CN102115204A - Method for preparing manganese sulfate, ferrous sulfate and calcium sulfate from manganese ore tailings - Google Patents
Method for preparing manganese sulfate, ferrous sulfate and calcium sulfate from manganese ore tailings Download PDFInfo
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- CN102115204A CN102115204A CN2010106154842A CN201010615484A CN102115204A CN 102115204 A CN102115204 A CN 102115204A CN 2010106154842 A CN2010106154842 A CN 2010106154842A CN 201010615484 A CN201010615484 A CN 201010615484A CN 102115204 A CN102115204 A CN 102115204A
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Abstract
The invention provides a method for preparing manganese sulfate, ferrous sulfate and calcium sulfate from manganese ore tailings. The manganese ore tailings are pulverized to powders of 80 meshes to 100 meshes, the powders react with an excessive amount of dilute hydrochloric acid, and the reaction product is filtered to produce a filtrate; an excessive amount of sodium sulfide is added to the filtrate, and the reaction liquid is filtered to produce a filter cake containing manganese sulfide, ferrous sulfide and calcium sulfide; the filter cake containing manganese sulfide, ferrous sulfide and calcium sulfide reacts with a sulfuric acid solution, the reaction product is filtered to produce a filter cake of calcium sulfate and a filtrate containing manganese sulfate and ferrous sulfate, and the filtrate containing manganese sulfate and ferrous sulfate is distilled under a reduced pressure to produce a saturated solution; the saturated solution is cooled at different temperatures according to the difference in solubility between manganese sulfate and ferrous sulfate at different temperatures, so as to produce manganese sulfate crystals and ferrous sulfate crystals respectively; the crystallization product is filtered and dried to obtain a manganese sulfate product and a ferrous sulfate product respectively; and the filter cake of calcium sulfate is washed, dried and pulverized to obtain a calcium sulfate product.
Description
Technical field
The present invention relates to the comprehensive utilization of manganese mine tailing, particularly, relate to a kind of method for preparing manganous sulfate, ferrous sulfate and calcium sulfate with the manganese mine tailing.
Background technology
In the modern industry, manganese and compound thereof are applied to the every field of national economy.Wherein Iron And Steel Industry is most important field, accounts for 90%～95% with the manganese amount, mainly as reductor and the sweetening agent in ironmaking and the steelmaking process, and is used for alloying.All the other manganese of 10%～5% are used for other industrial circles; as chemical industry (making the various manganese salts that contain), light industry (being used for battery, match, seal lacquer, soapmaking etc.), building materials industry (tinting material and the decolourant of glass and pottery), national defense industry, electronic industry; and environment protection and husbandry, or the like.In a word, manganese has crucial strategic position in national economy.
The manganese mine tailing is the waste that forms in the manganese production process, a lot of materials of the inside all can be under field conditions (factors) as the rainwater leaching and stripping, enter into soil and water body causes environmental pollution.For a long time, because the manganese mine tailing can not fully utilize, can only stack storage, take a large amount of land resources, the serious environmental that also causes is polluted, and another fermentation owing to can not fully utilize in the manganese mine tailing, has also caused a large amount of wastings of resources.
Therefore, be necessary to explore the novel method that the manganese tailings comprehensive is administered and used.
Summary of the invention
With the Xiangtan Manganese Mine is example, and manganese mine tailing main chemical compositions and quality percentage composition thereof are as follows: Mn29.11%, calcium oxide 0.78%, magnesium oxide 0.34%, silicon-dioxide 23.45%, iron 4.74%.The manganese that the manganese mine tailing is contained mainly is tetravalence manganese, i.e. MnO2, and it has stronger oxidisability under acidic conditions, for this reason, can the tetravalence manganese in the manganese mine tailing be reduced to bivalent manganese by adding reducing substances.Based on this, the invention provides and a kind ofly prepare the method for manganous sulfate with the manganese mine tailing, this method is simple to operate, and facility investment is few, and manganese recovery utilization rate height is worthy of popularization.
