CN104480314A - Method for recycling waste residue in manganese industry production - Google Patents

Method for recycling waste residue in manganese industry production Download PDF

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Publication number
CN104480314A
CN104480314A CN201410787589.4A CN201410787589A CN104480314A CN 104480314 A CN104480314 A CN 104480314A CN 201410787589 A CN201410787589 A CN 201410787589A CN 104480314 A CN104480314 A CN 104480314A
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filter
residue
liquid separation
solid
waste residue
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CN201410787589.4A
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CN104480314B (en
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赵阳臣
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赵阳臣
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for recycling waste residue in manganese industry production. The method comprises the specific following steps: (1) pre-processing filter residue; (2) adding acid and leaching; (3) carrying out filtering and solid-liquid separation on ore slurry; (4) recovering hematite powder; (5) recovering manganese carbonate concentrate; and (6) preparing a nitrogen-phosphorus compound fertilizer base material. By the method, hematite powder, manganese carbonate concentrate and the nitrogen-phosphorus compound fertilizer base material can be recovered from leached press-filtered residue, the process is simple and is easy to achieve industrialization and meanwhile, the content of the heavy metal ingredients is in completely in conformity with national associated standards, treated wastewater and waste residue are free of harmful ingredients such as heavy metals, the environmental pressure is alleviated and the method has great promotional values.

Description

Manganese industry produces the method that waste residue is recycled
Technical field
The invention belongs to abandoned mine slag for comprehensive and utilize technology, leach filter-press residues in particularly utilizing electrolytic metal Mn to produce and reclaim the method making multiple Chemicals.
Background technology
Manganese as one of important strategic resource of national economy, China the Eleventh Five-Year Plan period also by manganese as national strategy resource.At present, manganese obtains mainly through electrolytic process and reduction method, and electrolysis legal system manganese account for that pure manganese produces total amount more than 95%, the manufacturing enterprise of electrolytic metal Mn is all be raw material with rhodochrosite and pyrolusite, through sulfuric acid leaching → oxidizer oxidation ferrous iron → add ammoniacal liquor neutralizing hydrolysis deironing → leaching press filtration (filter-press residues) → filtrate → add SDD (Sodium Dimethyldithiocarbamate) heavy metal (Co, Ni, Cu) → secondary press filtration → filtrate to staticly settle → suction filtration clear liquid → electrolysis → electrolytic metal Mn.Its process produces and passes in and out filter-press residues in a large number, and slag rate reaches often produces one ton of electrolytic metal Mn leaching filter-press residues with regard to output 6-8 ton, is directly transported to slag storehouse and loses and put.And also containing many useful elements in this slag, as: the leaching filter-press residues of middle letter large Meng great Xin Meng industry company limited just has: manganous sulfate 12%, silicon-dioxide 30-40%, calcium sulfate 5-10%, magnesium sulfate 3-4%, aluminum oxide 13%, ironic hydroxide 20%, ammonium sulfate 2-3%, so not only lost valuable mineral wealth, and occupy a large amount of land resources, there is very big hidden danger to environmental pollution and geologic hazard.
Notification number is " a kind of technique of electrolytic manganese residues comprehensive utilization " its technique that patent document discloses of CN10306425B is reclaim soluble manganese and ammonium sulfate, remaining waste residue brickmaking with water cycle cleaning leached mud and evaporation concentration.Its shortcoming has only reclaimed part soluble manganese and ammonium sulfate, but fail to reclaim not leaching and water-fast valuable mineral, and power consumption water consumption is large, and cost recovery is too high.
Contriver reclaims the process of electrolytic manganese waste residue and conducts in-depth research, and applied for Patents: " electrolytic metal Mn, leached mud comprehensive reutilization method in Manganse Dioxide production ", the patent No. is ZL201210179516.8, this method have employed heavily, floating, the techniques such as magnetic separation and chemical-biological leaching carry out comprehensive reutilization, although reclaim valuable metal mineral and preparation composite fertilizer base-material more comprehensively, but operational path is oversize in implementation process, auxiliary material and the mechanical means of use are too many, floor space is too large, under the condition of continuous summing up experience and improvement of production process, invent more advanced practicality, the method of simple possible.
Summary of the invention
The object of this invention is to provide a kind of method that manganese industry produces waste residue recycling, the method can reclaim iron oxide red breeze, manganous carbonate concentrate, prepare Sodium Silicofluoride and compound nitrogen phosphate fertilizer base-material, with solve current waste residue recovery processing technique route long, use auxiliary material and mechanical means is many, place of production area large, the problem that loss is high.
