CN100567167C - A kind of method of producing manganous sulfate by manganese oxide ore - Google Patents
A kind of method of producing manganous sulfate by manganese oxide ore Download PDFInfo
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- CN100567167C CN100567167C CNB2007101515965A CN200710151596A CN100567167C CN 100567167 C CN100567167 C CN 100567167C CN B2007101515965 A CNB2007101515965 A CN B2007101515965A CN 200710151596 A CN200710151596 A CN 200710151596A CN 100567167 C CN100567167 C CN 100567167C
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Abstract
The invention provides and a kind ofly produce the method for manganous sulfate by manganese oxide ore, it comprises following processing step: a. manganese oxide ore, ferrous sulfate or sulphur, water is put into reactor; B. reaction; C. by solid-liquid separation, after wash heat is washed, get iron ore concentrate, filtrate for later use; D. the filtrate removal of impurities obtains manganese sulfate solution.The leaching yield of manganese can＞85%.The present invention produces that the manganous sulfate method is pollution-free, the time is short, manganese recovery ratio is high, problems such as the process that can overcome traditional method is tediously long, the rate of recovery is low, cost is high, contaminate environment, can increase substantially the rate of recovery and the leaching yield of manganese, inferior manganese oxide ore (particularly ferrimanganic ore deposit) can be utilized, and slag product can be become.The present invention has significant technical progress and outstanding substantive distinguishing features, can produce good economic and social benefit.
Description
Technical field
The present invention relates to produce the method for manganous sulfate, particularly relate to the method that manganous sulfate is produced in the ferrimanganic ore deposit by manganese oxide ore.
Background technology
Manganous sulfate is the main raw material of products such as preparation Manganse Dioxide, trimanganese tetroxide and electrolytic manganese.The existing method for preparing manganous sulfate with manganese ore reduction mainly contains three kinds:
1, coal reduction roast-sulfuric acid leaching.This method is a traditional processing technology, technology maturation, and the quality of manganous sulfate is better; But SO
2Flue gas is big, dust pollution is serious, and the consumption of coal amount is big.
2, two ore deposit roasting methods.Manganese ore and sulfurous iron ore separated pulverizing are mixed, and about 1 hour, water or dilute sulphuric acid leach then 500 ℃～700 ℃ roastings.This method can produce a large amount of SO equally
2Gas and dust.
3, wet reducing extract technology.Mix with manganese ore with reductive agent, leach in the aqueous solution under certain condition, produce manganous sulfate.This technology has been avoided the high-temperature roasting operation, can not produce SO
2Gas and dust, and technical process has been simplified in step leaching.
Wherein, the method that concrete report is produced manganous sulfate is more, as 1., application number CN91102845.5, denomination of invention: the novel process of wet producing manganese sulfate from two kinds of mine, this method adds sulphuric acid soln with poor, bad, useless manganiferous breeze and troilite powder, reacting by heating generates manganese sulfate solution, removes iron ion in the solution with the compressed-air actuated method of feeding again.Though this method production technology is comparatively ripe, the quantity of slag is very big, and underuses, and it is more to bring impurity into, the filtering and impurity removing difficulty.2., application number CN87102046, denomination of invention: with the method for producing manganous sulphate solution from manganese dioxide ore, this method is reductive agent with the sulfurous iron ore, directly soaks fine-graded dioxide ore for manganese with sulphuric acid soln, and its reaction formula is: FeS
2+ MnO
2+ 2H
2SO
4=MnSO
4+ FeSO
4+ 2H
2O+2S, temperature of reaction is 85 ℃～100 ℃, the reaction times is 2～4 hours, reaction end pH=6.8～7 o'clock, the leaching rate of Manganse Dioxide＞90%.Though this method production technology is comparatively ripe, leaching yield is higher, and the quantity of slag is very big, and underuses, and it is more to bring impurity into, the filtering and impurity removing difficulty.3., application number CN200310110442.3, denomination of invention: pyrolusite does not have the method that coal reduction prepares manganese sulfate solution, and this method pyrolusite is a raw material, biogas (CH
4) make reductive agent, generate the intermediate product that mainly contains MnO by reduction reaction, reduction reaction is carried out in two steps: a, make reductive agent with biogas, light biogas under the normal temperature aerobic conditions, the biogas burning makes pyrolusite powder become the red heat state; B, cut off the air supply, continue for biogas and continue to add pyrolusite powder, this moment red heat pyrolusite powder and biogas direct reaction, reaction is proceeded.With organism biogas (CH
