CN101260471B - A complete clean production process for extracting soluble manganese from manganese slag with anolyte - Google Patents
A complete clean production process for extracting soluble manganese from manganese slag with anolyte Download PDFInfo
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- CN101260471B CN101260471B CN2008101051077A CN200810105107A CN101260471B CN 101260471 B CN101260471 B CN 101260471B CN 2008101051077 A CN2008101051077 A CN 2008101051077A CN 200810105107 A CN200810105107 A CN 200810105107A CN 101260471 B CN101260471 B CN 101260471B
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- 239000011572 manganese Substances 0.000 title claims abstract description 156
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 115
- 239000002893 slag Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 238000000605 extraction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 18
- 239000000284 extract Substances 0.000 claims abstract description 16
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract 7
- 208000005156 Dehydration Diseases 0.000 claims abstract 3
- 230000018044 dehydration Effects 0.000 claims abstract 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 38
- 239000002184 metal Substances 0.000 abstract description 38
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000008151 electrolyte solution Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000000247 postprecipitation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种采用阳极液提取锰渣中可溶性锰的成套清洁生产工艺，包括以下步骤：a.将锰渣、电解金属锰生产过程中产生的阳极液输送到提取设备中，同时加入阳极液体积0～0.025倍的硫酸，锰渣与加入液体的固液重量比为1∶1～1∶15；b.通过搅拌使锰渣与阳极液充分混匀，即可获得提取液；c.提取液在提取设备中静置，使得提取液中的固体物质沉淀；d.将沉淀后的上清液过滤后直接返回至电解金属锰生产过程中的浸取氧化工序，用来制作电解液；将滤渣和提取设备中的沉渣输送到高效压滤设备进行脱水处理，将渣中的含水率降低到25％以下，渣送去锰渣场或资源化，压滤液经过过滤后返回浸取氧化工序，用来制作电解液。本发明还提供包括上述生产工艺的一种电解金属锰生产工艺。The invention discloses a complete set of clean production process for extracting soluble manganese in manganese slag by using anolyte, which comprises the following steps: a. transporting manganese slag and anolyte produced in the production process of electrolytic metal manganese to extraction equipment, and adding anode at the same time Sulfuric acid with a liquid volume of 0 to 0.025 times, the solid-liquid weight ratio of manganese slag to the added liquid is 1:1 to 1:15; b. The manganese slag and anolyte are fully mixed by stirring to obtain the extract; c. The extract is left standing in the extraction equipment, so that the solid matter in the extract is precipitated; d. After the supernatant after the precipitation is filtered, it is directly returned to the leaching and oxidation process in the electrolytic manganese metal production process, and is used to make the electrolyte; Transport the filter residue and the sediment in the extraction equipment to the high-efficiency filter press equipment for dehydration treatment, reduce the moisture content in the residue to below 25%, send the residue to the manganese residue field or recycle, and return the filter press liquid to the leaching and oxidation process after filtration , used to make electrolyte. The present invention also provides an electrolytic metal manganese production process including the above production process.
Description
Technical field
The present invention relates to recycle of electrolytic metal Mn industry resource and environment protection novel method, be specifically related to a kind of complete set of cleaning producing technique that from the manganese slag that electrolytic metal Mn produces, reclaims soluble manganese.
Background technology
In recent years, because the fast development of steel industry both at home and abroad, sharply increase the also fast development thereupon of the electrolytic metal manganese industry of China as the demand of the manganese of the deoxidation in ironmaking and the steelmaking process, sweetening agent.But simultaneously; because the electrolytic metal manganese industry is one " high material-consumption, high energy consumption, high pollution " " three high industry "; in recent years in fast development; face manganese resource scarcity, the environmental protection pressure problem and the challenge of aspect such as strictness day by day, have a strong impact on and restricting the health of industry, in order, Sustainable development.
Steps such as what current electrolytic metal Mn adopted is sulfuric acid to leach one electrolytic hydrometallurgy production technique, and its production process comprises powder process, sulfuric acid leaching, iron removal by oxidation, press filtration, purification, secondary press filtration, deep purifying, smart filter, electrolysis, passivation, rinsing, dry, peel off.In the production process of electrolytic metal Mn, need to consume resources such as a large amount of manganese carbonate ores, pyrolusite, sulfuric acid, ammoniacal liquor, electricity, produce a large amount of " waste water,waste gas and industrial residue " simultaneously.Protect reasons such as consciousness is not high, Technology backwardness, environment protection insufficient investment owing to the most of electrolytic metal Mn corporate environments of China; and enterprise distributes more concentrated relatively; to the on-site ecological environmental pollution of enterprise with destroy greatlyyer, have a strong impact on and threatening local resident's health and wellbeing.
