CN102225768B - Method for preparing ultra-fine active white carbon black by using manganese leached slag and manganese electrolysis waste acid - Google Patents
Method for preparing ultra-fine active white carbon black by using manganese leached slag and manganese electrolysis waste acid Download PDFInfo
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Abstract
The invention relates to a method for preparing ultra-fine active white carbon black by using manganese leached slag and manganese electrolysis waste acid. According to the invention, first, manganese leached slag is washed and neutralized by diluted acid and alkaline aqueous solution; the obtained filter residue strong alkaline solution is reacted and filtered, such that a filtrate is obtained; the filtrate is sequentially decolorized by using amino-terminated hyperbranched polyester and polyacrylamide with a number-average molar mass above 1000000 g/mol, such that a decolorized silicate aqueous solution is obtained; a particle activator is added to the solution, then decolorized manganese electrolysis waste acid is dropped to the solution; the obtained solution is reheated, reacted, filtered, washed, and dried, such that white carbon black is obtained. According to the present invention, white carbon black with a high added value can be produced by using waste slag and waste liquid discharged from a manganese mine enterprise, such that environment protection and comprehensive utilization of resources can be realized. The method also has advantages of simple technology, low cost, high added value, and is suitability for industrialized productions.
Description
Technical field
The present invention relates to the recycling field of industrial residue and waste liquid, be specifically related to a kind of method of utilizing manganese leached mud and electrolytic manganese spent acid to prepare superfine active carbon white.
Background technology
Manganese is to produce iron and steel and stainless raw material, is subjected to the pulling of Iron and Steel Production sustainable growth, and China is constantly soaring to the demand of manganese ore.China is iron alloy producing country as maximum in the world manganese, and manganese matter alloy output reached 7,450,000 tons in 2008.China is the very abundant country of manganese resource storage, but the average grade of manganese ore is lower, and the manganese ore reserves in the whole nation 93.6% belong to poor manganese ore.According to statistics, 1 ton of manganese of every electrolysis production will produce 6~7 tons of manganese leached muds and a large amount of spent acid, and, along with the acceleration of manganese ore exploitation and the continuous increase of manganese demand, produce the residue contamination that manganese produces and be on the rise, the research of therefore manganese leached mud and spent acid being recycled is imperative.
The relevant report that present domestic manganese leached mud is processed concentrates on the fields such as preparation material of construction, 4A molecular sieve mostly, and these techniques all will be through the operation of high-temperature calcination, and production cost is high, and the value-added content of product that obtains lower, essentially no economic benefit; Therefore utilizing the higher product of manganese leached mud supervene value and production technique thereof will be the development trend that manganese ore industry waste residue is processed.
White carbon black is widely used in the fields such as packing strengthening agent, printing ink thickening material, paint additive, synthetic grease and silicone grease viscosifying agent, curriery flatting agent, pesticide dispersing agent, papermaking weighting agent, the additive of synthetic resins (alkyd resin, the Elastic polyurethane), electric industry insulation and thermal insulation filler and daily-use chemical industry raw material of rubber, plastics.Superfine active carbon white as rubber reinforcing filler can improve vulcanized rubber article tensile strength, hardness, deflect, tear, abrasion, ageing-resistant performance, be light color, colour and the indispensable high-quality reinforcing filler of transparent rubber goods, be widely used as the reinforcement of the products such as colored rain boots, sports shoes, transparent adhesive tape sole, tire, rubber roll, cable; Strengthening agent as the plastics boardy product can improve its solidity to corrosion, weathering resistance and levelling property.Have relevant expert to estimate, under the drive of tire and shoe industry, China will increase with annual 8%~10% speed fast to the demand of white carbon black; The price of white carbon black then less because of particle, the larger price of specific surface area is higher.Chinese patent ZL200610035724.5 once reported and utilizes the less white bauxite waste residue of impurity to prepare active carbon white, but its silicon-dioxide is mainly used in the rubber materials that tensile strength is less demanding, productive rate is lower.So far there is not yet prepare take the more brown manganese leached mud of impurity and electrolytic manganese spent acid as main raw material particle diameter little, easily be scattered in rubbery system, keep rubber that report than high tensile, superfine active carbon white that added value is higher is arranged.
