CN106927507A - One kind electrolysis MnO2The method for preparing manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer with waste residue containing Mn in electrolysis Mn productions - Google Patents
One kind electrolysis MnO2The method for preparing manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer with waste residue containing Mn in electrolysis Mn productions Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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Abstract
The present invention discloses a kind of electrolytic MnO2 and is electrolysed the method that waste residue containing Mn prepares manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer during Mn is produced.Waste residue containing Mn is weighed first, adds clear water and H2SO4, temperature-programmed reaction, segmentation addition lime stone, Ca (OH)2、NH4HCO3、(NH4)2CO3、K2CO3、KOH、H2SO4, control is decomposed, converted, synthetic reaction condition, and product is separated by filtration, purifies, being concentrated by evaporation, crystallizing, drying acquisition MnCO3、CaSO4、(NH4)2SO4·K2SO4, Si- Al gangue slag products.The present invention is enabled to production electrolysis MnO2Waste residue containing Mn with electrolysis Mn is able to whole recyclings, without three industrial wastes discharge, obtains maximum recycling.
Description
Technical field
The present invention relates to chemical technology field, it is specifically related to administer electrolysis MnO2The manganese for being electrolysed the waste residue containing Mn of Mn is dirty
Dye, environmental protection, recycle manganese regenerated resources, prepare manganese carbonate（MnCO3）Ammonium sulfate compound potassium sulfate fertilizer（(NH4)2SO4·
K2SO4）A kind of method.
Background technology
Electrolysis MnO2Be mainly used in dry cell production, as alkali manganese type, mercury-free alkaline manganese type, lithium manganese type dry cell positive pole material
Material, the output and export volume of China's dry cell occupy first place in the world, and current China is electrolysed MnO2260,000 tons of annual production, due to the modern times
The development of the development of chemical industry, particularly electronics industry, to electrolysis MnO2Demand increase increasingly, its yield is also accordingly increasing
Plus.
Electrolysis Mn is mainly used in deoxidier, desulfurizing agent in steel and iron industry production steel alloy, stainless steel and process for making,
Steel and iron industry consumption is the 80% of the yield for being electrolysed Mn, and remaining 20% is consumed in and coloured controls gold, chemical industry, petroleum refining industry and magnetic
The industries such as material, 1,000,000 tons of current China electrolysis Mn annual productions, it has also become the maximum electrolysis Mn in the whole world is produced, exports and consumed
Big country, with the rising of the demand in market, is electrolysed the yield of Mn also in simultaneous growth.
Production electrolysis MnO2Manganese raw material with electrolysis Mn is manganese carbonate ore and manganese oxide ore, the explored manganese ore reserves of China
It is 5.92 hundreds of millions tons, is mainly to produce one of manganese ore state in the world, manganese ore quality manganese average grade about 22%, quality is generally poor, symbol
Close the rich manganese ore of international commodity level（Mn content >=48%）Ore deposit complete lack of rich manganese ore（Manganese oxide ore Mn content >=30%, carbonic acid
Manganese Mn content >=25%）Reserves are few, only 39,800,000 tons, account for the 6.71% of gross reserves, and China's manganese ore accounts for total storage based on poor manganese ore
The 93.29% of amount, main metal Mn contents are relatively low, and impurity component Si, Fe, Ca, Mg, P, K, Na, Al, S equal size is higher.
Main body manganese ore is manganese carbonate ore, accounts for the 92.35% of gross reserves, and manganese carbonate ore is mainly by manganese spar, calciorhodochrosite, manganese
Calcite, bannisterite, alabandite etc. are constituted, and secondary body manganese ore is manganese oxide ore, and manganese oxide ore is through secondary oxidation by manganese carbonate stone
Effect is gradually formed, mainly by groups such as pyrolusite, psilomelane, meta-manganic acid ore, cryptomelane, hausmannite, braunite, manganites
Into.Manganese ore associated minerals You Gao lin soil, silica, calcite, limonite, bloodstone, rhodonite gangue component etc..
To produce electrolysis MnO per year2260000 tons, 1,000,000 tons of meters of electrolysis Mn, are raw material with manganese carbonate ore, and containing Mn 20%, year needs
6,900,000 tons of manganese carbonate ore, MnO is electrolysed in output2In the production process of electrolysis Mn products, acidizing process and impurity elimination operation meeting
Form 5,200,000 tons of waste residue containing Mn, slag rate 75% or so, slag contains Mn 3~6%, equivalent 20.8 ten thousand tons~31.2 ten thousand tons of metal Mn/
Year.