At present in the electrolytic metal manganese industry, 1 ton of electrolytic metal Mn of every production produces 6～7 tons manganese slag, wherein owing to the reasons such as restriction of production technique, pressure filtering technique, make also residual many soluble manganese in the manganese slag, also contain a large amount of vitriol, ammonia nitrogen in the manganese slag simultaneously, the content of heavy metals such as arsenic, mercury, selenium is also higher.The annual manganese slag that produces 210,000 tons of enterprise of producing 30000 tons of electrolytic metal Mns per year, the whole outdoor storages of these manganese slags, in depositing process, especially when raining, produce a large amount of percolates, soluble manganese, vitriol, ammonia nitrogen etc. flow away thereupon, the severe contamination surrounding enviroment become the main Environmental Problems of electrolytic metal manganese industry.
It is reported that the someone utilizes water as extraction agent the soluble manganese in the manganese slag to be extracted, but because water consumption is bigger, calculate at 1: 10 by solid-to-liquid ratio, 1 ton of manganese slag needs 7 tons of water, calculate by the scale of producing 30000 tons of electrolytic metal Mn enterprises per year, produce 600～700 tons of manganese slags every day, need about 7000 tons water, and the electrolytic metal Mn factory of this scale only need to replenish 300 every day surplus ton water, will inevitably cause the system water can't balance if extracting solution is directly returned production process, problems such as water expansion occur.Therefore, extract soluble manganese in the manganese slag if use water as extraction agent, just can turn back in the production process after extracting solution need concentrate, and owing to the reason of current concentration technique, equipment, power consumption etc., cause spissated cost height, this method is infeasible economically.Therefore, using water as agent in advance, to extract the method for soluble manganese in the manganese slag inadvisable in actual production.
Therefore, the manganese slag is carried out recycling treatment, soluble manganese becomes one of bottleneck problem that needs to be resolved hurrily in the electrolytic metal Mn industry development in the recovery manganese slag.
Summary of the invention
The objective of the invention is soluble manganese in the manganese slag is extracted and utilization again.
For achieving the above object, adopt the lower concentration that produces in the electrolytic metal Mn production process to contain manganese liquid, be that anolyte is an extraction agent, soluble manganese in the manganese slag is extracted, improve the concentration of manganese in the anolyte, and turn back to system liquid process and make electrolytic solution again, when having avoided problems such as water expansion to occur, realized the purpose of resource utilization, can obviously improve economic benefit and cleaner production level that enterprise produces, meet the theory and the thinking of cleaner production and recycling economy, help increasing the sustained development of enterprises ability.
Particularly, the invention provides a kind of complete set of cleaning producing technique that adopts anolyte to extract soluble manganese in the manganese slag, it may further comprise the steps:
A. the anolyte that produces in manganese slag, the electrolytic metal Mn production process is transported in the extraction equipment, adds the sulfuric acid of 0～0.025 times of anolyte volume simultaneously, the manganese slag is 1: 1～1: 15 with the solid-liquid weight ratio that adds liquid;
B. make manganese slag and the abundant mixing of liquid by stirring, can obtain extracting solution;
C. extracting solution leaves standstill in extraction equipment, makes solid deposits in the extracting solution;
D. with the leaching oxidation operation that directly is back to behind the supernatant liquid filtering of post precipitation in the electrolytic metal Mn production process, be used for making electrolytic solution; Sediment in filter residue and the extraction equipment is transported to efficient filtering equipment carries out processed, the water ratio in the slag is reduced to below 25%, slag is sent to manganese slag field or resource utilization, and pressing filtering liquid returns the leaching oxidation operation after filtering, be used for making electrolytic solution.
Above-mentioned employing anolyte extracts the complete set of cleaning producing technique of soluble manganese in the manganese slag, and wherein this manganese slag can be the manganese slag that produces in the electrolytic metal Mn production process.
Above-mentioned employing anolyte extracts the complete set of cleaning producing technique of soluble manganese in the manganese slag, and wherein this anolyte can wherein contain Mn for the anolyte that produces after the electrolysis in sulfuric acid to leach-electrolytic metal Mn production process
2+10g/L～18g/L.
Above-mentioned employing anolyte extracts the complete set of cleaning producing technique of soluble manganese in the manganese slag, and wherein the abstraction reaction time of this step b can be 15～240 minutes.
