CN102701611A - Precipitation conversion method for removing sulfates from electrolytic manganese slag - Google Patents
Precipitation conversion method for removing sulfates from electrolytic manganese slag Download PDFInfo
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- CN102701611A CN102701611A CN2012102215403A CN201210221540A CN102701611A CN 102701611 A CN102701611 A CN 102701611A CN 2012102215403 A CN2012102215403 A CN 2012102215403A CN 201210221540 A CN201210221540 A CN 201210221540A CN 102701611 A CN102701611 A CN 102701611A
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- electrolytic manganese
- slag
- manganese slag
- manganese residues
- water
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Abstract
The invention provides a method for removing sulfates from electrolytic manganese slag, which comprises the following steps: mixing ammonium bicarbonate and electrolytic manganese slag in water so that calcium sulfate in the electrolytic manganese slag reacts with the ammonium bicarbonate to generate calcium carbonate and ammonium sulfate, filtering, and washing to obtain the desulfurized slag in which the sulfur content (on basis of SO3) is lower than 1%. The liquid ammonium sulfate which is concentrated to crystallize can be used for fertilizers, and can also be used for electrolytic manganese production. The high sulfur content in the electrolytic manganese slag restricts the addition amount in cement, so that the abundant electrolytic manganese slag can not be used and is piled in the environment so as to occupy the land and pollute the environment. When the method provided by the invention is used for treating the electrolytic manganese slag, the sulfur content can be reduced to lower than 1%; and thus, the treated electrolytic manganese slag can be used as a raw material to produce cement. The invention has the advantages of simple technique and low treatment cost, and is suitable for popularization.
Description
Technical field
The present invention relates to trade refuse and utilize the pre-treatment in the method, particularly a kind of electrolytic manganese residues and bicarbonate of ammonia reaction are to remove the method for vitriol in the slag.
Background technology
Electrolytic manganese residues is the waste residue that produces in the electrolytic metal Mn production process; Staple is silicon-dioxide, aluminum oxide, red stone and calcium sulfate etc., mainly is raw material with the rhodochrosite in China's electrolytic manganese production, and product per ton produces 5 ~ 7 tons in waste residue; At present; About 3,000,000 tons of China's electrolytic manganese production ability, YO is about 2,000,000 tons, the waste residue YO is more than 1,000 ten thousand tons.
For a long time, do not find ideal method for the processing of electrolytic manganese residues with utilization always.At present, only be used for cement additire on a small quantity, most electrolytic manganese residues are deposited in the environment, environment are caused have a strong impact on.Assign to see from the one-tenth of electrolytic manganese, remove behind the vitriol similarly, thereby can be used for producing cement and ceramic tile with the raw material of producing cement, ceramic tile etc.In recent years, also saw the report that some prepare ceramic tile or be used for cement admixture with electrolytic manganese residues, but, had a strong impact on performance of products, so also do not see industrialized utilization up at present because of sulphate content wherein is bigger.
Summary of the invention
Technical problem to be solved by this invention is the problem that is not easy to utilize to containing a large amount of vitriol in the electrolytic manganese residues, proposes a kind of method that removes sulphur in the electrolytic manganese residues, and this method may further comprise the steps:
(1) electrolytic manganese residues and water are pressed the mixed of 1:1 ~ 5;
(2) according to the content of sulphur in the electrolytic manganese residues (with SO
3Meter) extraordinarily goes into bicarbonate of ammonia with 1.5 ~ 3, under agitation reacted 1 ~ 10 hour, make vitriol be converted into carbonate deposition; Then
(3) filter, wash; And
(4) the concentrating filter liquor crystallization obtains ammonium sulfate, also can directly be used for electrolytic manganese production.