Current each manufacturing enterprise is all to take method of abandoning to process, and will contain Mn waste residues and be placed in mine tailing Ju landfills, without recovery profit
With, the loss of manganese regenerated resources is not only caused, while the waste residue containing Mn of outdoor accumulation also suffers from the drip washing of rainwater in Ju, formed
Manganese slurry penetrant, polluted-water and soil, destroy ecological environment.Therefore research treatment is electrolysed MnO2In electrolysis Mn productions
Waste residue containing Mn, reclaims manganese regenerated resources, prepares MnCO3, (NH4)2SO4·K2SO4Technical method, be extremely have realistic meaning
's.
It is being related to process waste residue containing Mn, recovery Mn regenerated resources are prepared in Mn Product Process, Chinese invention
CN101767827A and Chinese invention CN102140582B disclose two kinds of methods of recycling manganese sulfate by using electrolytic metal manganese waste slag,
Chinese invention CN101767802A discloses a kind of method of recycling ammonium sulphate from waste mineral slag of electrolytic manganese metal.
These three methods are all the low water-soluble manganese sulfates of the content being electrolysed in the waste residue containing Mn during Mn is produced with water dissolves
（In terms of manganese 1.14% or so）And ammonium sulfate（In terms of ammonia 0.82% or so）, then take different purification impurity eliminations, precipitate and separate, steaming
Hair concentration, crystallizing and drying technical matters, prepare manganese sulfate and ammonium sulfate product, and in the slag containing Mn in electrolysis Mn productions
Content water-insoluble Mn high（2.86~4.86%）With electrolysis MnO2Waste residue containing Mn in production does not separate and recover Mn regeneration
Resources technology process.
Waste residue containing Mn in water-soluble solution treatment electrolysis Mn productions, after preparing manganese sulfate and ammonium sulfate, still there is substantial amounts of containing
Mn residues are discharged, and environment can be polluted.
The content of the invention
The present invention is a kind for the treatment of electrolysis MnO2With electrolysis Mn waste residues, whole reclaiming resources, preparation MnC03(NH4)2SO4·K2SO4CaSO4Deng, and without the technology method of three industrial wastes discharge.MnC03As production chemistry Mn02, Mn-Al conjunctions
Gold, Mn-Si alloy raw materials and as electrolysis Mn02The manganese ore raw material of electrolysis Mn productions, (NH4)2SO4·K2SO4As composite nitrogen potassium
Chemical fertilizer, CaSO4It is used as the raw material that autoclave aerated concrete building block is produced with the Si-Al slags of surplus.
Technical scheme is as follows：
A kind of method for preparing manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer with waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions,
Comprise the following steps：
（1）By solid-to-liquid ratio 1:0.9~2 measures clear water or reuse washings, adds electrolysis MnO2With electrolysis Mn production in containing Mn
Waste residue stirring to pulp is into distributed slurry；
（2）Stirring adds sulfuric acid（H2SO4）, control slag acid to compare 1:0.18~0.7（Slag acid is than being waste residue containing Mn and sulfuric acid solution
Mass ratio）, the mol/L of acid concentration 1.08~4, temperature-programmed reaction, 85~200 DEG C of 0.5~6h of reaction of temperature, middle control reaction
Terminal slag contains Mn≤0.08%, after reaction terminates, adds appropriate reuse washings；
（3）To step（2）Lime stone slurry, mesh~120 mesh of dry powder fineness 80 are added in gained slurries；Or add Ca (OH)2Material
Slurry, addition is 1.01~1.3 times of theoretical value, and 0.5 ~ 4h, control slurry reaction terminal CaSO are reacted in 0~100 DEG C4Matter
Amount percentage composition 35 ~ 40%, is separated by filtration, and filter cake is gangue slag and CaSO4Mixture, filter cake is washed with clear water, solid mixture
As autoclave aerated concrete building block raw material of building materials, washing water reuse is in step（1）Slurry preparation；The main component of filtrate is
MnSO4Liquid；
（4）Step（3）Lime stone slurry, mesh~120 mesh of dry powder fineness 80, or Ca (OH) are continuously added in gained filtrate2Slurry,
0~40 DEG C of reaction temperature, 0.5~4h, control slurry reaction terminal pH 3~5.5；The NH of effusion3Gas is pumped into through airduct and sucks
Device, absorbent is made with dilute sulfuric acid, and absorbing liquid is dilute（NH4)2SO4Liquid, the solution after absorption circulates molten for follow-up evaporation and concentration
Liquid, is separated by filtration slurry, and filter cake is washed with clear water, and pH value is controlled to 6~7, and filter cake is CaSO4Precipitation, as steam pressurized mixed
Solidifying building block building material feedstock, the not outer row of washings, is back to the preparation containing Ca slurries, and filtrate is the MnSO containing K4Liquid；
（5）In the MnSO containing K4K is analyzed in liquid2O、(NH4)2SO4Content, with (NH4)2SO4·K2SO4In contain N 14%, containing K2O
11~14%, calculate (NH4)2CO3、NH4HCO3And K2CO3, KOH input amount and by amount of calculation put into, in 0~40 DEG C react 0.3
~4h, middle control reaction end pH are 8~10, take solution qualitative analysis without Mn2+Reaction, stops stirring, and slurry digestion time 3~
12h；
（6）Slurry is separated by filtration, filtrate is (NH4)2SO4·K2SO4Solution, filter cake is MnCO3Sediment, is washed with clear water, is washed
Water circulation is washed in step（1）Slurry preparation.