Si is (with SiO in the manganese leached mud
2Meter) content reaches 22~30wt%, and the waste acid liquor behind the electrolytic manganese can not directly discharge because acid concentration is higher, so these waste residues of disposal and utilization, waste liquid become more important to environment protection; Preparing superfine active carbon white with method of the present invention simultaneously can the satisfying the market needs, obtain economic benefit, can also solve the trouble and worry of electrolytic manganese dioxide manufacturer, is conducive to environment protection.
Summary of the invention
The technical problem to be solved in the present invention is to take full advantage of the method that the industrial residue of manganese source mill and waste liquid-manganese leached mud and electrolytic manganese spent acid prepare superfine active carbon white.
The present invention solves the problems of the technologies described above with following technical scheme:
1, the manganese leached mud is respectively washed 1 time with the dilute sulfuric acid aqueous solution of 0.1~0.15wt%, the alkaline aqueous solution of 0.05~0.1wt% successively, be washed till neutrality with tap water again, wherein dilute sulfuric acid aqueous solution and manganese leached mud weight ratio are 3.0~3.5: 1, and alkaline aqueous solution and manganese leached mud weight ratio are 3.0~3.5: 1;
2, with strong base solution reaction 2~5h under 121~130 ℃ of the filter residue after step 1 processing and 41~55wt%, filter and obtain filtrate, and water is washed till neutrality with filter residue; Wherein the mass ratio of strong base solution and raw material manganese leached mud is 2~3: 1;
3, the filtrate that step 2 is obtained under 40~80 ℃ successively with amine-terminated hyperbrancedization polyester, polyacrylamide decolouring more than the number-average molecular weight 1000000g/mol after, obtain aqueous silicate solution; Wherein the weight ratio of amine-terminated hyperbrancedization polyester and raw material manganese leached mud is 1: 100~150, and the weight ratio of polyacrylamide and raw material manganese leached mud is 1: 100~150;
4, join the aqueous silicate solution after the decolouring that obtains in the step 3 in the reactor, add the content that water is regulated silicon-dioxide in the filtrate, add the particle promoting agent, slowly drip again the electrolytic manganese waste acid liquor of processing through decolouring, pH value to solution is between 5~8, after dropwising, at 40~60 ℃ of lower reaction 0.5~2h, filtration, washing, drying obtain white carbon black again; The water that wherein adds and the weight ratio 2.5~3.0: 1 of raw material manganese leached mud; The consumption of particle promoting agent is 0.05~0.5% of raw material manganese leached mud weight.
Strong base solution is one or both in sodium hydroxide and the potassium hydroxide aqueous solution.
The preparation method of particle promoting agent is: 1.2mol dithiocarbonic anhydride, 1.2mol concentration are that 20% sodium hydroxide or 1.2mol concentration are 20% potassium hydroxide aqueous solution and contain 0.1mol Hyperbranched Polymer with Terminal Amido 300g powder and mix, stirring reaction is 6 hours under 40 ℃ of conditions, then crystallisation by cooling, filtration can obtain nabam pressed powder 336g or dithiocarbamic acid potassium pressed powder 342g.
The decolorizing treatment agent of electrolytic manganese waste acid liquor is gac, amine-terminated hyperbrancedization polyester, polyacrylamide, the process of decolouring is that spent acid solution is lower to activated carbon treatment decolouring in 5 minutes at 90~100 ℃, and then use successively amine-terminated hyperbrancedization polyester, the above polyacrylamide of number-average molecular weight 1000000g/mol is processed respectively decolouring in 5 minutes at 40~100 ℃, wherein the weight ratio of gac and spent acid solution is 1: 500~1000, the weight ratio of amine-terminated hyperbrancedization polyester and spent acid solution is 1: 5000~10000, and the weight ratio of polyacrylamide and raw material manganese leached mud is 1: 5000~10000.
Advantage and the beneficial effect of the inventive method are as follows:
(1) the present invention is first with diluted acid and the molten and molten impurity of alkali of diluted alkaline washing manganese leached mud remove portion acid, utilize amine-terminated hyperbrancedization polyester, polyacrylamide to deviate from the molten impurity of alkali behind manganese leached mud and the alkali reaction and deviate from sour molten impurity in the electrolytic manganese spent acid, make silicate solutions and waste acid liquor look light or colourless, guaranteed that the white carbon black product dioxide-containing silica is high.
