CN103214201B - Method for comprehensively utilizing electrolytic manganese residues - Google Patents
Method for comprehensively utilizing electrolytic manganese residues Download PDFInfo
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- CN103214201B CN103214201B CN201310133749.9A CN201310133749A CN103214201B CN 103214201 B CN103214201 B CN 103214201B CN 201310133749 A CN201310133749 A CN 201310133749A CN 103214201 B CN103214201 B CN 103214201B
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- Y—GENERAL 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
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Abstract
The invention discloses a method for comprehensively utilizing electrolytic manganese residues. The method comprises the following steps of: firstly carrying out flotation on electrolytic manganese residues in a flotation machine, and screening out dihydrate gypsum; carrying out strong magnetic separation on tailings subjected to flotation, and singling out ferromanganese bulk concentrate and tailings; smelting the ferromanganese bulk concentrate to obtain rich-manganese slag; and burning the dihydrate gypsum obtained through floatation with smelting waste heat so as to remove ammonia and sulfur for production of ammonia water and sulfuric acid and co-production of cement. The tailings discharged in the end are non-toxic and harmless and can be used for producing baking-free bricks, land rehabilitation or underground filling. According to the method, lots of manganese residues can be consumed, multiple related products are obtained while the environmental problem and the safety problem are solved, and thus the purposes of turning waste into wealth and cyclical utilization are achieved.
Description
Technical field
The invention belongs to mining industry and building material industry technical field, relate to a kind of method of electrolytic manganese residues comprehensive utilization.
Background technology
Electrolytic manganese residues is in manganous carbonate breeze, to add sulphuric acid soln to obtain manganese sulfate solution in order to produce the filter residue of electrolytic metal Mn or electrolytic manganese dioxide.Its production process is in reactor, to add sulphuric acid soln and the reaction of manganous carbonate breeze to generate manganous sulfate, then through purification process such as deironing sulphur removal; Then filter with pressure filter, filtrate enters electrolysis in electrolyzer, and the filter cake of discharge is so-called electrolytic manganese residues.Electrolytic manganese residues quantity discharged is quite large, every production 1 t electrolytic metal Mn, and the particle manganese slag tiny and that contain a certain amount of harmful element discharging is about 5～6t.The valuable metal such as residual a certain amount of ferromanganese in electrolytic manganese residues, ammonia and a large amount of calcium sulfate etc.Due to the existence of vitriol in electrolytic manganese residues, when electrolytic manganese residues is applied to brickmaking and other building materials, can cause that product easily gets damp and plays hickie.When electrolytic manganese residues should be used as fertilizer, can make soil compaction.So current electrolysis manganese slag can only be stored up processing.Store up these acidleach electrolytic manganese residues, increased on the one hand the expense such as enterprise's land acquisition and place disposal, the long-term stacking of electrolytic manganese manganese slag on the other hand, some harmful elements can permeate by soil layer, enter in earth's surface and underground water, affect groundwater resource, contaminate environment.At present, the existing considerable report about electrolytic manganese residues brickmaking, cement processed, composting material.But, owing to not resolving vitriol and the disadvantageous effect of ammonia to brick, cement, fertilizer in manganese slag in existing electrolytic manganese residues treatment technology, cause these technology all could not be successfully for the production of practice.Because existing electrolytic manganese residues processing exists technical problem, find at present the quite difficulty of Tailings Dam of storing up electrolytic manganese residues, the normal production of considerable part electrolytic metal Mn and electrolytic manganese dioxide enterprise is restricted.How effectively to develop electrolytic manganese residues, become manganese industry technical barrier the most in the urgent need to address.
The patent No. is 200810044775 to disclose the technique of a kind of electrolytic manganese residues comprehensive utilization, and this invention is reclaimed recyclable materials in electrolytic manganese residues by repeatedly washing, filtering, and solves problem of environmental pollution.But this invention still fails to make full use of the available stock in manganese slag.