For achieving the above object, technological line of the present invention is achieved in that
Manganese industry produces the method that waste residue is recycled, and concrete technology comprises as lower part: (1) filter residue pre-treatment; (2) Ore Leaching is added; (3) slurry filtration and solid-liquid separation; (4) iron oxide red breeze reclaims; (5) manganous carbonate concentrate reclaims; (6) compound nitrogen phosphate fertilizer base-material preparation.
Described filter residue pre-treatment is first added water by filter residue after mixing to pulverize as ore pulp, and then by after screw classifier classification, the ore particle making not cross 100 mesh sieves through wet-type ball mill fine grinding until cross 100 mesh sieves.Because of the solid block of electrolytic manganese, Manganse Dioxide filter residue to be liquid content be 28-30%, under water state must be had, in disintegrating machine, shatter into ore pulp; The size-grade distribution of ore pulp is generally 84% and crosses 100 mesh sieves, and 16% does not cross 100 mesh sieves, namely has 84% ore particle to be the screen underflow of 100 mesh sieves, has 16% ore particle to be the screen overflow of 100 mesh sieves.Ore particle on 16% sieve is made to enter the granularity requirements that wet-type ball mill fine grinding reaches leaching so ore pulp carries out classification through screw classifier.
The described Ore Leaching that adds in ore pulp, adds the vitriol oil, hierarchy of control pH≤1.5, makes Fe3+, Mn2+ leach in ore pulp with ionic condition;
Described slurry filtration and solid-liquid separation squeeze into pressure filter with wear-resisting resistance to acid attack Pulp pump to carry out solid-liquid separation, and gained filter cake does peroxophosphoric acid calcareous fertilisers use, and gained filtrate enters the process of lower step operation;
It is once neutralize in the obtained filtrate of step (3) that described iron oxide red breeze reclaims, and add ammonium alkali and regulate pH to 4-5, make Fe (OH) 3 Precipitation, through pressure filter press filtration, gained filter cake washing dries to obtain iron oxide red breeze;
It is Two-step neutralization in the obtained filtrate of step (4) that described manganous carbonate concentrate reclaims, add ammonium alkali again and regulate pH7.2-8, make MnSO4 Precipitation, diaphragm filter press press filtration solid-liquid separation, gained filter cake washing dries to obtain manganous carbonate concentrate, it is 7 that the gained filtrate vitriol oil is neutralized to pH, sends cycling use of water pond back to;
Concrete steps prepared by described compound nitrogen phosphate fertilizer base-material are:
1. filter cake recirculated water obtained in step (3) is pulverized pulping in pulverizer, put into bucket with slurry;
2. add P2O5 content be >=26% fluorine-containing low ground phosphate rock stir and be made into slurry, enter mixing reactor, for subsequent use;
3. the vitriol oil hybrid reaction 3-5min of weight concentration more than 90% is added, inflow belt formation chamber reaction 30min after completing;
4. send into aerobic fermentation tank slaking 7-15d, dry and pulverize and get final product;
Described ammonium alkali is the one in bicarbonate of ammonia, volatile salt or ammoniacal liquor.
Described through acid fog absorption tower formed silicate fluoride solution content lower than 8% time, enter circulating water pool.
The present invention compared with prior art its advantage is:
One, ferrimanganic resource can be reclaimed more fully and effectively.
(1) shatter classification by thin up again and clean grinding, which decrease the degree of supersaturation of CaSO4, also destroy the CaSO4 wrap film being wrapped in ore particle surface and ore particle is more easily leached;
(2) press filtration solid-liquid separation under low pH value, avoids metal ion and follows filter residue with colloidal and walk, lost iron, manganese metal, add the heavy metal content of filter residue.
Two, utilize and make precipitation agent by the fertilizer ammonium alkali (NH4HCO3, (NH4) 2CO3, NH3H2O) of the volatile easy loss of thermally labile and not only reclaimed iron, manganese metal, and (NH4) 2SO4 nitrogen manure raw material that the ammonium alkali fertilizer that makes easily to run off becomes stable.
Three, (NH4) 2SO4 a large amount of in the monocalcium phosphate utilizing ground phosphate rock and strong sulfuric acid response to generate and the filter residue aqueous solution reacts and generates monoammonium phosphate and prepare NP composite fertilizer base-material.