4) make reductive agent, can not bring solid impurity into, easily obtain comparatively purified manganous sulfate, but biogas (CH
4) reducing power is relatively poor, speed of response is slow, and leaching yield is low, and the quantity of slag is very big, and underuses.4., application number: CN89105118.x, denomination of invention: a kind of production method of manganous sulfate, this method adopt the manganese ore of manganese content＞8% to mix with the rice skin and put into reaction tank, and the adding dilute sulphuric acid reacts at normal temperatures.The mass ratio of each raw material is: manganese ore: the rice skin: dilute sulphuric acid=5～10: 1: 7～15.When the pH=5 of reactant, leach manganese sulfate solution, slag is through repeatedly draining after the washing, and the highly concentrated solution that obtains is made manganese sulfate product through deironing, evaporation, crystallization, drying, pulverizing and packing.Make reductive agent with organism rice skin, can not bring the impurity that difficulty is removed into, easily obtain comparatively purified manganous sulfate, but rice skin reducing power is poor, long reaction time, leaching yield is low, and the quantity of slag is very big, and underuses.5., the surplus beautiful show of Sun Yaguang, the applied research of hydrocarbon polymer wet processing manganese-silver ore, Chinese manganese industry .2004,22 (1): 1-14 discloses hydrocarbon polymer and has soaked manganese-cyaniding and soak silver-colored principle, processing condition and application.Utilize hydrocarbon polymer and Manganse Dioxide reactions such as starch, sucrose, when the leaching yield of manganese is 96%, rate of loss＜2% of silver; Soak the manganese slag and adopt the sodium cyanide desilver, the sodium cyanide consumption is the 1Kg/t slag, leaches 3h that the leaching yield of silver is 94.15%; Total recovery＞92.27% of silver.With starch and sucrose is reductive agent, and the impurity of introducing is less, easily obtain comparatively purified manganese sulfate solution, but its price is higher, causes cost higher, and the quantity of slag is bigger, underuses.6. flat Song of Yang Ming and pay a Li Guobin, chaff-sulfuric acid directly soaks the research of preparation of manganese condition, inorganic chemicals industry .2005,02, disclosing with rice bran and western Hunan pyrolusite is raw material, rice bran-sulfuric acid is directly soaked the processing condition that manganese prepares manganous sulfate study.The result shows that the optimum process condition that rice bran-sulfuric acid process is soaked manganese is; Soak 250 ℃ of manganese temperature, the sulfuric acid massfraction accounts for 50%, soaks manganese time 75min, and the rice bran consumption is 20% of a pyrolusite quality, and the sulfuric acid consumption is 110% of its theoretical consumption, and the leaching yield of manganese can reach more than 95%.With rice bran is reductive agent, and the impurity of introducing is less, easily obtains comparatively purified manganese sulfate solution, but the hydrolysis saccharogenesis is comparatively difficult, needs higher temperature of reaction in order to improve leaching yield, cause energy consumption higher, and the quantity of slag is bigger, underuses.7. the flat Huang Kelong of poplar children; Pure plant powder-sulfuric acid process directly leaches the practice of pyrolusite, Chinese Mining Industry .2001, and 10 (5): 54-56, studied with pure plant powder-vitriol oil method and directly leached the novel method of pyrolusite.Test-results shows: the leaching yield of manganese is subjected to the influence of factors such as pyrolusite consumption, vegetable material powder consumption, vitriol oil consumption, extraction temperature and reaction times in the pyrolusite, and wherein the consumption of the vitriol oil has the greatest impact to the leaching yield of manganese.Optimum process condition is: sour ore deposit ratio is 2～3.1 (mL: g), pyrolusite: pure plant powder=210～313: 1, liquid-solid ratio is 3: 1, extraction temperature is 90 ℃～95 ℃, extraction time is 3h, this moment, the leaching yield of manganese can reach more than 95%, pure plant powder is made reductive agent, and the impurity of introducing is less, easily obtains comparatively purified manganese sulfate solution, can also utilize local various pure plant powder resources, but the hydrolysis saccharogenesis is difficulty comparatively, need consume a large amount of sulfuric acid in order to improve leaching yield, causes cost to improve, and the quantity of slag is bigger, underuses.Above-mentioned document all is in acidic aqueous solution, leaches the method for manganese oxide ore with ferrous sulfate or the reduction of other reductive agent.The method energy consumption height, the pollution that prepare manganous sulfate weigh, reagent consumption is big, cost is high, flow process is tediously long because the adding of acid makes.