Summary of the invention
The present invention, for solving the deficiencies in the prior art, provides a kind of technique simple, with low cost, in solving the environmental problem and potential safety hazard of electrolytic manganese residues, obtains multiple related product, and reaching turns waste into wealth, the method for the electrolytic manganese residues comprehensive utilization of recycle.
Concrete technical scheme of the present invention is as follows:
A method for electrolytic manganese residues comprehensive utilization is first carried out electrolytic manganese residues flotation in flotation machine, selects dihydrate gypsum; Again the tailings after flotation is carried out to high intensity magnetic separation, select ferromanganese collective concentrate and tailings; Ferromanganese collective concentrate is smelted and is obtained rich manganese slag; Smelt dihydrate gypsum calcining deamination, desulfurization jointly producing cement that waste heat obtains for flotation, the ammonia reclaiming in calcination process and sulphur content are not prepared ammoniacal liquor and sulfuric acid.
Above-described flotation is divided into the section of roughly selecting and selected section of bis flotation technique, and the described section of roughly selecting adopts two slightly to sweep a smart flow process, and described selected section adopts one slightly to sweep three smart flow processs, control dihydrate gypsum containing gypsum 85%
It is that adjusting agent is sodium carbonate that the above-described section of roughly selecting adopts flotation reagent, and inhibitor is Sodium hexametaphosphate 99 and water glass, and collecting agent is soap; The consumption of sodium carbonate, Sodium hexametaphosphate 99, water glass, soap is respectively: 500-1000 gram/ton, 300-600 gram/ton, 1000 grams/ton, 250-400 gram/ton.
Above-described selected section of employing flotation reagent is that inhibitor is acidic water glass, and collecting agent is soap; The consumption of water glass, soap is respectively: 800-1200 gram/ton, 15 grams/ton.
Magneticstrength in above-described high intensity magnetic separation step is 15000-17000 Gauss, and the ferromanganese content of controlling ferromanganese concentrate is greater than 30%.
The desulfurated plaster jointly producing cement of the dihydrate gypsum that above-described flotation obtains after calcining, the ferromanganese collective concentrate that magnetic separation obtains is produced rich manganese slag, byproduct ammoniacal liquor and sulfuric acid return to Electrolytic Manganese Metal Plant and make raw materials for production, and tailings returns reclaims or filling or the non-burning brick raw material of do production.
Advantage of the present invention is:
1, the present invention adopts flotation technology, deviate from the calcium sulfate in manganese slag, the ferromanganese metal in manganese slag is reclaimed in magnetic separation, and the nontoxic tailings after magnetic separation can be used for producing non-burning brick, also can be for land reclamation or filling in mine, be conducive to solve environmental problem and the safety problem of electrolytic manganese residues.
2, in the present invention, the dihydrate gypsum of flotation can be calcined desulfurization sulfuric acid processed, reclaim ammonia and desulfurated plaster jointly producing cement; The ferromanganese collective concentrate that high intensity magnetic separation reclaims can be used for producing rich manganese slag, makes full use of resource, reach turn waste into wealth, the object of recycle.
3, the present invention utilizes and produces the waste heat of rich manganese slag and supplement the common heat producing of a certain amount of high sulphur coal again and carry out dihydrate gypsum calcining desulfurization (relieving haperacidity) jointly producing cement, reclaims ammonia simultaneously, thereby reaches the object of energy-conserving and environment-protective.
Additive source in the present invention is wide, and price is low, and cost is low; Processing technological flow of the present invention is simple, easy to operate simultaneously, is beneficial to very much popularization.
Brief description of the drawings
Fig. 1 is the process flow diagram of floatation process of the present invention;
Fig. 2 is the process flow diagram of the method for electric manganese slag comprehensive utilization of the present invention.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is further described.