Technical scheme of the present invention is as follows: a kind ofly prepare the method for manganous sulfate, ferrous sulfate and calcium sulfate with the manganese mine tailing, this method comprises following concrete steps:
Steps A: the manganese mine tailing is pulverized to the 80-100 order, mixed with excessive dilute hydrochloric acid solution, make hydrochloric acid and MnO2, calcium oxide, magnesium oxide and iron reaction generate Manganous chloride tetrahydrate, calcium chloride, magnesium chloride and iron protochloride; Filtering reacting liquid is removed insoluble silicon-dioxide, is contained mainly that chlorination is ferrous, the filtrate of calcium chloride, magnesium chloride and Manganous chloride tetrahydrate;
Step B: in the filtrate of steps A gained, add excessive sodium sulphite, stir reaction down, generate manganese sulfide precipitation, Iron sulfuret precipitation and sulfurated lime precipitation, filtering reacting liquid, obtain the filter cake of Containing Sulfur manganese, Iron sulfuret and sulfurated lime, contain chlorion, magnesium ion, sodium ion and sulfonium ion in the filtrate;
Step C: filter cake and sulphuric acid soln reaction with step B gained Containing Sulfur manganese, Iron sulfuret and sulfurated lime obtain the reaction solution of sulfur acid manganese, ferrous sulfate and calcium sulfate and discharge hydrogen sulfide; Stink damp body and function sodium hydroxide solution absorbs, and obtains sodium sulphite; Sodium sulphite returns step B recycling;
Step D: with the reacting liquid filtering of step C gained sulfur acid manganese, ferrous sulfate and calcium sulfate, obtain the filtrate of calcium sulfate filter cake and sulfur acid manganese and ferrous sulfate, the filtrate of sulfur acid manganese and ferrous sulfate is sent into alkali press that underpressure distillation is a saturated solution in the distiller, solubleness different under differing temps according to manganous sulfate and ferrous sulfate, crystallisation by cooling under different temperature, separate out manganous sulfate crystal and ferrous sulfate crystal respectively, filter, drying is obtained manganese sulfate product, ferrous sulfate product respectively;
Step e:, obtain the calcium sulfate product with step D gained calcium sulfate filter cake washing, drying and pulverizing.
The method for preparing manganous sulfate, ferrous sulfate and calcium sulfate with the manganese mine tailing of the present invention, made full use of manganese, iron and calcium that the manganese mine tailing contains, its step is simple, and facility investment is few, and manganous sulfate, ferrous sulfate and calcium sulfate yield are higher, are methods that is worthy of popularization.
Embodiment
Embodiment 1: a kind ofly prepare the method for Manganous chloride tetrahydrate, iron protochloride and calcium chloride with the manganese mine tailing, this method comprises following concrete steps:
Steps A: the manganese mine tailing is pulverized to the 80-100 order, mixed with excessive dilute hydrochloric acid solution, make hydrochloric acid and MnO2, calcium oxide, magnesium oxide and iron reaction generate Manganous chloride tetrahydrate, calcium chloride, magnesium chloride and iron protochloride; Filtering reacting liquid is removed insoluble silicon-dioxide, is contained mainly that chlorination is ferrous, the filtrate of calcium chloride, magnesium chloride and Manganous chloride tetrahydrate;
Step B: in the filtrate of steps A gained, add excessive sodium sulphite, stir reaction down, generate manganese sulfide precipitation, Iron sulfuret precipitation and sulfurated lime precipitation, filtering reacting liquid, obtain the filter cake of Containing Sulfur manganese, Iron sulfuret and sulfurated lime, contain chlorion, magnesium ion, sodium ion and sulfonium ion in the filtrate;
Step C: filter cake and hydrochloric acid soln reaction with step B gained Containing Sulfur manganese, Iron sulfuret and sulfurated lime obtain containing the reaction solution of Manganous chloride tetrahydrate, iron protochloride and calcium chloride and discharge hydrogen sulfide; Stink damp body and function sodium hydroxide solution absorbs, and obtains sodium sulphite; Sodium sulphite returns step B recycling;
Step D: the reaction solution that step C gained is contained Manganous chloride tetrahydrate, iron protochloride and calcium chloride is sent into alkali and is pressed that underpressure distillation is a saturated solution in the distiller, different according to Manganous chloride tetrahydrate, iron protochloride with calcium chloride solubleness, crystallisation by cooling under different temperature, separate out Manganous chloride tetrahydrate crystal, iron protochloride crystal and calcium chloride crystal respectively, filter, obtained Manganous chloride tetrahydrate product, iron protochloride product and calcium chloride product respectively.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of being submitted to.