Four, manganese resource and phosphate rock resource can be utilized to be engaged in produce electrolytic metal Mn and phosphorization product and the target that realizes without waste sludge discharge.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that manganese industry produces the method that waste residue is recycled.
See in figure, concrete technology of the present invention is as follows: first manganese filter-press residues adds water and carry out pulverizing and ball milling, then enriching sulfuric acid leaching; Ore pulp press filtration, filter cake enters reactor, and add the vitriol oil and fluorine-containing low ground phosphate rock, compound nitrogen phosphate fertilizer is made in solid slaking; Filtrate once neutralizes press filtration again, and filter cake washing is dried and obtained iron oxide red; Filtrate Two-step neutralization, press filtration, washing and drying obtains manganous carbonate concentrate.
Embodiment
Embodiment one
1, leaching filter-press residues 1000g and 8L clear water is taken, put into disintegrating machine to shatter and be made into ore pulp, and cross 100 eye mesh screens, screen underflow enters chemical combination agitation vat, screen overflow enters minigrinder and adds 2L clear water and together grind rear mistake 100 eye mesh screen and with adding chemical combination agitation vat, start stirrer, stir with 65 turns/min stirring velocity.
2, measure 98%H2SO4500ml, add in mix and blend bucket while stirring, continue to stir about 4h, measuring pH value is 1.5, stops stirring.
3, filter solid-liquid separation, filter residue is put well and is continued to employ, and filtrate puts into neutralizing hydrolysis agitation vat, starts stirrer, stirs with 65 turns/min stirring velocity.
4, slowly add NH4HCO3 powder while stirring, once neutralize, test soln pH value, when PH is 4, stop adding NH4HCO3, continue to be stirred to bubble-free and produce, stop stirring.
5, filter solid-liquid separation, filtrate puts into neutralization precipitation agitation vat, and filter residue clear water washs three times, and neutralization precipitation agitation vat together put into by washing water, and after washing, the iron oxide red breeze that 168gFe content is 35% is dried and obtained to filter residue at 107 DEG C.The results are shown in survey report 1.
6, start neutralization precipitation agitation vat stirrer and stir with 65 turns/min rotating speed, slowly adding NH4HCO3 powder while stirring, Two-step neutralization is test soln pH value simultaneously, when PH is 7.2, stop adding NH4HCO3 powder, continue to be stirred to bubble-free and produce, stop stirring.
7, filter solid-liquid separation, filtrate puts into neutralization precipitation agitation vat, and filter residue clear water washs three times, and washings is put into and agitation vat in the lump, and the MnCO3 concentrate that 125gMn content is 31% is dried and obtained to filter residue at 107 DEG C, sees examining report 2.
8, in starting and agitation vat stirrer stirring with the stirring velocity of 65 turns/min, add 98%H2SO4 while stirring, test pH value simultaneously, when PH is 7.2, stop adding 98%H2SO4, continue to be stirred to when bubble-free produces and stop stirring, and solution is put into circulation bucket to get circulation use ready.
9, to measure in " Section 8 " solution 2L in circulation bucket to put into disintegrating machine with the filter residue in " Section 3 " and shatter into ore pulp, pour in " Section 9 " middle hybrid reaction bucket, start agitator, and be that 65 turns/min stirs with rotating speed, clear water is injected and absorbs bucket to 2/3 place.
10, take containing P2O5 be 30%, SiO2 be 3.42% ground phosphate rock 1000g, add in " Section 10 " hybrid reaction bucket, after stirring 3min, measure 98%H2SO4 solution 500ml again and slowly add hybrid reaction bucket, stop after 15min stirring, material in hybrid reaction bucket is put into maturation tub slaking 15d.
11, dried at 107 DEG C by material in maturation tub after 15d, shatter into compound nitrogen phosphate fertilizer base-material, its content is: P2O510%, N4%.Heavy metal: Cr3mg/kg, Cd0.2mg/kg, Pb0.05mg/kg, Hg0mg/kg, As0.21mg/kg.See examining report 3.Contriver carries out heavy metal content detection to the waste water after process simultaneously, and above heavy metal component does not all detect, and the effective complexing with heavy metal in maturing process of compound nitrogen phosphate fertilizer base-material is described, waste water and dregs heavy metal free composition after treatment pollutes.And the heavy metal content showing obtained compound nitrogen phosphate fertilizer base-material kind in survey report 3 data all reaches the innoxious index of fertilizer product (national standard, industry standard).
The every effective substance result of attached embodiment 1 below.