Embodiment 1:
A kind of method of electrolytic manganese residues comprehensive utilization, first electrolytic manganese residues is carried out in flotation machine to flotation, select dihydrate gypsum, flotation adopts the bis flotation technique of the section of roughly selecting and selected section, and the section of roughly selecting employing flotation reagent is that adjusting agent is sodium carbonate, and inhibitor is Sodium hexametaphosphate 99 and water glass, collecting agent is soap, the consumption of flotation reagent sodium carbonate is that 500 grams/ton, the consumption of Sodium hexametaphosphate 99 are 600 grams/ton, and the consumption of water glass is 1000 grams/ton, and the consumption of soap is 400 grams/ton.Selected section adopts flotation reagent is that inhibitor is acidic water glass, and collecting agent is soap, and wherein the consumption of acidic water glass is that 1200 grams/ton, the consumption of soap are 15 grams/ton.The described bis flotation section of roughly selecting adopts two slightly to sweep a smart flow process, and described selected section adopts one slightly to sweep three smart flow processs, control dihydrate gypsum containing gypsum 85%.Again the tailings after flotation is carried out to high intensity magnetic separation in magneticstrength is 15000 Gausses' magnetic field, select ferromanganese collective concentrate and tailings, the ferromanganese content of controlling ferromanganese collective concentrate is greater than 30%; Ferromanganese concentrate is smelted and is obtained rich manganese slag; The waste heat of smelting is calcined for dihydrate gypsum together with high sulphur coal; Dihydrate gypsum is first dried according to a conventional method, after mixing, carries out raw material preparation with coal dust, clay, then calcines, and obtains grinding and producing cement after grog, and the ammonia reclaiming in process and sulphur content are not prepared ammoniacal liquor and sulfuric acid.Ammoniacal liquor and sulfuric acid can return to Electrolytic Manganese Metal Plant and make raw materials for production, and tailings returns reclaims or filling or the non-burning brick raw material of do production.
Embodiment 2:
A kind of method of electrolytic manganese residues comprehensive utilization, first electrolytic manganese residues is carried out in flotation machine to flotation, select dihydrate gypsum, flotation adopts the bis flotation technique of the section of roughly selecting and selected section, and the section of roughly selecting employing flotation reagent is that adjusting agent is sodium carbonate, and inhibitor is Sodium hexametaphosphate 99 and water glass, collecting agent is soap, the consumption of flotation reagent sodium carbonate is that 700 grams/ton, the consumption of Sodium hexametaphosphate 99 are 500 grams/ton, and the consumption of water glass is 1000 grams/ton, and the consumption of soap is 300 grams/ton.Selected section adopts flotation reagent is that inhibitor is acidic water glass, and collecting agent is soap, and wherein the consumption of acidic water glass is that 1000 grams/ton, the consumption of soap are 15 grams/ton.The described bis flotation section of roughly selecting adopts two slightly to sweep a smart flow process, and described selected section adopts one slightly to sweep three smart flow processs, control dihydrate gypsum containing gypsum 85%.Again the tailings after flotation is carried out to high intensity magnetic separation in magneticstrength is 16000 Gausses' magnetic field, select ferromanganese collective concentrate and tailings, the ferromanganese content of controlling ferromanganese collective concentrate is greater than 30%; Ferromanganese concentrate is smelted and is obtained rich manganese slag; The waste heat of smelting is calcined for dihydrate gypsum together with high sulphur coal; Dihydrate gypsum is first dried according to a conventional method, after mixing, carries out raw material preparation with coal dust, clay, then calcines, and obtains grinding and producing cement after grog, and the ammonia reclaiming in process and sulphur content are not prepared ammoniacal liquor and sulfuric acid.Ammoniacal liquor and sulfuric acid can return to Electrolytic Manganese Metal Plant and make raw materials for production, and tailings returns reclaims or filling or the non-burning brick raw material of do production.
