CN1311340A - Method for producing manganese carbonate from manganese sulfate in waste manganese mud - Google Patents
Method for producing manganese carbonate from manganese sulfate in waste manganese mud Download PDFInfo
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- CN1311340A CN1311340A CN 00113297 CN00113297A CN1311340A CN 1311340 A CN1311340 A CN 1311340A CN 00113297 CN00113297 CN 00113297 CN 00113297 A CN00113297 A CN 00113297A CN 1311340 A CN1311340 A CN 1311340A
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- manganese
- slag
- carbonate
- manganous
- sulfate
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Abstract
This invention relates to prodn. of manganese carbonate from manganese sulfate in waste manganese ore mud. It this invention, manganese ore powder is steeped with sulfuric acid for prepn. of sulfuric solution, then the slag is used as raw material. The slag is washed with water and then recovering manganese sulfate. After removing foreigh matters, it is reacted with carbonates (e.g. ammonium bicarbonate) to produe manganese carbounate. Other kinds of managese product can be produced therefrom. This method is suitable for manufacturers who produce manganese products from manganese ore powder and sulfuric acid.
Description
The present invention relates to a kind of method of producing manganous carbonate, particularly a kind of waste manganese mud that utilizes soaks the method that the manganous sulfate in the slag is produced manganous carbonate.
Manganous sulfate, electrolytic metal Mn, the production of manganese goods such as electrolytic manganese dioxide, all be earlier manganese carbonate ore (rhodochrosite) to be used sulfuric acid to leach, make manganese sulfate solution, behind impurity removal and purification, be used for producing various corresponding manganese goods again, waste manganese mud behind sulfuric acid to leach soaks in the slag, and the manganese sulfate solution that contains weight about 30% own has been drained as refuse together in company with soaking slag.Through measuring and calculating, an electrolytic manganese dioxide factory that produces 10000 tons per year soaks the manganous sulfate that emits the slag from giving up and be converted to pure manganese up to more than 700 tons every year; Produce 3000 tons of electrolytic manganese factories per year for one, annual pure manganese of from soak slag, draining also up to 150 tons about.This has not only greatly wasted valuable Mineral resources, and the useless solubility manganous sulfate that soaks in the slag is returned environment and brought very big pollution.It is few that waste manganese mud soaks the manganese sulfate solution relative quantity of carrying secretly in the slag, though reclaiming with water extraction is most economical way, but because the manganese sulfate solution after reclaiming is very rare, add the manganese sulfate solution that reclaims is also wanted purification refine, the more cost that makes of operation is higher, and is if will reclaim the production that liquid is directly used in electrolytic metal Mn or electrolytic manganese dioxide, then very uneconomical economically, therefore, all manganese goods factories of China all do not recycle the manganous sulfate that waste manganese mud soaks in the slag to be carried secretly.Estimate not following 5000 tons of the annual pure manganese of wasting therefrom.So, if can solve the recycling waste manganese mud effectively and soak the manganous sulfate of carrying secretly in the slag, manganese resource is fully used, and can obtains favorable economic benefit, can also reduce environmental pollution simultaneously, its economy and society meaning is all very great.
The object of the present invention is to provide a kind of technology simple, the waste manganese mud that utilizes that production cost is low soaks the method that the manganous sulfate in the slag is produced manganous carbonate.
The objective of the invention is to realize by following approach: utilize waste manganese mud to soak the method that the manganous sulfate in the slag is produced manganous carbonate, it is to adopt following step:
1) will leach the waste manganese mud behind the manganese sulfate solution soaks in the leaching groove jar of slag input belt stirrer, add the 1-4 water doubly soak slag weight, add solubility villiaumite and dissolvable sulfide, make that calcium ions is lower than 20PPM in the solution, metal ion is lower than 10PPM, fully stirs;
2) stir leaching about 0.5 hour, after the filtration filtrate is beaten to high-order storage tank I
In standby;
3) with the soluble carbon hydrochlorate with deionized water by weight 1: 4-8 dissolving, mistake
Filter back is beaten extremely in the high-order storage tank II standby;
4) under agitation, that manganese sulfate solution in header tank I and the II and carbonate is molten
Liquid injects reaction kettle for reaction simultaneously with the thread shape, its consumption press manganous sulfate with
The carbonate mol ratio is 1: 1-6 feeds intake, and behind reinforced the finishing, continues to stir
Reacted about 0.5 hour;
5) with the reactant centrifugation, throw out is changed in the rinse bath, add go from
Sub-water stirred after 10 minutes, and centrifugation repeats above-mentioned washing operation 2
-3 times;
6) will wash good throw out 55-60 ℃ of oven dry down, obtain manganese carbonate product.
The solubility villiaumite that adds is Sodium Fluoride or Neutral ammonium fluoride, and dissolvable sulfide is sodium sulphite or ammonium sulfide, and the soluble carbon hydrochlorate is bicarbonate of ammonia or sodium bicarbonate or yellow soda ash.