Table 1 survey report 1
Sampling observation sample Sample quality Fe content %
Iron oxide red breeze 50 35
Table 2 survey report 2
Sampling observation sample Sample quality Fe content %
Manganous carbonate concentrate 50 31.0
Table 3 survey report 3
Embodiment two
1, leaching filter-press residues 1000g is taken, measure " Section 8 " circulation bucket 2/3 water in example (), put into disintegrating machine to shatter and be made into ore pulp, and cross 100 eye mesh screens, screen underflow enters chemical combination agitation vat, screen overflow enters minigrinder and adds the remaining water of precedent " Section 8 " circulation bucket and together grind, and rear full mistake 100 eye mesh screen also with adding chemical combination agitation vat, starting stirrer and stirring with 65 turns/min stirring velocity.
2, measure 98%H2SO4500ml, add in chemical combination agitation vat while stirring, continuing to stir 4h measurement pH value is 1.0, stops stirring.
3, solid-liquid separation is filtered: filter residue puts adapted well, and filtrate puts into neutralizing hydrolysis agitation vat, starts stirrer, stirs with 65 turns/min stirring velocity.
4, slowly add (NH4) 2CO3 powder while stirring, once neutralize, measure solution pH value, when PH is 4.5, stop adding (NH4) 2CO3 powder, continue to be stirred to bubble-free and produce, stop stirring.
5, filter solid-liquid separation, filtrate puts into neutralization precipitation agitation vat, and filter residue clear water washs three times, and neutralization precipitation agitation vat together put into by washing water, and washing filter residue is dried and obtains the iron oxide red breeze of 200gFe content 41% at 107 DEG C, sees examining report 4.
6, start neutralization precipitation agitation vat stirrer, and stir with 65 turns/min stirring velocity, add while stirring
(NH4) 2CO3 powder, Two-step neutralization, simultaneously test soln pH value, when PH is 7.5, stop adding (NH4) 2CO3 powder, continues to be stirred to bubble-free and produce, stop stirring.
7, filter solid-liquid separation, filtrate is put into and agitation vat, and filter residue clear water washs three times, and washings is put into and agitation vat in the lump, and filter residue is dried and obtained 150g at 107 DEG C, and the manganous carbonate concentrate of Mn content 38.8%, is shown in examining report 5.
8, in starting and agitation vat stirrer, and stir with 65 turns/min stirring velocity, add 98%H2SO4 solution while stirring, test soln pH value simultaneously, when PH is 7, stop adding 98%H2SO4, continue to be stirred to bubble-free and produce, stop stirring, and liquid is put into circulation bucket to get circulation use ready.
9, measure liquid 2L in " Section 8 " circulation bucket to put into disintegrating machine with the filter residue of " Section 3 " and shatter into ore pulp, add in the hybrid reaction bucket of example () " Section 9 ", start agitator, and stir with 65 turns/min rotating speed.
10, take containing P2O5 be 30%, SiO2 be 3.42% ground phosphate rock 1000g, add in hybrid reaction agitation vat, stir 3min, then measure 98%H2SO4 solution 500ml and slowly add in hybrid reaction bucket, stir 15min and stop stirring.Material in hybrid reaction bucket is put into maturation tub slaking 12d.
11, dried at 107 DEG C of temperature by material in maturation tub after 12d and shatter into compound nitrogen phosphate fertilizer base-material, its content is for being shown in examining report 6.
The every effective substance result of attached embodiment 2 below.
Table 4 survey report 4
Sampling observation sample Sample quality Fe content %
Iron oxide red breeze 50 41
Table 5 survey report 5
Sampling observation sample Sample quality Fe content %
Manganous carbonate concentrate 50 38
Table 6 survey report 6
Embodiment three
1, leaching filter-press residues 1000g is taken, measure 2/3 water in " example (two) Section 8 " circulation bucket, put into disintegrating machine to shatter and be made into ore pulp, and cross 100 eye mesh screens, screen underflow enters chemical combination agitation vat, in screen overflow and " example (two) Section 8 " circulation bucket, remaining water adds minigrinder in the lump and grinds, and entirely adds chemical combination agitation vat through 100 eye mesh screens afterwards.Start stirrer to stir with 65 turns/min stirring velocity.
2, measure 98%H2SO4, add in chemical combination agitation vat while stirring, continue to stir 4h, measuring pH value is 0.5, stops stirring.
3, filter solid-liquid separation, filter residue is put well for subsequent use, and filtrate puts into neutralizing hydrolysis agitation vat, starts stirrer and stirs with 65 turns/min stirring velocity.