(NH4)2SO4·K2SO4Solution is evaporated concentration, crystallisation by cooling, centrifugation and dry post processing, obtains
(NH4)2SO4·K2SO4Chemical fertilizer；Specially：
In (NH4)2SO4·K2SO4In solution, the sulfuric acid solution adjustment pH value 3~4 that mass fraction is 10~30%, heating are added
It is concentrated by evaporation, as (NH) in concentrate2SO4When content reaches 400~660g/L, stop heating, 0~20 DEG C of crystallisation by cooling；
Crystalline solid is centrifuged（It is preferred that inserting link-suspended basket centrifuge separation）, wet solids is after drying butt (NH4)2SO4·K2SO4Composite chemical fertilizer, filtrate is (NH4)2SO4·K2SO4Mother liquor, returns and is concentrated by evaporation operation.
The MnCO obtained in said process3As production chemistry MnO2, Mn-AI alloy Mn-Si alloy raw materials and as production
Electrolysis MnO2It is electrolysed the manganese ore raw material of Mn.
The beneficial effects of the present invention are：
（1）The present invention is enabled to production electrolysis MnO2With electrolysis Mn waste residue containing Mn be able to whole recyclings, not only without
Three industrial wastes are discharged, and cause that waste residue obtains maximum recycling, MnCO3As production chemistry MnO2, Mn-Al
Alloy, Mn-Si alloy raw materials and production electrolysis MnO2With the manganese ore raw material of electrolysis Mn, (NH4)2SO4·K2SO4It is compound as nitrogen potassium
Fertilizer；CaSO4With the raw material that Si-Al gangues slag is used as production autoclave aerated concrete building block construction material.
（2）The method of the present invention, the yield of Mn can be up to more than 98%, or even close to 100%, (NH4)2SO4·K2SO4Receive
Rate can also be up to more than 98%, gained (NH4)2SO4·K2SO4, quality can reach GB535-1995/XG-2003 standards, meet
The requirement of chemical fertilizer；Mn-Al slags, CaSO4Compound material and CaSO4Can serve as producing autoclave aerated concrete building block raw material, preparation
Autoclave aerated concrete building block quality can reach GB11968-2006 standards.
Specific embodiment
The present invention is described in further details with reference to specific embodiment, but the present invention is not limited thereto.
Embodiment
Measure H2O 450ml are inserted in 2000ml there-necked flasks, open stirring, add the waste residue containing Mn of Mn contents 4.5%
（Butt）500g, breaks into distributed slurry, adds the industrial sulphuric acid 70ml that mass fraction is 98%, and temperature programming to 140 DEG C of constant temperature is stirred
Reaction is mixed, the outlet mouth of pipe connects serpentine condenser infinite reflux, after reaction 30min, start middle control, Mn contains during feeding slurry mixes analysis slag
Amount, during reaction 80min, Mn contents 0.073% in slag stop heating, add H2O 200ml stirrings natural cooling is cooled to 80 DEG C；
To the lime stone water slurry that solid content is 50% is added in above-mentioned slurries, 60~65 DEG C of reactions of temperature are middle to control slag
CaSO4Weight/mass percentage composition 36.4%, stops addition lime stone water slurry, adds appropriate H2O, pours out slurry, uses vavuum pump suction filtration,
Slurry is separated by filtration, 200ml H are taken2O washs filter cake by several times, and preceding 100ml washings are incorporated to filtrate, rear 100ml washings bottling
The slurry of waste residue containing Mn is prepared in reuse；Obtain MnSO4Filtrate 600ml, containing Mn 3.6%, containing K 0.2%, filter cake is Si-Al slags, containing H2O
28.6%, wet feed weight 583g, containing Mn 0.058%, CaSO4 36.4%、SiO2 40.5%、Al2O3 15.6%、MgO 6.1%、
Fe2O3 0.86%th, remaining 0.5%；Mn direct yields reach 98.48%；
In the MnSO containing K4In liquid, the lime stone water slurry that solid content is 50% is added, 60min, the NH of effusion are reacted in 26 DEG C3
Gas is pumped into dilute H2SO4Absorber, slurry pH value 4.0 is separated with vavuum pump suction filtration, takes clear water 300ml filter washes cake to cleaning solution pH value
It is 7, filter cake is CaSO4Precipitation, wet feed contains H2O 31.8%, weight 56.9g, CaSO4Content 93.15%, 150ml is incorporated to before washings
Filtrate, the not outer row of rear 150ml reuses, for preparing the slurry of waste residue containing Mn, filtrate is the MnSO containing K4Liquid.