(2) adopt the particle promoting agent to come in-situ modified white carbon black, be conducive to the dispersion of white carbon black and the consistency of raising and rubber; The particle promoting agent is a class sulfo-dimethylamino formate simultaneously, also is the promotor of the vulcanization of rubber, product of the present invention is added to cross-linking density and the mechanical property that can improve rubber in the rubber.
(3) the amino hyper-branched polyester of band can be good for coordination by hydrogen with the hydroxyl on white carbon black surface; form the organic protective layer of one deck; white carbon black is disperseed easily; particle diameter reduces; specific surface area improves; the consistency of the polymkeric substance such as white carbon black and rubber, plastics improves, and is conducive to improve quality and the added value of white carbon black.
(4) effectively utilize the waste residue of manganese ore enterprise generation and the white carbon black of waste liquid production high added value, be conducive to the comprehensive utilization of environment protection and resource; And have that technique is simple, with low cost, added value is high, be suitable for the advantages such as suitability for industrialized production.
Embodiment
So far there are no utilizing manganese leached mud and electrolytic manganese spent acid to prepare the report of superfine active carbon white, key is to contain the impurity such as iron, magnesium, zirconium, chromium in manganese leached mud and the electrolytic manganese spent acid, and these impurity will directly have influence on quality and the whiteness of white carbon black.The present invention utilizes diluted acid and dilute alkaline soln washing manganese leached mud that some impurity are dissolved in acid or the alkali and is removed, utilize the molten impurity of alkali in the silicate solutions after amine-terminated hyperbrancedization polyester, polyacrylamide are deviate from manganese leached mud and alkali reaction, deviate from the sour molten impurity in the electrolytic manganese spent acid, because amine-terminated hyperbrancedization polyester contains effectively complexing foreign pigment of a large amount of amino, just might obtain faint yellow extremely colourless silicate solutions and waste acid liquor, also could obtain high silicon dioxide content and high-grade white carbon black product.
Secondly, the particle promoting agent that the present invention adopts is a class sulfo-dimethylamino formate, and in-situ modified white carbon black makes its surface can connect some particle active groups, be conducive to dispersion in the white carbon black application process and the consistency of raising and rubber, improve cross-linking density and the mechanical property of rubber.。
In addition; the amino hyper-branched polyester of band can be good for coordination by hydrogen with the hydroxyl on white carbon black surface; form the organic protective layer of one deck; not only can effectively reduce the free energy on white carbon black surface and easily dispersion; reduce particle diameter; increasing specific surface area, the simultaneously existence of these organic groups make the consistency raising of white carbon black and the polymkeric substance such as rubber, plastics, are conducive to improve quality and the added value of white carbon black.
Below in conjunction with specific embodiment the inventive method is described further, the used material that does not have specified otherwise is the commercially available prod.
Amine-terminated hyperbrancedization polyester is to contain 12 amino, amino Aromatic Hyperbranched Polyesters resins of the end of number-average molecular weight about 3000g/mol of end, is provided by Suzhou HyperT Resin Science ﹠ Technology Co., Ltd., and its chemical structure is as follows:
Embodiment 1
The preparation of particle promoting agent: (following examples together)
1.2mol dithiocarbonic anhydride, 1.2mol concentration are 20% aqueous sodium hydroxide solution and contain amine-terminated hyperbrancedization of 0.1mol polyester (300g) powder and mix, stirring reaction is 6 hours under 40 ℃ of conditions, then crystallisation by cooling, filtration, can obtain nabam pressed powder 336g, similar way can obtain dithiocarbamic acid potassium pressed powder.