Embodiment 3:
A kind of method of electrolytic manganese residues comprehensive utilization, first electrolytic manganese residues is carried out in flotation machine to flotation, select dihydrate gypsum, flotation adopts the bis flotation technique of the section of roughly selecting and selected section, and the section of roughly selecting employing flotation reagent is that adjusting agent is sodium carbonate, and inhibitor is Sodium hexametaphosphate 99 and water glass, collecting agent is soap, the consumption of flotation reagent sodium carbonate is that 900 grams/ton, the consumption of Sodium hexametaphosphate 99 are 400 grams/ton, and the consumption of water glass is 1000 grams/ton, and the consumption of soap is 280 grams/ton.Selected section adopts flotation reagent is that inhibitor is acidic water glass, and collecting agent is soap, and wherein the consumption of acidic water glass is that 900 grams/ton, the consumption of soap are 15 grams/ton.The described bis flotation section of roughly selecting adopts two slightly to sweep a smart flow process, and described selected section adopts one slightly to sweep three smart flow processs, control dihydrate gypsum containing gypsum 85%.Again the tailings after flotation is carried out to high intensity magnetic separation in magneticstrength is 16500 Gausses' magnetic field, select ferromanganese collective concentrate and tailings, the ferromanganese content of controlling ferromanganese collective concentrate is greater than 30%; Ferromanganese concentrate is smelted and is obtained rich manganese slag; The waste heat of smelting is calcined for dihydrate gypsum together with high sulphur coal; Dihydrate gypsum is first dried according to a conventional method, after mixing, carries out raw material preparation with coal dust, clay, then calcines, and obtains grinding and producing cement after grog, and the ammonia reclaiming in process and sulphur content are not prepared ammoniacal liquor and sulfuric acid.Ammoniacal liquor and sulfuric acid can return to Electrolytic Manganese Metal Plant and make raw materials for production, and tailings returns reclaims or filling or the non-burning brick raw material of do production.
Embodiment 4:
A kind of method of electrolytic manganese residues comprehensive utilization, first electrolytic manganese residues is carried out to flotation in flotation medicine machine, select dihydrate gypsum, flotation adopts the section of roughly selecting and the bis flotation technique of selected section, it is that adjusting agent is sodium carbonate that the section of roughly selecting adopts flotation reagent, inhibitor is Sodium hexametaphosphate 99 and water glass, collecting agent is soap, the consumption of flotation reagent sodium carbonate is that 1000 grams/ton, the consumption of Sodium hexametaphosphate 99 are 300 grams/ton, the consumption of water glass is 1000 grams/ton, and the consumption of soap is 250 grams/ton.Selected section adopts flotation reagent is that inhibitor is acidic water glass, and collecting agent is soap, and wherein the consumption of acidic water glass is that 800 grams/ton, the consumption of soap are 15 grams/ton.The described bis flotation section of roughly selecting adopts two slightly to sweep a smart flow process, and described selected section adopts one slightly to sweep three smart flow processs, control dihydrate gypsum containing gypsum 85%.Again the tailings after flotation is carried out to high intensity magnetic separation in magneticstrength is 17000 Gausses' magnetic field, select ferromanganese collective concentrate and tailings, the ferromanganese content of controlling ferromanganese collective concentrate is greater than 30%; Ferromanganese concentrate is smelted and is obtained rich manganese slag; The waste heat of smelting is calcined for dihydrate gypsum together with high sulphur coal; Dihydrate gypsum is first dried according to a conventional method, after mixing, carries out raw material preparation with coal dust, clay, then calcines, and obtains grinding and producing cement after grog, and the ammonia reclaiming in process and sulphur content are not prepared ammoniacal liquor and sulfuric acid.Ammoniacal liquor and sulfuric acid can return to Electrolytic Manganese Metal Plant and make raw materials for production, and tailings returns reclaims or filling or the non-burning brick raw material of do production.