The present invention is with the reaction of the calcium sulfate in bicarbonate of ammonia and the electrolytic manganese residues, makes water-fast calcium sulfate be converted into water-soluble ammonium sulfate, reaction formula:
CaSO
4?+?2NH
4HCO
3?=?CaCO
3?+?(NH
4)
2SO
4?+?CO
2?+?H
2O
Electrolytic manganese residues and water blended ratio are 1:1 ~ 5 in the step (1), and preferably, ratio is 1:2.
The amount of bicarbonate of ammonia is that the amount of sulphur in the electrolytic manganese residues is (with SO in the step (2)
3Meter) 1.5 ~ 3 times, preferably, the amount of bicarbonate of ammonia is that the amount of sulphur in the electrolytic manganese residues is (with SO
3The meter) 2 times.
The reaction times is 1 ~ 10 hour in the step (2), and preferably, the reaction times is 3 ~ 5 hours.
Can wash after filtering in the step (3), also can not wash, preferably, with the water yield washing of water consumption in the step (1), the gained washings is used for step (1) and electrolytic manganese residues blending water.
Embodiment
The following stated is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also are regarded as protection scope of the present invention.
Embodiment 1
(1) get electrolytic manganese residues, wherein sulphur content is (with SO
3Meter) be 21.2%, by the mixed of every kg slag 2 premium on currency (or former washings);
(2) press 1.9 times of amount of sulphur in the slag, the ratio of promptly every kg slag 0.4kg bicarbonate of ammonia adds bicarbonate of ammonia, stirs reaction down 5 hours;
(3) filter, and by every kg slag with 2 liters of washing water washings, the washings collection is used for mixing of second leg electrolytic manganese residues and water;
(4) filtered liq obtains ammonium sulfate solids through the evaporation concentration post crystallization in thickener.Mother liquor after the Crystallization Separation returns evaporation concentration.
(butt, sulphur is with SO for sulfur-bearing in the filter cake behind the filtration washing
3Meter) is 0.35%, can be used for porcelain making brick, cement slurry fully.
Embodiment 2
(1) get electrolytic manganese residues, wherein sulphur content is 17.7%, by the mixed of every kg slag 4 premium on currency;
(2) press 2.54 times of amount of sulphur in the slag, the ratio of promptly every kg slag 0.45kg bicarbonate of ammonia adds bicarbonate of ammonia, stirs reaction down 1 hour;
(3) filter (not washing);
(4) filtered liq obtains ammonium sulfate solids through the evaporation concentration post crystallization in thickener.Mother liquor after the Crystallization Separation returns evaporation concentration.
(butt, sulphur is with SO for sulfur-bearing in the filter cake after the filtration
3Meter) is 0.97%, can be used for porcelain making brick and cement slurry fully.
Embodiment 3
(1) get electrolytic manganese residues, wherein sulphur content is 16.5%, by the mixed of every kg slag 1.2 premium on currency (or former washings);
(2) press 1.94 times of amount of sulphur in the slag, the ratio of promptly every kg slag 0.32kg bicarbonate of ammonia adds bicarbonate of ammonia, stirs reaction down 7 hours;
(3) filter, and by every kg slag with 1.2 liters of washing water washings, the washings collection is used for mixing of second leg slag and water;
(4) filtered liq directly is used for the batching of electrolytic manganese production.
(butt, sulphur is with SO for sulfur-bearing in the filter cake behind the filtration washing
3Meter) is 0.61%, can be used for porcelain making brick and cement slurry fully.
Embodiment 4
(1) get electrolytic manganese residues, wherein sulphur content is 18.3%, by the mixed of every kg slag 3 premium on currency (or former washings);
(2) press 2.73 times of amount of sulphur in the slag, the ratio of promptly every kg slag 0.5kg bicarbonate of ammonia adds bicarbonate of ammonia, stirs reaction down 10 hours;
(3) filter, and by every kg slag with 1.2 liters of washing water washings, the washings collection is used for mixing of second leg slag and water;
(4) filtered liq directly is used for the batching of electrolytic manganese production.
(butt, sulphur is with SO for sulfur-bearing in the filter cake behind the filtration washing
3Meter) is 0.33%, can be used for porcelain making brick and cement slurry fully.