Above-mentioned employing anolyte extracts the complete set of cleaning producing technique of soluble manganese in the manganese slag, and wherein the time of staticly settling of this step c can be 15～60 minutes.
On the other hand, the present invention also provides a kind of production technique of electrolytic metal Mn, comprise sulfuric acid to leach oxidation, purification and electrolysis step, wherein, use the anolyte that produces after the electrolysis in the electrolysis step that the manganese slag that produces in the purifying step is carried out second extraction, with directly being back to the leaching oxidation operation behind the supernatant liquid filtering after extracting, be used for making electrolytic solution, wherein this second extraction may further comprise the steps:
A. the anolyte that produces in manganese slag, the electrolytic metal Mn production process is transported in the extraction equipment, adds the sulfuric acid of 0～0.025 times of anolyte volume simultaneously, the manganese slag is 1: 1～1: 15 with the solid-liquid weight ratio that adds liquid;
B. make manganese slag and the abundant mixing of liquid by stirring, can obtain extracting solution;
C. extracting solution leaves standstill in extraction equipment, makes solid deposits in the extracting solution;
D. with the leaching oxidation operation that directly is back to behind the supernatant liquid filtering in the extraction equipment in the electrolytic metal Mn production process, be used for making electrolytic solution; Sediment in filter residue and the extraction equipment is transported to efficient filtering equipment carries out processed, the water ratio in the slag is reduced to below 25%, slag is sent to manganese slag field or resource utilization, and pressing filtering liquid returns the leaching oxidation operation after filtering, be used for making electrolytic solution.
Beneficial effect of the present invention is, this technology is improved on the basis of the existing production technique of electrolytic metal Mn enterprise, utilize the soluble manganese in the anolyte extraction manganese slag, and extracting solution is turned back to production process make electrolytic solution, problems such as water expansion when reclaiming manganese, have been avoided, also reduce the discharging of pollutent in the manganese slag simultaneously, reduced the manganese ore consumption and the production cost of unit product, helped continuing, developing in a healthy way of enterprise.This process for cleanly preparing technology has less investment, easy to operate, low cost and other advantages, has good economic benefit and environmental benefit.Extract soluble manganese in the manganese slag by the present invention, at least can extract in the manganese slag 50% soluble manganese, it is 1.7t/100t manganese slag, to electrolytic metal Mn enterprise (the manganese slag year generation: 210,000 t) of producing 30000 t per year, manganese about recyclable 3600t of year, the 1t electrolytic metal Mn is by 20000 yuan/t, can directly increase by 7,200 ten thousand yuan of the output values, the production cost of deduction 50%, 3,600 ten thousand yuan of direct economic benefits, reduce about 25000 tons of consumptions of manganese ore (ore grade 18), annual simultaneously the minimizing about pollutent manganese discharging 3600t.
Description of drawings
Fig. 1 is that the present invention adopts anolyte to extract the process flow sheet of soluble manganese in the manganese slag.
Fig. 2 is electrolytic metal Mn technological process of production figure in the prior art.
Fig. 3 is the improved electrolytic metal Mn technological process of production of the present invention figure.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to following embodiment.
Figure 1 shows that the present invention adopts anolyte to extract the process flow sheet of a preferred implementation of soluble manganese in the manganese slag.Processing step comprises: the anolyte that a. produces after with electrolysis in manganese slag, the electrolytic metal Mn production process is transported in the extraction equipment, add a certain proportion of industrial sulphuric acid simultaneously, add-on is 0～0.025 (with the volume ratio of anolyte), and the manganese slag is 1: 1～1: 15 with the solid-liquid weight ratio that adds liquid; B. make manganese slag and the abundant mixing of liquid by stirring, can obtain extracting solution; C. extracting solution leaves standstill in extraction equipment, makes solid deposits in the extracting solution to realize solid-liquid separation; D. with the leaching oxidation operation that directly is back to behind the supernatant liquid filtering of post precipitation in the electrolytic metal Mn production process, be used for making electrolytic solution; Sediment in filter residue and the extraction equipment is transported to efficient filtering equipment carries out processed, the water ratio in the slag is reduced to below 25%, slag is sent to manganese slag field or resource utilization, and pressing filtering liquid returns the leaching oxidation operation after filtering, be used for making electrolytic solution.