The present invention utilizes waste manganese mud to soak manganous sulfate in the slag, and to produce the method technology of manganous carbonate simple, used device is few, employing is with water extraction, adding fluorochemical and sulfide removal of impurities carries out simultaneously, make technical process simple, the manganous sulfate that employing leaches out with soluble carbon acid salt solution precipitation becomes the method for manganese carbonate product, has solved in the infusion manganous sulfate and has crossed rare and difficulty that be difficult to recycle; It is the various purity of raw material production manganous carbonate that the manganese carbonate product that adopts this method to produce can reach with electrolytic metal Mn, and cost has only the latter half.This method be applicable to all various be the raw material production manganous sulfate with sulfuric acid and manganese ore powder, electrolytic metal Mn, the producer of electrolytic manganese dioxide and all relevant manganese goods uses.
With embodiment the present invention is described in further detail below:
Embodiment one: soaking slag with the waste manganese mud of electrolytic manganese dioxide factory is that raw material is implemented method of the present invention:
The manganous sulfate refined soln concentration of electrolytic manganese dioxide factory is about 140gMn/L, and waste manganese mud soaks the manganous sulfate concentration of carrying secretly in the slag with 100gMn/L, and its proportion d=1.5 calculates.
Get waste manganese mud and soak 3 tons of inputs of slag 8M
3In the leaching can, add 4 tons of entry, start agitator, add 2Kg sodium sulphite, (calcium in the check leaching solution and copper, lead, cadmium, the isoionic content of mercury, as add Neutral ammonium fluoride or sodium sulphite when not reaching requirement), stir after 30 minutes, will leach thing pressure filter press filtration, (not limpid as solution, carry out the press filtration second time or vacuum filtration), refined liquid is squeezed in the high-order storage tank I standby with pump.
Take by weighing bicarbonate of ammonia 180Kg,, beat to the high-order storage tank II solution standby with filtration pump with deionized water 2 tons of dissolvings.
Manganese sulfate solution in the high-order storage tank I is put half (about 2 tons) to volume 8M
3Reactor in, start agitator, under the normal temperature, the ammonium bicarbonate soln in manganese sulfate solution in the high-order storage tank I and the high-order storage tank II is injected reactor simultaneously with constant speed.Feed intake finish after, continued stirring reaction 20 minutes, after the natural subsidence, the venting supernatant liquid, lower sediment changes the whizzer centrifugation over to, changes precipitation over to 1M then
3In the rinse bath, add deionized water 300Kg agitator treating after 10 minutes, centrifuging, precipitation is again with aforesaid method washing 2 times, the product that centrifugation obtains is put into enamel or Stainless Steel Disc, 55-60 ℃ of oven dry down, gets about manganese carbonate product 75Kg, quality can reach GB10503-89 I-III type, and the rate of recovery of manganous carbonate is about 75%.
Embodiment two: raw material still soaks slag for the waste manganese mud with electrolytic manganese dioxide factory
Get waste manganese mud and soak 3 tons of slags, drop into 8M
3In the leaching can, add 4 tons of entry, start agitator and stir after 20 minutes, with pressure filter press filtration (not adding fluorochemical or sulfide).Each step is all identical with embodiment one later on.Can get about manganese carbonate product 75Kg, quality is the general industry manganous carbonate, and the rate of recovery of manganous carbonate is about 75%.
Embodiment three: soaking slag with the waste manganese mud of electrolytic metal Mn factory is raw material
The manganous sulfate refined soln concentration of electrolytic manganese dioxide factory is about 38gMn/L, and waste manganese mud soaks the manganous sulfate concentration of carrying secretly in the slag with 35g/L, and its proportion d=1.3 calculates.
Get waste manganese mud and soak 3 tons of slags, drop into 8M
3In the leaching can, add 4 tons of entry, all the other operations are all carried out (wherein the bicarbonate of ammonia consumption is 100Kg, adds 1.5 tons of dissolvings of water) by embodiment one.Can get about manganese carbonate product 30Kg GB10503-89 I-III type.
Claims (3)
1. one kind is utilized waste manganese mud to soak the method that the manganous sulfate in the slag is produced manganous carbonate, it is characterized in that adopting following step:
1) will leach the waste manganese mud behind the manganese sulfate solution and soak soaking of slag input belt stirrer
Get in the groove jar, add the 1-4 water doubly that soaks slag weight, add soluble fluoride
Salt and dissolvable sulfide make that calcium ions is lower than 20PPM in the solution, contain
Metal ion is lower than 10PPM, fully stirs;
2) stir leaching about 0.5 hour, after the filtration filtrate is beaten to high-order storage tank I
In standby;
3) with the soluble carbon hydrochlorate with deionized water by weight 1: 4-8 dissolving, mistake
Filter back is beaten extremely in the high-order storage tank II standby;
4) under agitation, that manganese sulfate solution in header tank I and the II and carbonate is molten
Liquid injects reaction kettle for reaction simultaneously with the thread shape, its consumption press manganous sulfate with
The carbonate mol ratio is 1: 1-6 feeds intake, and behind reinforced the finishing, continues to stir
Reacted about 0.5 hour;
5) with the reactant centrifugation, throw out is changed in the rinse bath, add go from
Sub-water stirred after 10 minutes, and centrifugation repeats above-mentioned washing operation 2
-3 times;
6) will wash good throw out 55-60 ℃ of oven dry down, and obtain manganous carbonate and produce
Product.