Claims (5)
1. from electrolytic manganese residues, remove the method for vitriol, it is characterized in that may further comprise the steps:
(1) electrolytic manganese residues mixes with water by a certain percentage;
(2) according to the amount of sulphur in the electrolytic manganese residues (with SO
3Meter) adds bicarbonate of ammonia with certain proportion, under agitation react for some time;
(3) filter, wash;
(4) the concentrating filter liquor crystallization obtains ammonium sulfate, also can directly be used for electrolytic manganese production.
2. the method for claim 1 is characterized in that, the ratio of electrolytic manganese residues and water is 1:1 ~ 5 in the said step (1).
3. the method for claim 1 is characterized in that, the amount that the add-on of volatile salt is pressed sulphur in the slag in the said step (2) is (with SO
31.5 ~ 3 extraordinarily going into meter).
4. the method for claim 1 is characterized in that, the reaction times in the said step (2) is 1 ~ 10 hour.
5. the method for claim 1 is characterized in that, also can be the washings in the step (3) with electrolytic manganese residues blended water in the said step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102215403A CN102701611A (en) | 2012-06-30 | 2012-06-30 | Precipitation conversion method for removing sulfates from electrolytic manganese slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102215403A CN102701611A (en) | 2012-06-30 | 2012-06-30 | Precipitation conversion method for removing sulfates from electrolytic manganese slag |
Publications (1)
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|---|---|
| CN102701611A true CN102701611A (en) | 2012-10-03 |
Family
ID=46894742
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| CN2012102215403A Pending CN102701611A (en) | 2012-06-30 | 2012-06-30 | Precipitation conversion method for removing sulfates from electrolytic manganese slag |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923977A (en) * | 2012-11-15 | 2013-02-13 | 吉首大学 | Method capable of utilizing sulfate-free electrolytic manganese residue to prepare common silica cement |
| CN103466830A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for recycling electrolytic manganese metal anode waste liquor |
| 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 |
| CN114804177A (en) * | 2022-04-08 | 2022-07-29 | 中冶南方都市环保工程技术股份有限公司 | Industrial solid waste electrolytic manganese slag mineralized CO 2 Resource utilization method |
| CN115784289A (en) * | 2022-12-07 | 2023-03-14 | 西南科技大学 | Method and system for preparing light calcium carbonate by electrolyzing manganese slag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884098A (en) * | 2005-06-24 | 2006-12-27 | 朱作远 | Technology for producing manganese sulphate by gypsum and ammonia circulation method |
| 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 |
-
2012
- 2012-06-30 CN CN2012102215403A patent/CN102701611A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884098A (en) * | 2005-06-24 | 2006-12-27 | 朱作远 | Technology for producing manganese sulphate by gypsum and ammonia circulation method |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923977A (en) * | 2012-11-15 | 2013-02-13 | 吉首大学 | Method capable of utilizing sulfate-free electrolytic manganese residue to prepare common silica cement |
| CN103466830A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for recycling electrolytic manganese metal anode waste liquor |
| 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 |
| CN114804177A (en) * | 2022-04-08 | 2022-07-29 | 中冶南方都市环保工程技术股份有限公司 | Industrial solid waste electrolytic manganese slag mineralized CO 2 Resource utilization method |
| CN114804177B (en) * | 2022-04-08 | 2023-09-05 | 中冶南方都市环保工程技术股份有限公司 | Mineralized CO of industrial solid waste electrolytic manganese slag 2 Resource utilization method |
| CN115784289A (en) * | 2022-12-07 | 2023-03-14 | 西南科技大学 | Method and system for preparing light calcium carbonate by electrolyzing manganese slag |
| CN115784289B (en) * | 2022-12-07 | 2024-04-30 | 西南科技大学 | Method and system for preparing light calcium carbonate from electrolytic manganese slag |
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Application publication date: 20121003 |