Other has the bibliographical information pyrolusite to prepare manganous sulfate: Zhang Qiwei, pyrolusite prepares the technological principle and the technology of manganous sulfate, Sanming Professional Univ.'s journal, wherein discloses acid ferrous sulfate or pickle solution processing pyrolusite and has produced manganous sulfate 2000 the 3rd phases (publication in August).Leaching the difference of reacting with acidity of medium has three kinds of different products, when the neutral solution condition: MnO
2+ 2FeSO
4+ 2H
2O=MnSO
4+ Fe (OH) SO
4+ Fe (OH)
3, when low sulphuric acid soln condition, MnO
2+ 2FeSO
4+ H
2SO
4=MnSO
4+ 2Fe (OH) SO
4, during the peracid solutions condition: MnO
2+ 2FeSO
4+ 2H
2SO
4=MnSO
4+ Fe
2(SO
4)
3+ 2H
2O, no matter in acidity or neutral solution, ferrous sulfate can both use Manganse Dioxide to be converted into manganous sulfate.Wherein, Fe (OH)
3, ferric subsulfate is the colloidal material, be difficult to manganous sulfate and Fe (OH)
3, ferric subsulfate separates, the colloidal material easily is covered in pyrolusite thing surface simultaneously, hinders reaction and carries out smoothly; In order to prevent this reaction, the leaching reaction is controlled in the acidic medium usually to be carried out; Therefore, under neutrallty condition, utilize manganese oxide ore and ferric sulfate prepared in reaction manganous sulfate,,, do not have industrial utilization to be worth because above-mentioned technology barrier is difficult to realize suitability for industrialized production though can overcome the shortcoming for preparing manganous sulfate at acidic conditions.Do not have under neutrallty condition at present yet and can successfully manganese oxide ore be produced manganous sulfate, make full use of the pertinent literature report of the method for waste products simultaneously.
Summary of the invention
Technical scheme of the present invention has provided the method that a kind of energy consumption is low, pollution is little, reagent consumption is little, cost is low, flow process is simply produced manganous sulfate.
A kind ofly produce the method for manganous sulfate by manganese oxide ore, it comprises following processing step:
A, manganese oxide ore, ferrous sulfate or sulphur, water are put into closed reactor;
B, under 120～350 ℃ of conditions of temperature, the reaction times is more than 30 minutes;
C, by solid-liquid separation, after wash heat is washed, iron ore concentrate, filtrate for later use;
D, filtrate removal of impurities obtain manganese sulfate solution.
With the pyrolusite is example: the reaction formula of b step is as follows:
Main reaction:
MnO
2+2FeSO
4+H
2O＝MnSO
4+Fe
2O
3+H
2SO
4
Side reaction:
MnO
2+2FeSO
4+2H
2SO
4＝MnSO
4+Fe
2(SO
4)
3+2H
2O
Ferric oxide is a kind of powder (being commonly called as iron oxide red) of reddish-brown.