4, slowly add the ammoniacal liquor containing NH330% while stirring, once neutralize, simultaneously test soln pH value, when PH is 5, stop adding ammoniacal liquor, continue to be stirred to bubble-free and produce, stop stirring.
5, filter solid-liquid separation, filtrate puts into neutralization precipitation bucket, and filter residue clear water washs three times, and neutralization precipitation bucket together put into by washing water, and washing filter residue is dried and obtains 284g at 107 DEG C, and Fe content is the iron oxide red breeze of 45%, sees examining report 7.
6, start neutralization precipitation agitation vat stirrer and stir with 65 turns/min stirring velocity, slowly adding the ammoniacal liquor containing NH330% while stirring, Two-step neutralization, test soln pH value simultaneously, when pH value is 8, stops adding ammoniacal liquor, continue to be stirred to bubble-free to produce, stop stirring.
7, filter solid-liquid separation, filtrate is put into and agitation vat, and filter residue clear water washs three times, during washings adds in the lump and in agitation vat.Washing filter residue is dried and obtains 155g at 107 DEG C, and Mn content is Mn (OH) 2 concentrate of 34.0%, sees examining report 8.
8, in starting and agitation vat stirrer stirring with 65 turns/min stirring velocity, slowly add 98%H2SO4 while stirring, test soln pH value simultaneously, when pH value is 7, stop adding 98%H2SO4, continue to be stirred to when bubble-free produces and stop stirring, and liquid is put into circulation bucket recycle to get ready.
9, measure liquid 2L in " Section 8 " circulation bucket, put into disintegrating machine with the filter residue of " Section 3 " and shatter into ore pulp, add in the hybrid reaction bucket of " example () the 9th ", start stirrer and stir with 65 turns/min stirring velocity.
10, take containing P2O5 be 30%, SiO2 be 3.42% ground phosphate rock 1000g, add in hybrid reaction bucket and stir 3min, then measure 98%H2SO4500ml and slowly add in hybrid reaction bucket, stop during 15min stirring.Material in hybrid reaction bucket is put into maturation tub slaking 15d.
11, in starting and agitation vat stirrer stirring with 65 turns/min stirring velocity, add ammoniacal liquor while stirring, measure pH value simultaneously, when pH value is 6.5, stop adding ammoniacal liquor, continue to be stirred to when bubble-free produces stopping stirring, and it is for subsequent use that liquid is put into the following circulation of circulation bucket.
Material in maturation tub after slaking 15d is dried at 107 DEG C and shatters and obtain compound nitrogen phosphate fertilizer base-material, the results are shown in survey report 9.
Table 7 survey report 7
Sampling observation sample Sample quality Fe content %
Iron oxide red breeze 50 45
Table 8 survey report 8
Sampling observation sample Sample quality Fe content %
Manganous carbonate concentrate 50 34.0
Table 9 survey report 9

Claims (3)

1. manganese industry produces the method that waste residue is recycled, and it is characterized in that: concrete technology is as follows: (1) filter residue pre-treatment; (2) Ore Leaching is added; (3) slurry filtration and solid-liquid separation; (4) iron oxide red breeze reclaims; (5) manganous carbonate concentrate reclaims; (6) compound nitrogen phosphate fertilizer base-material preparation;
Described filter residue pre-treatment is first added water by filter residue after mixing to pulverize as ore pulp, and then by after screw classifier classification, the ore particle making not cross 100 mesh sieves through wet-type ball mill fine grinding until cross 100 mesh sieves;
The described Ore Leaching that adds in ore pulp, adds the vitriol oil make Fe 3+, Mn 2+leach in ore pulp with ionic condition;
Described slurry filtration and solid-liquid separation squeeze into pressure filter with wear-resisting resistance to acid attack Pulp pump to carry out solid-liquid separation, and gained filter cake does peroxophosphoric acid calcareous fertilisers use, and gained filtrate enters the process of lower step operation;
It is once neutralize in the obtained filtrate of step (3) that described iron oxide red breeze reclaims, and adds ammonium alkali and regulates pH to 4-5, make Fe (OH) 3precipitation, through pressure filter press filtration, gained filter cake washing dries to obtain iron oxide red breeze;
It is Two-step neutralization in the obtained filtrate of step (4) that described manganous carbonate concentrate reclaims, then adds ammonium alkali adjustment pH7.2-8, makes MnSO 4precipitation, pressure filter press filtration solid-liquid separation, gained filter cake washing dries to obtain manganous carbonate concentrate, and it is 7 that the gained filtrate vitriol oil is neutralized to pH, sends cycling use of water pond back to;
Concrete steps prepared by described compound nitrogen phosphate fertilizer base-material are:
1. filter cake recirculated water obtained in step (3) is pulverized pulping in pulverizer, put into bucket with slurry;
2. P is added 2o 5content be>=26% not fluorine-containing ground phosphate rock stir and be made into slurry, enter mixing reactor, for subsequent use;
3. the vitriol oil hybrid reaction 3-5min of weight concentration more than 90% is added, inflow belt formation chamber reaction 30min after completing;
4. send into aerobic fermentation tank slaking 7-15d, dry and pulverize and obtain compound nitrogen phosphate fertilizer base-material.