Embodiment 1:
Adopting above-mentioned processing step, is raw material with the manganese slag, is extraction agent (Mn wherein with the anolyte that produces in the electrolytic metal Mn production process
2+Concentration is 14.5g/L), add the sulfuric acid of 0.025 times of anolyte volume simultaneously, be under 1: 2 the condition in solid-to-liquid ratio, manganese slag and anolyte be abundant mixing in extraction equipment, under 30～65 ℃ condition, and 60 minutes abstraction reaction time, can obtain yellowish extracting solution, Mn in the extracting solution
2+Concentration be 25g/L, extracting solution leaches operation through the oxidation that directly turns back to after filtering in the production process, is used for making electrolytic solution.
Embodiment 2:
Adopting above-mentioned processing step, is raw material with the manganese slag, is extraction agent (Mn wherein with the anolyte that produces in the electrolytic metal Mn production process
2+Concentration is 14g/L), be under 1: 6 the condition in solid-to-liquid ratio, manganese slag and anolyte abundant mixing in extraction equipment under 15～45 ℃ condition, 30 minutes abstraction reaction time, can obtain yellowish extracting solution, Mn in the extracting solution
2+Concentration be 22g/L, extracting solution leaches operation through the oxidation that directly turns back to after filtering in the production process, is used for making electrolytic solution.
Embodiment 3:
Adopting above-mentioned processing step, is raw material with the manganese slag, is extraction agent (Mn wherein with the anolyte that produces in the electrolytic metal Mn production process
2+Concentration is 14g/L), be under 1: 10 the condition in solid-to-liquid ratio, manganese slag and anolyte abundant mixing in extraction equipment under 30～45 ℃ condition, 20 minutes abstraction reaction time, can obtain yellowish extracting solution, Mn in the extracting solution
2+Concentration be 17g/L, extracting solution leaches operation through the oxidation that directly turns back to after filtering in the production process, is used for making electrolytic solution.
Embodiment 4:
Adopting above-mentioned processing step, is raw material with the manganese slag, is extraction agent (Mn wherein with the anolyte that produces in the electrolytic metal Mn production process
2+Concentration is 13.5g/L,), add industrial sulphuric acid simultaneously, add-on is 0.015 (with the volume ratio of anolyte), is under 1: 15 the condition in solid-to-liquid ratio, manganese slag and anolyte abundant mixing in extraction equipment, under 15～30 ℃ condition, 15 minutes abstraction reaction time can obtain yellowish extracting solution, Mn in the extracting solution
2+Concentration be 14.5g/L, extracting solution leaches operation through the oxidation that directly turns back to after filtering in the production process, is used for making electrolytic solution.
On the other hand, the present invention also provides a kind of production technique of electrolytic metal Mn, Figure 2 shows that the electrolytic metal Mn technological process of production in the prior art.Its step comprises powder process, sulfuric acid leaching, press filtration, purification, secondary press filtration, deep purifying, smart filter, electrolysis, passivation, rinsing, dries, peels off etc.Figure 3 shows that the electrolytic metal Mn technological process of production of a kind of preferred implementation of the present invention.Relatively two kinds of schemas as seen, improvements of the present invention are to have increased the manganese slag that uses the anolyte that produces after the electrolysis in the electrolysis step to produce in to purifying step to carry out second extraction on the basis of original process, and directly be back to the leaching oxidation operation behind the supernatant liquid filtering after will extracting, be used for making electrolytic solution.Its technology and equipment are simple, but can be implemented in not produce under the water swellable prerequisite soluble manganese in the manganese slag is extracted and utilization again.
Claims (6)
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| CN101899583B (en) * | 2009-05-25 | 2012-12-12 | 中国环境科学研究院 | Integrative method of two-stage acid leaching, washing and filter pressing for manganese powder pickle liquor |
| CN102191378B (en) * | 2010-03-15 | 2013-12-18 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN105274580B (en) * | 2015-11-15 | 2018-01-12 | 王兆兵 | The method that electrolytic manganese produces reclaimed water and manganese slag for comprehensive utilizes |
| CN107699714B (en) * | 2017-09-19 | 2019-08-09 | 四川大学 | A method suitable for preparing manganese sulfate electrolyte by leaching pyrolusite with sulfur dioxide |
| CN110735155B (en) * | 2018-09-27 | 2021-06-22 | 庞炼红 | Method for producing electrolytic manganese metal and co-producing manganese dioxide |
| CN110479207A (en) * | 2019-07-26 | 2019-11-22 | 铜仁学院 | A kind of method that the alkali fusion activation of electrolytic manganese residues microwave prepares high adsorption value fluorite |
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| CN1052292A (en) * | 1990-03-05 | 1991-06-19 | 刘建湘 | From the potassium permanganate waste residue, extract the method for Manganse Dioxide |
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