The reaction formula of manganese oxide ore and sulphur is:
2H
2O+3S＝2H
2S+SO
2
3MnO
2+S+4H
+＝3Mn
2++SO
4 2-+2H
2O
Wherein, the weight proportion of manganese, ferrous sulfate, water is in the described manganese oxide ore: 1 part in manganese, anhydrous slufuric acid is ferrous 〉=and 3 parts, water 〉=20 part.Further preferably, the weight proportion of manganese, ferrous sulfate, water is in the described manganese oxide ore: manganese: anhydrous slufuric acid is ferrous: water is: 1: 3-200: 20-1000.
Wherein, the weight proportion of manganese, sulphur, water is 4 parts in manganese, sulphur 〉=1 part, water 〉=20 part in the described manganese oxide ore.Further preferably, the weight proportion of manganese, sulphur, water is in the described manganese oxide ore: manganese: sulphur: water is 4: 1-200: 20-3000.
Wherein, described manganese oxide ore is for containing MnO
2, Mn
2O
3, Mn
3O
4Or the manganese mineral of MnO, manganese content 〉=8%w/w.
Wherein, the total content 〉=20%w/w of manganese and iron in the described manganese oxide ore.
Wherein, described ferrous sulfate is solid or the copperas solution that contains any crystal water.
Wherein, use agitator to stir in the reaction process described in the b step, stirring velocity is 20～500 rev/mins.The further preferable reaction temperature of b step is 140～180 ℃.
Wherein, reaction times 〉=30 described in the b step minute.
In the described reaction conditions of b step, pressure is 0.1～20Mpa.Further preferably, pressure is 0.1～1Mpa.
In the inventive method, manganese is leached in the manganese oxide ore (particularly ferrimanganic ore deposit).Leaching yield can＞85%.
In the titanium powder plant production process, can produce a large amount of ferrous sulfate.One ton of titanium white of every production is wanted ferrous sulfate by-product (FeSO
47H
2O) 3.5～4 tons.According to incompletely statistics, China's titanium white industrial by-product ferrous sulfate surpasses 1,000,000 tons/year, is a kind of abundant, cheap resource of originating.The present invention has made full use of titanium white by product thing ferrous sulfate and has been used as reductive agent leaching manganese oxide ore (particularly ferrimanganic ore deposit), do not need to consume sulfuric acid, when obtaining manganese sulfate solution, slag can also sell that (content of iron is high more in the ferrimanganic ore deposit as iron ore concentrate, the grade of iron is high more in the iron ore concentrate), there is not the big problem of the quantity of slag, also becomes the disused auxiliary matter ferrous sulfate effective way comparatively of handling titanium white by product.The also available sulphur of the present invention replaces ferrous sulfate to leach manganese oxide ore (particularly ferrimanganic ore deposit) as reductive agent, realizes effective leaching of manganese.
The present invention is a raw material with manganese oxide ore (particularly ferrimanganic ore deposit) and ferrous sulfate (or sulphur), under certain temperature and pressure, react, can more efficiently realize the leaching of manganese, and have short, manganese recovery ratio advantages of higher of reaction times, the leaching yield of manganese can＞85%.That the advantage of present method is is pollution-free, the time is short, manganese recovery ratio is high, problems such as the process that can overcome traditional method is tediously long, the rate of recovery is low, cost is high, contaminate environment, can increase substantially the rate of recovery and the leaching yield of manganese, inferior manganese oxide ore (particularly ferrimanganic ore deposit) can be utilized, and slag product can be become.
In sum: under temperature of the present invention, pressure condition, utilize ferrous sulfate, reaction generates manganous sulfate and smart iron ore, does not almost have waste, and very cleans.The present invention has significant technical progress and outstanding substantive distinguishing features, can produce good economic and social benefit.