2. utilize waste manganese mud to soak the method that the manganous sulfate in the slag is produced manganous carbonate according to claim 1, it is characterized in that the solubility villiaumite that adds is Sodium Fluoride or Neutral ammonium fluoride, dissolvable sulfide is sodium sulphite or ammonium sulfide.
3. utilize waste manganese mud to soak the method that the manganous sulfate in the slag is produced manganous carbonate according to claim 1, it is characterized in that the soluble carbon hydrochlorate is bicarbonate of ammonia or sodium bicarbonate or yellow soda ash.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001132970A CN1180100C (en) | 2000-02-28 | 2000-02-28 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001132970A CN1180100C (en) | 2000-02-28 | 2000-02-28 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1311340A true CN1311340A (en) | 2001-09-05 |
| CN1180100C CN1180100C (en) | 2004-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001132970A Expired - Fee Related CN1180100C (en) | 2000-02-28 | 2000-02-28 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
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| CN (1) | CN1180100C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579685B (en) * | 2009-06-10 | 2010-10-27 | 重庆大学 | Method for processing and utilizing electrolytic manganese waste residue |
| WO2011009351A1 (en) * | 2009-07-20 | 2011-01-27 | 贵州红星发展股份有限公司 | Method for circularly purifying manganese sulfate and manganese carbonate |
| CN101704553B (en) * | 2009-07-20 | 2012-11-07 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
| CN102839286A (en) * | 2012-09-26 | 2012-12-26 | 中信锦州金属股份有限公司 | Method for recycling bivalent manganese in electrolytic manganese leached residues |
| CN102887545A (en) * | 2012-10-15 | 2013-01-23 | 兰州大学 | Method for preparing electronic-grade manganese carbonate from manganese-copper-zinc-cobalt-calcium chloride solution |
| CN103789542A (en) * | 2014-01-20 | 2014-05-14 | 中南大学 | Wet-process reduction leaching method of manganese oxide mineral |
| CN105481019A (en) * | 2015-12-18 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | Method for removing alkaline-earth metal and heavy metal impurities in manganese sulfate solution |
| CN108752059A (en) * | 2018-07-04 | 2018-11-06 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN109097578A (en) * | 2018-07-17 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using aniline reduction electrolytic manganese anode mud |
| CN110127766A (en) * | 2019-07-02 | 2019-08-16 | 贵州中伟资源循环产业发展有限公司 | A kind of preparation process of LITHIUM BATTERY manganese sulfate solution |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
-
2000
- 2000-02-28 CN CNB001132970A patent/CN1180100C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579685B (en) * | 2009-06-10 | 2010-10-27 | 重庆大学 | Method for processing and utilizing electrolytic manganese waste residue |
| WO2011009351A1 (en) * | 2009-07-20 | 2011-01-27 | 贵州红星发展股份有限公司 | Method for circularly purifying manganese sulfate and manganese carbonate |
| CN101704553B (en) * | 2009-07-20 | 2012-11-07 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
| CN102839286A (en) * | 2012-09-26 | 2012-12-26 | 中信锦州金属股份有限公司 | Method for recycling bivalent manganese in electrolytic manganese leached residues |
| CN102887545B (en) * | 2012-10-15 | 2014-09-24 | 兰州大学 | Method for preparing electronic-grade manganese carbonate from manganese-copper-zinc-cobalt-calcium chloride solution |
| CN102887545A (en) * | 2012-10-15 | 2013-01-23 | 兰州大学 | Method for preparing electronic-grade manganese carbonate from manganese-copper-zinc-cobalt-calcium chloride solution |
| CN103789542A (en) * | 2014-01-20 | 2014-05-14 | 中南大学 | Wet-process reduction leaching method of manganese oxide mineral |
| CN103789542B (en) * | 2014-01-20 | 2015-10-07 | 中南大学 | A kind of wet reducing leaching method of manganese oxide mineral |
| CN105481019A (en) * | 2015-12-18 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | Method for removing alkaline-earth metal and heavy metal impurities in manganese sulfate solution |
| CN108752059A (en) * | 2018-07-04 | 2018-11-06 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN108752059B (en) * | 2018-07-04 | 2021-05-11 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN109097578A (en) * | 2018-07-17 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using aniline reduction electrolytic manganese anode mud |
| CN110127766A (en) * | 2019-07-02 | 2019-08-16 | 贵州中伟资源循环产业发展有限公司 | A kind of preparation process of LITHIUM BATTERY manganese sulfate solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1180100C (en) | 2004-12-15 |
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Owner name: XIANGTAN UNIV. Free format text: FORMER OWNER: DENG JIANCHENG Effective date: 20040604 |
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Effective date of registration: 20040604 Address after: 411105 scientific research office, Xiangtan University, Xiangtan, Hunan Applicant after: Xiangtan University Address before: 411105 No. 11, No. 106, Beidou village, Xiangtan University, Xiangtan, Hunan Applicant before: Deng Jiancheng |
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