The preparation of superfine active carbon white:
(1) 100g manganese leached mud is respectively washed 1 time with the aqueous sodium hydroxide solution 300g of dilute sulfuric acid aqueous solution 350g, the 0.10wt% of 0.10wt% successively, be washed till neutrality with tap water again;
(2) with the sodium hydroxide solution 300g of filter residue and 41wt%, react 5h about 121 ℃, filter, and with distilled water filter residue is washed till neutrality, washings is incorporated into filtrate, collects filtrate;
(3) with step (2) gained filtrate stirring respectively with amine-terminated hyperbrancedization of 1.0g polyester, polyacrylamide more than the 0.70g number-average molecular weight 1000000g/mol successively about 40 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous silicate solution;
(4) get electrolytic manganese waste acid liquor 1000g, after using gac 2.0g decolouring to process 5min about 90 ℃, stirring respectively with amine-terminated hyperbrancedization of 0.2g polyester, polyacrylamide more than the 0.13g number-average molecular weight 1000000g/mol successively about 40 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous sulfuric acid;
(5) aqueous silicate solution that step (3) is obtained joins in the reactor, adds water 250g, and 0.05g nabam pressed powder slowly drips the aqueous sulfuric acid of step (4) under the stirring at room condition, to the pH value of solution be 5-8.React 2h again about 40 ℃, filter, be washed to barium chloride solution and can't detect till the sulfate ion, gained is deposited in dry 5h about 120 ℃, obtains white carbon black 42g, and after testing, the index of gained white carbon black product is as shown in table 1.
Embodiment 2
(1) 100g manganese leached mud is respectively washed 1 time with the aqueous sodium hydroxide solution 350g of dilute sulfuric acid aqueous solution 320g, the 0.07wt% of 0.12wt% successively, be washed till neutrality with tap water again;
(2) with the sodium hydroxide solution 200g of filter residue and 55wt%, react 3h about 130 ℃, filter, and with distilled water filter residue is washed till neutrality, washings is incorporated into filtrate, collects filtrate;
(3) with step (2) gained filtrate stirring respectively with amine-terminated hyperbrancedization of 0.8g polyester, polyacrylamide more than the 1.0g number-average molecular weight 1000000g/mol successively about 60 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous silicate solution;
(4) get electrolytic manganese waste acid liquor 1000g, after using gac 1.0g decolouring to process 5min about 95 ℃, stirring respectively with amine-terminated hyperbrancedization of 0.15g polyester, polyacrylamide more than the 0.10g number-average molecular weight 1000000g/mol successively about 60 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous sulfuric acid;
(5) aqueous silicate solution that step (3) is obtained joins in the reactor, adds water 280g, and 0.30g dithiocarbamic acid potassium pressed powder slowly drips the aqueous sulfuric acid of step (4) under the stirring at room condition, to the pH value of solution be 4-6.React 1.5h again about 50 ℃, filter, be washed to barium chloride solution and can't detect till the sulfate ion, gained is deposited in dry 5h about 120 ℃, obtains white carbon black 46g, and after testing, the index of gained white carbon black product is as shown in table 1.
Embodiment 3
(1) 100g manganese leached mud is respectively washed 1 time with the aqueous sodium hydroxide solution 330g of dilute sulfuric acid aqueous solution 300g, the 0.05wt% of 0.15wt% successively, be washed till neutrality with tap water again;
(2) with the potassium hydroxide solution 250g of filter residue and 45wt%, react 2h about 125 ℃, filter, and with distilled water filter residue is washed till neutrality, washings is incorporated into filtrate, collects filtrate;
(3) with step (2) gained filtrate stirring respectively with amine-terminated hyperbrancedization of 1.0g polyester, polyacrylamide more than the 0.8g number-average molecular weight 1000000g/mol successively about 80 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous silicate solution;
(4) get electrolytic manganese waste acid liquor 1000g, after using gac 1.5g decolouring to process 5min about 100 ℃, stirring respectively with amine-terminated hyperbrancedization of 0.10g polyester, polyacrylamide more than the 0.20g number-average molecular weight 1000000g/mol successively about 80 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous sulfuric acid;
(5) aqueous silicate solution that step (3) is obtained joins in the reactor, adds water 300g, and 0.50g dithiocarbamic acid potassium pressed powder slowly drips the aqueous sulfuric acid of step (4) under the stirring at room condition, to the pH value of solution be 4-6.React 0.5h again about 60 ℃, filter, be washed to barium chloride solution and can't detect till the sulfate ion, gained is deposited in dry 5h about 120 ℃, obtains white carbon black 49g, and after testing, the index of gained white carbon black product is as shown in table 1.