The embodiment of invention
Reaction among the embodiment is all carried out in encloses container.For example in autoclave, carry out.
[embodiment 1]
120g ferrimanganic ore deposit (is contained manganese 22.47; Iron 32.7%), the 330g iron vitriol mixes, and adds 1.2L water, temperature is 350 ℃, pressure 1MPa, stirring velocity transfers to 200 rev/mins, reacts 0.5 hour.The manganese leaching yield reaches 95%, cinder grade TFe 〉=60%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 2]
120g ferrimanganic ore deposit (is contained manganese 22.47; Iron 32.7%), 18g sulphur mixes, and adds 550mL water, temperature is 180 ℃, pressure 20MPa, stirring velocity transfers to 200 rev/mins, reacts 1.5 hours.Leaching yield reaches 90%, cinder grade TFe 〉=45%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 3]
The 120g pyrolusite (is contained manganese 20.47; Iron 8.7%), the 135g iron vitriol mixes, and adds 0.5L water, temperature is 160 ℃, pressure 0.7MPa, stirring velocity transfers to 200 rev/mins, reacts 3 hours.The manganese leaching yield reaches 72%, cinder grade TFe 〉=50%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 4]
120g ferrimanganic ore deposit (is contained manganese 22.47; Iron 32.7%), 7g sulphur mixes, and adds 0.5L water, temperature is 300 ℃, pressure 8.5MPa, stirring velocity transfers to 20 rev/mins, reacts 1 hour.The manganese leaching yield reaches 92%, cinder grade TFe 〉=45%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 5]
120g ferrimanganic ore deposit (is contained manganese 22.47; Iron 32.7%), the 330g iron vitriol mixes, and adds 1.2L water, temperature is 200 ℃, pressure 1.8MPa, stirring velocity transfers to 450 rev/mins, reacts 1.5 hours.The manganese leaching yield reaches 97%, cinder grade TFe 〉=60%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 6]
120g ferrimanganic ore deposit (is contained manganese 10.05; Iron 45.8%), the 4420g iron vitriol mixes, and adds 12L water, temperature is 180 ℃, pressure 1MPa, stirring velocity transfers to 200 rev/mins, reacts 3 hours.The manganese leaching yield reaches 94%, cinder grade TFe 〉=68%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 7]
120g ferrimanganic ore deposit (is contained manganese 26.3; Iron 15.5%), the 220g iron vitriol mixes, and adds 1.4L water, temperature is 180 ℃, pressure 1MPa, stirring velocity transfers to 200 rev/mins, reacts 3 hours.The manganese leaching yield reaches 86%, cinder grade TFe 〉=55%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 8]
120g ferrimanganic ore deposit (is contained manganese 26.3; Iron 15.5%), the 220g iron vitriol mixes, and adds 1.4L water, temperature is 120 ℃, 0.3MPa, stirring velocity transfers to 500 rev/mins, reacts 10 hours.The manganese leaching yield reaches 85%, cinder grade TFe 〉=45%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 9]
120g ferrimanganic ore deposit (is contained manganese 10.05; Iron 45.8%), 603g sulphur mixes, and adds 9L water, temperature is 180 ℃, pressure 20MPa, stirring velocity transfers to 200 rev/mins, reacts 1.5 hours.Leaching yield reaches 90%, cinder grade TFe 〉=52%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
[embodiment 10]
120g ferrimanganic ore deposit (is contained manganese 10.05; Iron 45.8%), 603g sulphur mixes, and adds 9L water, temperature is 140 ℃, pressure 18MPa, stirring velocity transfers to 200 rev/mins, reacts 1.5 hours.Leaching yield reaches 84%, cinder grade TFe 〉=48%, the manganese sulfate solution that is obtained can reach product requirements such as producing electrolytic manganese, Manganse Dioxide, trimanganese tetroxide after conventional method removal of impurities, also can direct condensing crystal, drying sell as product after conventional method removal of impurities.