In the MnSO containing K4In liquid, industry (NH is added4)2CO3 35g, 20min is stirred in 26 DEG C, adds industrial K2CO3
8g, stirs 20min, and control reaction end pH value 8~9 is aged 3h, and middle control takes the K that solution sample mass fraction is 10%2CO3It is fixed
Property is without Mn2+Reaction.
Slurry, filter cake 100ml H are separated with vavuum pump suction filtration20 washing, washings are incorporated to filtrate, and filter cake is MnCO3It is wet
Material, containing H2O 30.8%, dry basis 53.8g, MnCO3Content 86.35%, filtrate is (NH4)2SO4·K2SO4Liquid,
Filling (NH4)2SO4·K2SO4In the beaker of solution, the sulfuric acid solution that mass fraction is 10% is added dropwise, adjusts pH=4, then
Beaker is inserted into water-bath, when being concentrated by evaporation to dope proportion 1.3~1.35 for 100 DEG C, beaker natural cooling crystallization is taken out, obtained
Wet (NH4)2SO4·K2SO4Crystal, after inserting centrifuge drying, enters thermostatic drying chamber drying, obtains dry (NH4)2SO4·K2SO4
54g, the mother liquor reuse of centrifuge dripping is concentrated by evaporation, (NH4)2SO4·K2SO4Yield 98.1%, (NH4)2SO4·K2SO4Middle N content
14.8%、K2O 11.2%, quality reaches GB535-1995/XG-2003 standards.
Mn-Al slags, CaSO4Compound material and CaSO4As production autoclave aerated concrete building block raw material, the steaming for preparing is tested
Pressing aero-concrete building block quality reaches GB11968-2006 standards, and the cubic compressive strength of wherein building block is：Production sample
4.074Mpa, experiment sample 4.647 Mpa.
Claims (10)
1. it is a kind of produced with electrolytic MnO2 and electrolysis Mn in waste residue containing Mn prepare the side of manganese carbonate and ammonium sulfate compound potassium sulfate fertilizer
Method, it is characterised in that comprise the following steps：
（1）Electrolysis MnO is added in clear water or reuse washings2With the waste residue containing Mn in electrolysis Mn productions, stirring to pulp is into uniform
Slurry；
（2）In step（1）Slurry in, add sulfuric acid reacted；
（3）In step（2）Completion slurry in, add slurry containing Ca reacted, control slurry reaction terminal, then filtering divide
From filter cake is CaSO4With Si-Al gangue mixtures, filter cake is washed with clear water, washing water reuse is in step（1）Slurry preparation,
The main component of filtrate is MnSO4Liquid；
（4）In step（3）MnSO4In liquid, continuously add slurry containing Ca and reacted, control slurry reaction terminal pH, while inhaling
Receive effusion containing NH3Gas；
（5）By step（4）Complete slurry filtration to separate, with clear water filter wash cake, filter cake is CaSO4Precipitation, control is fixed in taking washing water sample
Property analysis, in the preparation containing Ca slurries, filtrate is the MnSO containing K to washing water reuse4Liquid；
（6）In step（5）MnSO containing K4In liquid, ammonium salt and sylvite raw material is added to be reacted, middle control reaction end pH, sampling
Middle control qualitative analysis, slurry is aged；
（7）The slurry filtration that will be aged is separated, and filter cake is MnCO3Precipitation, is washed, wet MnCO with clear water3As production chemistry
MnO2, Mn-Al alloys, Mn-Si alloy raw materials and as production electrolysis MnO2The manganese ore raw material of Mn is electrolysed, washing water reuse is in containing
The preparation of Mn waste residue slurries；Filtrate is (NH4)2SO4·K2SO4Liquid；
（8）In step（7）(NH4)2SO4·K2SO4In liquid, dilute H is added2SO4Adjustment pH value, heating evaporation concentration, works as concentrate
In contain (NH4)2SO4When reaching finite concentration, stop heating concentrate；
（9）By step（8）Concentrate crystallisation by cooling, crystal centrifugation, wet solids is dry (NH through drying4)2SO4·
K2SO4Composite chemical fertilizer, filtrate is (NH4)2SO4·K2SO4Mother liquor, mother liquor is returned and is concentrated by evaporation operation.
2. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulphur
The method of sour K composite fertilizer, it is characterised in that step（1）In, waste residue containing Mn is 1 with the solid-to-liquid ratio of clear water or reuse washings:
0.9~2.
3. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulphur
The method of sour K composite fertilizer, it is characterised in that step（2）In, the acid of its slag is than being 1:0.18~0.7, the concentration of sulfuric acid is 1.08
~4 mol/L；Step（2）Reaction temperature be 85~200 DEG C；0.5~6h of reaction time, using temperature programming, middle control reaction
Terminal, slag contains Mn≤0.08%.
4. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulphur
The method of sour K composite fertilizer, it is characterised in that step（3）Slurry containing Ca be lime stone slurry or Ca (OH)2Slurry, lime stone
Mesh~120 mesh of dry powder fineness 80, addition is 1.01~1.3 times of theoretical value, and reaction temperature is 0~100 DEG C, and the reaction time is
0.5~4h, control slurry reaction terminal CaSO4Weight/mass percentage composition 35 ~ 40%.
5. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulphur
The method of sour K composite fertilizer, it is characterised in that step（4）Reaction temperature be 0~40 DEG C, the reaction time be 0.5~4h；Control
Slurry reaction terminal pH is 3~5.5.
6. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulphur
The method of sour K composite fertilizer, it is characterised in that step（5）In, control qualitative analysis is without Mn in taking washing water sample2+Reaction, CaSO4
Precipitation is used as autoclave aerated concrete building block raw material of building materials.
7. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulphur
The method of sour K composite fertilizer, it is characterised in that step（6) in, ammonium salt and sylvite refer to NH4HCO3、(NH4)2CO3With KOH,
K2CO3, by (NH4)2SO4·K2SO4In composite chemical fertilizer, containing N 14%, containing K2The component of O 11~14% calculates NH3Salt and K salt plus
Enter amount, reaction temperature is 0~40 DEG C, and the reaction time is 0.3~4h, and the middle anti-terminal pH of control is 8~10, and qualitative point is controlled in sampling
Folding is to take solution to be Mn2+Qualitative analysis, slurry digestion time be 3~12h.
8. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate potassium sulfate
The method of composite fertilizer, it is characterised in that step（8）In, add dilute H2SO4Adjustment pH value, dilute H2SO4Mass fraction for 10~
30%, the pH 3~4 of regulation；When in concentrate contain (NH4)2SO4Refer to 400~660 g/L during finite concentration.
9. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate potassium sulfate
The method of composite fertilizer, it is characterised in that step（9）In, crystallisation by cooling temperature is 0~20 DEG C.
10. waste residue containing Mn in electrolytic MnO2 and electrolysis Mn productions according to claim 1 prepares manganese carbonate and ammonium sulfate sulfuric acid
The method of K composite fertilizer, it is characterised in that step（4）In, absorb effusion containing NH3Gas, absorber is pumped into using airduct, is inhaled
Receipts agent is dilute H2SO4, absorbing liquid is (NH4)2SO4Liquid.
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| CN108752059A (en) * | 2018-07-04 | 2018-11-06 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN109321944A (en) * | 2018-11-22 | 2019-02-12 | 云南创磷业技术有限公司 | A kind of method of electrolytic manganese by-product waste residue comprehensive utilization |
| CN114524460A (en) * | 2020-11-23 | 2022-05-24 | 中集环境科技有限公司 | Potassium-manganese-containing acid sludge recycling process and potassium-manganese-containing acid sludge recycling system |
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| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108752059A (en) * | 2018-07-04 | 2018-11-06 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN108752059B (en) * | 2018-07-04 | 2021-05-11 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN109321944A (en) * | 2018-11-22 | 2019-02-12 | 云南创磷业技术有限公司 | A kind of method of electrolytic manganese by-product waste residue comprehensive utilization |
| CN114524460A (en) * | 2020-11-23 | 2022-05-24 | 中集环境科技有限公司 | Potassium-manganese-containing acid sludge recycling process and potassium-manganese-containing acid sludge recycling system |
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