Embodiment 4
(1) 100g manganese leached mud is respectively washed 1 time with the potassium hydroxide aqueous solution 320g of dilute sulfuric acid aqueous solution 310g, the 0.09wt% of 0.11wt% successively, be washed till neutrality with tap water again;
(2) with the potassium hydroxide solution 300g of filter residue and 50wt%, react 4h about 125 ℃, filter, and with distilled water filter residue is washed till neutrality, washings is incorporated into filtrate, collects filtrate;
(3) with step (2) gained filtrate stirring respectively with amine-terminated hyperbrancedization of 1.0g polyester, polyacrylamide more than the 0.9g number-average molecular weight 1000000g/mol successively about 70 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous silicate solution;
(4) get electrolytic manganese waste acid liquor 1000g, after using gac 1.2g decolouring to process 5min about 95 ℃, stirring respectively with amine-terminated hyperbrancedization of 0.10g polyester, polyacrylamide more than the 0.18g number-average molecular weight 1000000g/mol successively about 100 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous sulfuric acid;
(5) aqueous silicate solution that step (3) is obtained joins in the reactor, adds water 300g, and 0.40g nabam pressed powder slowly drips the aqueous sulfuric acid of step (4) under the stirring at room condition, to the pH value of solution be 4-6.React 1.0h again about 50 ℃, filter, be washed to barium chloride solution and can't detect till the sulfate ion, gained is deposited in dry 5h about 120 ℃, obtains white carbon black 52g, and after testing, the index of gained white carbon black product is as shown in table 1.
Embodiment 5
(1) 100g manganese leached mud is respectively washed 1 time with the potassium hydroxide aqueous solution 320g of dilute sulfuric acid aqueous solution 300g, the 0.05wt% of 0.12wt% successively, be washed till neutrality with tap water again;
(2) with the aqueous sodium hydroxide solution 250g of filter residue and 40wt%, react 2h about 125 ℃, filter, and with distilled water filter residue is washed till neutrality, washings is incorporated into filtrate, collects filtrate;
(3) with step (2) gained filtrate stirring respectively with amine-terminated hyperbrancedization of 0.9g polyester, polyacrylamide more than the 0.9g number-average molecular weight 1000000g/mol successively about 50 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous silicate solution;
(4) get electrolytic manganese waste acid liquor 1000g, after using gac 2.0g decolouring to process 5min about 90 ℃, stirring respectively with amine-terminated hyperbrancedization of 0.12g polyester, polyacrylamide more than the 0.20g number-average molecular weight 1000000g/mol successively about 70 ℃ after the 5min decolouring processes, obtain faint yellow to colourless aqueous sulfuric acid;
(5) aqueous silicate solution that step (3) is obtained joins in the reactor, adds water 270g, and 0.10g nabam pressed powder slowly drips the aqueous sulfuric acid of step (4) under the stirring at room condition, to the pH value of solution be 4-6.React 2h again about 45 ℃, filter, be washed to barium chloride solution and can't detect till the sulfate ion, gained is deposited in dry 5h about 120 ℃, obtains white carbon black 48g, and after testing, the index of gained white carbon black product is as shown in table 1.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this technical field can understand content of the present invention and is implemented; but can not limit protection scope of the present invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
The performance index of the superfine active carbon white of embodiment 1 to embodiment 5 are relatively referring to table 1, and all test indexs are all carried out according to corresponding industry standard or national standard.
