag and weigh 100% water, cooperate pressure filter to carry out the washing of three stage countercurrents by stirring pulping, make that manganese ion concentration is at 11g/L in the slag washing water, ammonium sulfate carries out solid-liquid separation then at 35g/L, manganous sulfate content 1.4g/kg in the slag, ammonium sulfate content 1.4g/kg, total yield 95.7%, filter residue send brickmaking, filtrate send preheater to be preheating to 80 ℃, send reactor then;

(2) in reactor, filtrate is heated to 75 ℃, generates calcium sulfate, ammonia and manganous hydroxide respectively with calcium hydroxide reaction, and in 0.5 hour reaction times, the band negative pressure (200mmHg) in the reaction vessel;

(3) ammonia of reaction generation enters the absorption tower, and ammonia is absorbed by water and becomes ammoniacal liquor in the absorption tower, is stored in then in the ammoniacal liquor storage tank, makes neutralizing agent and uses;

(4) calcium sulfate and the manganous hydroxide suspension of reaction generation, by the pressure filter press filtration, after carrying out solid-liquid separation, filtrate is returned the recycling of step (1) washing procedure, and filter residue send infusion fluid preparation vehicle intercropping neutralizing agent usefulness, but the manganous hydroxide replacing partial ammonia water in the filter residue, regulate the ph value, reach the purpose that reclaims manganese simultaneously, calcium sulfate does not then react, and helps the effect of filter.

By reclaim altogether 4820 kilograms of manganous hydroxides; 1800 kilograms of ammonia.Energy consumption: ton manganese power consumption 480 kilowatt-hours; 2.2 tons in ton ammonia consumption coal.Production cost: 1285 yuan of ton manganese cost recovery; 2389 yuan of ton ammonia cost recovery, manganese recovery ratio 88.6%, ammonia recovery 80%.

Embodiment 4

Still get electrolytic manganese factory leached mud, liquid content 30% in the filter residue, manganous sulfate content 110g/L (Mn40g/L) in the above-mentioned solution, ammonium sulfate content 120g/L.Treatment step is as follows:

(1) washery slag part, in leached mud, add slag and weigh 80% water, cooperate pressure filter to carry out the washing of three stage countercurrents by stirring pulping, make that manganese ion concentration is greater than 15g/L in the slag washing water, ammonium sulfate is greater than 45g/L, carry out solid-liquid separation then, manganous sulfate content 1.5g/kg in the slag, ammonium sulfate content 1.5g/kg, total yield 95%, filter residue send brickmaking factory, and filtrate is sent reactor;

(2) manganous sulfate and ammonium bicarbonate soln reaction in the reactor, temperature of reaction is controlled at 30 ℃, and reaction generates ammonium sulfate, carbonic acid gas and manganous carbonate, 2 hours reaction times respectively;

(3) solid-liquid separation and washing are carried out in the suspension that has reacted pressure filter press filtration, and filter cake is made neutralizing agent usefulness, and filtrate send next process to reclaim ammonia;

(4) in reactor, ammonium sulfate filtrate is heated to 90 ℃ and calcium hydroxide reaction, generate calcium sulfate and ammonia respectively, 2 hours reaction times, negative pressure-20mmHg in the reaction vessel.The ammonia that reaction generates enters the absorption tower, and ammonia is absorbed by water and becomes ammoniacal liquor in the absorption tower, be stored in then buy car in installments in the ammoniacal liquor storage tank between neutralization use.

By reclaim altogether 4742 kilograms of manganous carbonates; 3869 kilograms of ammonia.Energy consumption: ton manganese power consumption 640 kilowatt-hours; 0.9 ton in ton ammonia consumption coal.Production cost: 2629 yuan of ton manganese cost recovery; 1550 yuan of ton ammonia cost recovery, manganese recovery ratio 71.5%, ammonia recovery 89%.

Embodiment 5

Still get electrolytic manganese factory leached mud, liquid content 30% in the filter residue after the press filtration, manganous sulfate content 110g/L (Mn40g/L) in the above-mentioned solution, ammonium sulfate content 120g/L.Treatment step is as follows:

(1) in leached mud, adds slag and weigh 80% water, cooperate pressure filter to carry out the washing of three stage countercurrents by stirring pulping, manganese ion concentration 15g/L in the slag washing water, ammonium sulfate content 45g/L carries out solid-liquid separation then, the manganous sulfate content 1.5g/kg in the slag, ammonium sulfate content 1.5g/kg, total yield 95%, filter residue send brickmaking, and filtrate is sent reactor;

(2) manganous sulfate and ammonia soln reaction in reactor, temperature of reaction is controlled at 30 ℃, and reaction generates ammonium sulfate and manganous hydroxide respectively, and 2 hours reaction times is so that the manganous hydroxide crystal growth helps solid-liquid separation and improves yield.

(3) suspension that has reacted carries out solid-liquid separation and washing with pressure filter, reclaims the manganous hydroxide that obtains, and send the chemical combination workshop to make system liquid and neutralization replacing partial ammonia water, regulates the pH value, and manganese then becomes manganese sulfate solution; Filtrate is sent next process to reclaim ammonia and is used;

(4) ammoniumsulphate soln that the original ammonium sulfate and second step generate in the slag washing water is heated to 95 ℃ and generates calcium sulfate and ammonia respectively with calcium hydroxide reaction in reactor, 2 hours reaction times, in the container-the 40mmHg negative pressure.The ammonia that reaction generates enters the absorption tower, and ammonia is absorbed by water and becomes ammoniacal liquor in the absorption tower, be stored in then buy car in installments in the ammoniacal liquor storage tank between neutralization use.