Claims (1)
1. one kind prepares the method for manganous sulfate, ferrous sulfate and calcium sulfate with the manganese mine tailing, it is characterized in that this method comprises following concrete steps:
Steps A: the manganese mine tailing is pulverized to the 80-100 order, mixed with excessive dilute hydrochloric acid solution, make hydrochloric acid and MnO2, calcium oxide, magnesium oxide and iron reaction generate Manganous chloride tetrahydrate, calcium chloride, magnesium chloride and iron protochloride; Filtering reacting liquid is removed insoluble silicon-dioxide, is contained mainly that chlorination is ferrous, the filtrate of calcium chloride, magnesium chloride and Manganous chloride tetrahydrate;
Step B: in the filtrate of steps A gained, add excessive sodium sulphite, stir reaction down, generate manganese sulfide precipitation, Iron sulfuret precipitation and sulfurated lime precipitation, filtering reacting liquid, obtain the filter cake of Containing Sulfur manganese, Iron sulfuret and sulfurated lime, contain chlorion, magnesium ion, sodium ion and sulfonium ion in the filtrate;
Step C: filter cake and sulphuric acid soln reaction with step B gained Containing Sulfur manganese, Iron sulfuret and sulfurated lime obtain the reaction solution of sulfur acid manganese, ferrous sulfate and calcium sulfate and discharge hydrogen sulfide; Stink damp body and function sodium hydroxide solution absorbs, and obtains sodium sulphite; Sodium sulphite returns step B recycling;
Step D: with the reacting liquid filtering of step C gained sulfur acid manganese, ferrous sulfate and calcium sulfate, obtain the filtrate of calcium sulfate filter cake and sulfur acid manganese and ferrous sulfate, the filtrate of sulfur acid manganese and ferrous sulfate is sent into alkali press that underpressure distillation is a saturated solution in the distiller, solubleness different under differing temps according to manganous sulfate and ferrous sulfate, crystallisation by cooling under different temperature, separate out manganous sulfate crystal and ferrous sulfate crystal respectively, filter, drying is obtained manganese sulfate product, ferrous sulfate product respectively;
Step e:, obtain the calcium sulfate product with step D gained calcium sulfate filter cake washing, drying and pulverizing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106154842A CN102115204A (en) | 2010-12-31 | 2010-12-31 | Method for preparing manganese sulfate, ferrous sulfate and calcium sulfate from manganese ore tailings |
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| CN2010106154842A CN102115204A (en) | 2010-12-31 | 2010-12-31 | Method for preparing manganese sulfate, ferrous sulfate and calcium sulfate from manganese ore tailings |
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| CN102115204A true CN102115204A (en) | 2011-07-06 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274470A (en) * | 2013-06-17 | 2013-09-04 | 中南大学 | Method for preparing electronic-grade manganese sulfate by utilizing tungsten ore alkaline leaching slag |
| CN103274471A (en) * | 2013-06-17 | 2013-09-04 | 中南大学 | Method for preparing electronic-grade manganese sulfate by utilizing ferro-manganese alloy furnace slag |
| CN104556236A (en) * | 2014-12-23 | 2015-04-29 | 湖北浩元材料科技有限公司 | Preparation method of battery-grade manganese sulfate |
| CN109354071A (en) * | 2018-11-21 | 2019-02-19 | 安徽工业大学 | A method of LITHIUM BATTERY manganese sulfate is produced using manganese tailing and Titanium white waste sulfuric acid |
| CN109399723A (en) * | 2018-12-03 | 2019-03-01 | 安徽工业大学 | A method of electrolytic manganese dioxide is produced using manganese tailing and Titanium white waste sulfuric acid |
-
2010
- 2010-12-31 CN CN2010106154842A patent/CN102115204A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274470A (en) * | 2013-06-17 | 2013-09-04 | 中南大学 | Method for preparing electronic-grade manganese sulfate by utilizing tungsten ore alkaline leaching slag |
| CN103274471A (en) * | 2013-06-17 | 2013-09-04 | 中南大学 | Method for preparing electronic-grade manganese sulfate by utilizing ferro-manganese alloy furnace slag |
| CN103274470B (en) * | 2013-06-17 | 2014-12-10 | 中南大学 | Method for preparing electronic-grade manganese sulfate by utilizing tungsten ore alkaline leaching slag |
| CN103274471B (en) * | 2013-06-17 | 2014-12-10 | 中南大学 | Method for preparing electronic-grade manganese sulfate by utilizing ferro-manganese alloy furnace slag |
| CN104556236A (en) * | 2014-12-23 | 2015-04-29 | 湖北浩元材料科技有限公司 | Preparation method of battery-grade manganese sulfate |
| CN104556236B (en) * | 2014-12-23 | 2016-05-04 | 湖北浩元材料科技有限公司 | A kind of preparation method of LITHIUM BATTERY manganese sulfate |
| CN109354071A (en) * | 2018-11-21 | 2019-02-19 | 安徽工业大学 | A method of LITHIUM BATTERY manganese sulfate is produced using manganese tailing and Titanium white waste sulfuric acid |
| CN109354071B (en) * | 2018-11-21 | 2020-11-24 | 安徽工业大学 | Method for producing battery-grade manganese sulfate by using manganese tailings and waste sulfuric acid of titanium white |
| CN109399723A (en) * | 2018-12-03 | 2019-03-01 | 安徽工业大学 | A method of electrolytic manganese dioxide is produced using manganese tailing and Titanium white waste sulfuric acid |
| CN109399723B (en) * | 2018-12-03 | 2020-11-24 | 安徽工业大学 | Method for producing electrolytic manganese dioxide by using manganese tailings and titanium dioxide waste sulfuric acid |
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Application publication date: 20110706 |