Claims (10)
1, a kind ofly produce the method for manganous sulfate by manganese oxide ore, it comprises following processing step:
A, put into closed reactor with manganese oxide ore, ferrous sulfate and water or with manganese oxide ore, sulphur and water;
B, under 120～350 ℃ of conditions of temperature, the reaction times is more than 30 minutes;
C, by solid-liquid separation, after wash heat is washed, iron ore concentrate, filtrate for later use;
D, filtrate removal of impurities obtain manganese sulfate solution.
2, according to claim 1ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: described manganese oxide ore is for containing MnO
2, Mn
2O
3, Mn
3O
4Or the manganese mineral of MnO, manganese content 〉=8%w/w.
3, according to claim 1ly produce the method for manganous sulfate, it is characterized in that: the total content 〉=20%w/w of manganese and iron in the described manganese oxide ore by manganese oxide ore.
4, according to claim 1ly to produce the method for manganous sulfate, it is characterized in that: manganese in the described manganese oxide ore, be in the weight proportion of the ferrous ferrous sulfate of anhydrous slufuric acid, water by manganese oxide ore: 1 part in manganese, anhydrous slufuric acid is ferrous 〉=3 parts, water 〉=20 part.
5, according to claim 4ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: manganese in the described manganese oxide ore, in the weight proportion of the ferrous ferrous sulfate of anhydrous slufuric acid, water be: manganese: anhydrous slufuric acid is ferrous: water is: 1: 3-200: 20-1000.
6, according to claim 1ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: the weight proportion of manganese, sulphur, water is in the described manganese oxide ore: 4 parts in manganese, sulphur 〉=1 part, water 〉=20 part.
7, according to claim 6ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: the weight proportion of manganese, sulphur, water is in the described manganese oxide ore: manganese: sulphur: water is 4: 1-200: 20-3000.
8, according to claim 1ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: the temperature of b step is 140～180 ℃.
9, according to claim 1ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: the pressure of b step is 0.1～20Mpa.
10, according to claim 1ly produce the method for manganous sulfate by manganese oxide ore, it is characterized in that: use agitator to stir in the b step reaction process, stirring velocity is 20～500 rev/mins.
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| CN101709391B (en) * | 2009-11-30 | 2011-07-13 | 中信锦州铁合金股份有限公司 | Method for producing electrolytic manganese metal by lixiviating sinter ore by adding ferrous sulphate in replacement of manganese carbonate ore |
| CN101837959B (en) * | 2010-05-14 | 2012-11-07 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
| CN102220491A (en) * | 2011-06-03 | 2011-10-19 | 郭永锴 | Method for recovering manganese from manganese ore, manganese tailing and manganese slag through continuous pressurization and acid leaching process |
| CN102424365B (en) * | 2011-07-27 | 2013-07-24 | 湖南省泸溪县金旭治化有限责任公司 | Recycling method of tail gas from pyrolusite reduction and sulfuric acid coproduction in fluidized bed furnace |
| CN102605187A (en) * | 2011-10-10 | 2012-07-25 | 云南建水锰矿有限责任公司 | Method for producing manganese sulfate by manganese-rich slag through pressure leaching |
| CN106148734B (en) * | 2015-03-27 | 2019-01-15 | 余先莉 | A technique for comprehensive utilization ferrous sulfate produces electrolytic manganese |
| CN106756001A (en) * | 2016-12-29 | 2017-05-31 | 宁夏天元锰业有限公司 | A kind of method of the production electrolytic manganese metal for comprehensively utilizing electrolytic manganese residues |
| CN107574310A (en) * | 2017-09-19 | 2018-01-12 | 南京工业大学 | A kind of method for efficiently leaching copper in waste printed circuit board |
| CN112551589A (en) * | 2020-11-24 | 2021-03-26 | 湘西蒙成科技有限责任公司 | Energy-saving reduction method of manganese dioxide, manganese dioxide and application |
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