Table 1
Claims (3)
1. method of utilizing manganese leached mud and electrolytic manganese spent acid to prepare superfine active carbon white is characterized in that processing step is:
⑴ respectively wash the manganese leached mud 1 time with the dilute sulfuric acid aqueous solution of 0.1~0.15wt%, the alkaline aqueous solution of 0.05~0.1wt% successively, be washed till neutrality with tap water again, wherein dilute sulfuric acid aqueous solution and manganese leached mud weight ratio are 3.0~3.5:1, and alkaline aqueous solution and manganese leached mud weight ratio are 3.0~3.5:1;
⑵ the filter residue after process step ⑴ and the strong base solution of 41~55wt% filter and obtain filtrate, and water are washed till neutrality with filter residue at 121~130 ℃ of lower reaction 2~5h; Wherein the mass ratio of strong base solution and raw material manganese leached mud is 2~3:1;
⑶ the filtrate that obtain step ⑵ under 40~80 ℃ successively with amine-terminated hyperbrancedization polyester, polyacrylamide decolouring more than the number-average molecular weight 1000000g/mol after, obtain aqueous silicate solution; Wherein the weight ratio of amine-terminated hyperbrancedization polyester and raw material manganese leached mud is 1:100~150, and the weight ratio of polyacrylamide and raw material manganese leached mud is 1:100~150;
⑷ the aqueous silicate solution after with the decolouring that obtains among the step ⑶ joins in the reactor, add the content that water is regulated silicon-dioxide in the filtrate, add the particle promoting agent, slowly drip again the electrolytic manganese waste acid liquor of processing through decolouring, pH value to solution is between 5~8, after dropwising, at 40~60 ℃ of lower reaction 0.5~2h, filtration, washing, drying obtain white carbon black again; The water that wherein adds and the weight ratio 2.5~3.0:1 of raw material manganese leached mud; The consumption of particle promoting agent is 0.05~0.5% of raw material manganese leached mud weight.
2. the method for utilizing manganese leached mud and electrolytic manganese spent acid to prepare superfine active carbon white as claimed in claim 1, the preparation method who it is characterized in that the particle promoting agent is: 1.2mol dithiocarbonic anhydride, 1.2mol concentration are that 20% sodium hydroxide or 1.2mol concentration are 20% potassium hydroxide aqueous solution and contain 0.1mol Hyperbranched Polymer with Terminal Amido 300g powder and mix, stirring reaction is 6 hours under 40 ℃ of conditions, then crystallisation by cooling, filtration can obtain nabam pressed powder 336g or dithiocarbamic acid potassium pressed powder 342g.
3. the method for utilizing manganese leached mud and electrolytic manganese spent acid to prepare superfine active carbon white as claimed in claim 1, the decolorizing treatment agent that it is characterized in that the electrolytic manganese waste acid liquor is gac, amine-terminated hyperbrancedization polyester, polyacrylamide, the process of decolouring is that spent acid solution is lower to activated carbon treatment decolouring in 5 minutes at 90~100 ℃, and then use successively amine-terminated hyperbrancedization polyester, the above polyacrylamide of number-average molecular weight 1000000g/mol is processed respectively decolouring in 5 minutes at 40~100 ℃, wherein the weight ratio of gac and spent acid solution is 1:500~1000, the weight ratio of amine-terminated hyperbrancedization polyester and spent acid solution is 1:5000~10000, and the weight ratio of polyacrylamide and raw material manganese leached mud is 1:5000~10000.
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CN105197941B (en) * | 2015-10-16 | 2017-07-21 | 中南民族大学 | The method that a kind of utilization manganese carbonate leached mud and electrolytic manganese spent acid prepare high activity white carbon |
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GB823215A (en) * | 1955-11-15 | 1959-11-11 | Bruce Williams | Method for recovering manganese compounds from manganese-containing materials |
CN101161591A (en) * | 2006-10-09 | 2008-04-16 | 中国矿业大学(北京) | A method for preparing schistose nanometer magnesium hydroxide and sphericity nanometer white carbon black using zillerite gangue |
CN101973555A (en) * | 2010-10-20 | 2011-02-16 | 中南民族大学 | Method for preparing white carbon black and manganese fertilizer from manganese leaching residue |
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GB823215A (en) * | 1955-11-15 | 1959-11-11 | Bruce Williams | Method for recovering manganese compounds from manganese-containing materials |
CN101161591A (en) * | 2006-10-09 | 2008-04-16 | 中国矿业大学(北京) | A method for preparing schistose nanometer magnesium hydroxide and sphericity nanometer white carbon black using zillerite gangue |
CN101973555A (en) * | 2010-10-20 | 2011-02-16 | 中南民族大学 | Method for preparing white carbon black and manganese fertilizer from manganese leaching residue |
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