By reclaim altogether 3423 kilograms of manganous hydroxides; 1500 kilograms of ammonia.Energy consumption: ton manganese power consumption 640 kilowatt-hours; 2.0 tons in ton ammonia consumption coal.Production cost: 3215 yuan of ton manganese cost recovery; 1945 yuan of ton ammonia cost recovery, manganese recovery ratio 66.5%, ammonia recovery 90%.

More than several embodiment all the manganese slag can be carried out harmless treatment and reclaim wherein manganese and ammonia, that is reclaimed is solid and gas, can not destroy the solution equilibria of electrolytic manganese production line; There is not new pollutent to produce environmental friendliness; Raw materials consumption is few, and energy consumption is low, and production cost is low, uses device structure simple, and technical process is short, and operation control is easy.But compare, embodiment 4 is because of having added bicarbonate of ammonia, and cost is higher relatively, and the yield of manganous carbonate not high (approximately 70-75%); Embodiment 5 makes precipitation agent with recovery ammonia, has only increased the consumption of calcium hydroxide, but because the existence of ammonium sulfate, the manganous hydroxide precipitation is (about 70%) not exclusively, and quite a few has entered in the calcium sulfate precipitation when ammonia still process; And the raw material that adds among the embodiment 1 only has calcium hydroxide, and is evaporated owing to the ammonia overwhelming majority in the reaction later stage, and the manganous hydroxide precipitation is more complete, so embodiment 1 scheme is best.

Claims (1)

1. a manganese slag harmlessness is handled and comprehensive utilization method, it is characterized in that, may further comprise the steps: (1) to the manganese slag wash, press filtration, will cause the manganous sulfate and the ammonium sulfate of environmental pollution from leached mud, to separate; (2) with slag washing water and precipitation agent reaction, the excessive 5-10% of the precipitation agent of adding, reaction times 0.5-3 hour, temperature of reaction 30-100 ℃, mn ion in the slag washing water is changed into manganous hydroxide or manganous carbonate is precipitated out, carry out solid-liquid separation then, realize recovery manganese; (3) will reclaim the reaction of later solution of manganese and milk of lime, temperature of reaction 60-100 ℃, reaction times 0.5-3 hour, reaction pressure 0 is to-200mmHg, make ammonium sulfate be converted into ammonia and calcium sulfate, ammonia absorbs into ammoniacal liquor by absorption unit, and solidliquid mixture is filtered, isolate solid calcium sulphate, filtrate is returned the recycle of step (1) washery slag operation;
Described precipitation agent is ammoniacal liquor, volatile salt, bicarbonate of ammonia or calcium hydroxide.
CN2009103081936A 2009-10-12 2009-10-12 Method for innocent treatment and comprehensive utilization of manganese slag CN101691633B (en)

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CN102021346A (en) * 2011-01-06 2011-04-20 中国环境科学研究院 Method for recovering soluble manganese in electrolytic manganese waste residue
CN102839286A (en) * 2012-09-26 2012-12-26 中信锦州金属股份有限公司 Method for recycling bivalent manganese in electrolytic manganese leached residues
CN102912146A (en) * 2012-11-13 2013-02-06 波鹰(厦门)科技有限公司 Two-membrane process manganese recovery method
CN103173627B (en) * 2013-04-12 2014-07-09 中南大学 Method for promoting separation of valuable metals and calcic gangue minerals in waste residue
CN103540953B (en) * 2013-10-17 2016-01-27 北京阳光欣禾科技有限公司 A kind of method of comprehensive utilization of pyrometallurgical manganese ore slag
CN103787644B (en) * 2013-12-13 2015-06-03 毛耀辉 Method for preparing sintered bricks from pressure filtration residues
CN103922926A (en) * 2014-04-17 2014-07-16 绍兴县远程树脂科技有限公司 Process for purifying residual solid waste generated after alkali peeling wastewater treatment
CN104357662B (en) * 2014-11-04 2016-06-15 中国环境科学研究院 A kind of harmless treatment process of electrolytic manganese residues
CN104946890A (en) * 2015-07-15 2015-09-30 贵州红星发展大龙锰业有限责任公司 Method for synchronously recycling ammonia and manganese in manganese metal chemical combination slag
CN106927507B (en) * 2017-03-29 2018-05-22 湘潭市环境保护科学研究院 A kind of electrolysis MnO2With the method that waste residue containing Mn prepares manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer in electrolysis Mn productions
CN108273516A (en) * 2017-10-12 2018-07-13 北京森泉伟业科技有限公司 A kind of method that electrolytic manganese residues prepare effective catalyst and catalyzing hydrogen peroxide oxidative degradation methylene blue
CN107522324A (en) * 2017-10-23 2017-12-29 贵州松桃金瑞锰业有限责任公司 Electrolytic manganese production Manganese in Waste Water recovery and waste water, the technique of waste gas integrated treatment
CN108728634B (en) * 2018-06-08 2020-02-28 中南大学 Harmless treatment method for electrolytic manganese slag
CN108483501B (en) * 2018-07-04 2020-05-19 绵阳师范学院 Comprehensive utilization method of electrolytic manganese slag washing liquid
CN108842052A (en) * 2018-07-06 2018-11-20 中南大学 The method of comprehensive utilization of electrolytic manganese anode slag and electrolytic manganese crystallization double salt
CN108842053A (en) * 2018-07-06 2018-11-20 中南大学 The method of comprehensive utilization of Low grade manganese ore and electrolytic manganese crystallization double salt
CN109554546A (en) * 2018-10-24 2019-04-02 西南科技大学 A kind of method of electrolytic manganese residues harmless treatment and resource utilization

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