2. manganese industry according to claim 1 produces the method that waste residue is recycled, and it is characterized in that: described in add the vitriol oil, control pH≤1.5 when adding Ore Leaching.
3. manganese industry according to claim 1 produces the method that waste residue is recycled, and it is characterized in that: described ammonium alkali is the one in bicarbonate of ammonia, volatile salt or ammoniacal liquor.
CN201410787589.4A 2014-12-17 2014-12-17 Method for recycling waste residue in manganese industry production CN104480314B (en)

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CN105084421A (en) * 2015-09-22 2015-11-25 赵阳臣 Method for preparing high-purity manganese carbonate through comprehensive utilization of mid-low-grade pyrolusite
CN105152153A (en) * 2015-09-22 2015-12-16 赵阳臣 Comprehensive recycling method for leaching residues in electrolytic manganese metal production
CN105152152A (en) * 2015-09-22 2015-12-16 赵阳臣 Method for preparing high-purity manganese carbonate and by-products through middle-low-grade rhodochrosite
CN105197941A (en) * 2015-10-16 2015-12-30 中南民族大学 Method for preparing high-activity white carbon black through utilizing manganese carbonate leaching residues and electrolytic manganese waste acid
CN105274580A (en) * 2015-11-15 2016-01-27 王兆兵 Method for comprehensively using water and manganese slag in electrolytic manganese production
CN106381387A (en) * 2016-09-09 2017-02-08 北京科技大学 Method for preparing high-purity manganese phosphate from low-grade rhodochrosite leaching liquid
CN108863334A (en) * 2018-07-16 2018-11-23 广东清大同科环保技术有限公司 A method of manganese-zinc ferrite absorbing material is prepared using useless ash is cast
CN109701749A (en) * 2019-01-22 2019-05-03 云南磷化集团有限公司 A kind of method of nitric acid pretreatment direct flotation phosphorus concentrate

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CN105084421A (en) * 2015-09-22 2015-11-25 赵阳臣 Method for preparing high-purity manganese carbonate through comprehensive utilization of mid-low-grade pyrolusite
CN105152153A (en) * 2015-09-22 2015-12-16 赵阳臣 Comprehensive recycling method for leaching residues in electrolytic manganese metal production
CN105152152A (en) * 2015-09-22 2015-12-16 赵阳臣 Method for preparing high-purity manganese carbonate and by-products through middle-low-grade rhodochrosite
CN105197941A (en) * 2015-10-16 2015-12-30 中南民族大学 Method for preparing high-activity white carbon black through utilizing manganese carbonate leaching residues and electrolytic manganese waste acid
CN105274580A (en) * 2015-11-15 2016-01-27 王兆兵 Method for comprehensively using water and manganese slag in electrolytic manganese production
CN106381387A (en) * 2016-09-09 2017-02-08 北京科技大学 Method for preparing high-purity manganese phosphate from low-grade rhodochrosite leaching liquid
CN106381387B (en) * 2016-09-09 2018-04-13 北京科技大学 A kind of method that high-purity phosphoric acid manganese is prepared from low grade rhodochrosite leachate
CN108863334A (en) * 2018-07-16 2018-11-23 广东清大同科环保技术有限公司 A method of manganese-zinc ferrite absorbing material is prepared using useless ash is cast
CN108863334B (en) * 2018-07-16 2021-02-09 广东清大同科环保技术有限公司 Method for preparing manganese-zinc ferrite wave-absorbing material by using casting waste ash
CN109701749A (en) * 2019-01-22 2019-05-03 云南磷化集团有限公司 A kind of method of nitric acid pretreatment direct flotation phosphorus concentrate

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