Claims (3)
1. a method for electrolytic manganese residues comprehensive utilization, is characterized in that: first electrolytic manganese residues is carried out in flotation machine to flotation, select dihydrate gypsum; Again the tailings after flotation is carried out to high intensity magnetic separation, select ferromanganese collective concentrate and tailings; Ferromanganese collective concentrate is smelted and is obtained rich manganese slag; Smelt dihydrate gypsum calcining deamination, desulfurization jointly producing cement that waste heat obtains for flotation, the ammonia reclaiming in calcination process and sulphur content are not prepared ammoniacal liquor and sulfuric acid;
Described flotation is divided into two step process, and the section of roughly selecting flotation adopts two slightly to sweep a smart flow process, and selected section adopts one slightly to sweep three smart flow processs, obtains dihydrate gypsum containing gypsum 85%;
Described roughing flotation section adopts flotation reagent to be: adjusting agent is sodium carbonate, inhibitor is Sodium hexametaphosphate 99 and water glass, collecting agent is soap, and the consumption of sodium carbonate, Sodium hexametaphosphate 99, water glass, soap is respectively: 500-1000 gram/ton, 300-600 gram/ton, 1000 grams/ton, 250-400 gram/ton;
Selected section of employing flotation reagent of described flotation is that inhibitor is acidic water glass, and collecting agent is soap; The consumption of acidic water glass, soap is respectively: 800-1200 gram/ton, 15 grams/ton.
2. the method for a kind of electrolytic manganese residues comprehensive utilization according to claim 1, is characterized in that: the magneticstrength in described high intensity magnetic separation operation is 15000-17000 Gauss, and the ferromanganese content of controlling ferromanganese collective concentrate is greater than 30%.
3. the method for a kind of electrolytic manganese residues comprehensive utilization according to claim 1, it is characterized in that: the dihydrate gypsum that described electrolytic manganese residues flotation obtains is desulfurization jointly producing cement after calcining, the ferromanganese collective concentrate that magnetic separation obtains is produced rich manganese slag, byproduct ammoniacal liquor and sulfuric acid return to Electrolytic Manganese Metal Plant and make raw materials for production, and tailings returns reclaims or filling or the non-burning brick raw material of do production.
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| CN104131167A (en) * | 2014-07-11 | 2014-11-05 | 广西大学 | Method for recovering selenium and manganese in manganese anode slime by using microwaves |
| CN104141049B (en) * | 2014-08-04 | 2016-10-12 | 云南天地行节能科技有限公司 | The integrated treatment of a kind of zinc slag utilizes technique |
| CN105461264B (en) * | 2015-11-20 | 2018-05-08 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of manganese ore slag bake-free brick and preparation method thereof |
| CN107129203B (en) * | 2017-04-25 | 2019-04-30 | 三峡大学 | A kind of electrolytic manganese residues base paste filling material and preparation method thereof |
| CN107601528A (en) * | 2017-10-19 | 2018-01-19 | 重庆前跃环境治理有限公司 | A kind of electrolytic manganese residues reclaim processing technology |
| CN108264233B (en) * | 2018-02-05 | 2021-05-14 | 北京工业大学 | Method for comprehensively utilizing electrolytic manganese slag and preparing microcrystalline glass |
| CN111644269B (en) * | 2020-06-02 | 2022-04-29 | 中蓝长化工程科技有限公司 | Method for comprehensively utilizing electrolytic manganese slag resources |
| CN114715944A (en) * | 2020-12-22 | 2022-07-08 | 杨成龙 | Preparation of high-purity manganese sulfate by manganese tailings high-pressure crystallization |
| CN114289174B (en) * | 2021-11-17 | 2023-11-24 | 镇康县振兴矿业开发有限责任公司 | Quality improvement and silicon reduction process and device for iron ore concentrate |
| CN114455893B (en) * | 2022-01-27 | 2023-06-09 | 中国地质科学院矿产综合利用研究所 | Method for treating pollution of electrolytic manganese slag tailing pond by cementing controlled release |
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| CN101306425B (en) * | 2008-06-24 | 2010-06-02 | 卿富安 | Electrolytic manganese slag comprehensive utilization technique |
| CN101371998A (en) * | 2008-08-27 | 2009-02-25 | 花垣县强桦矿业有限责任公司 | Flotation method of low ore grade manganous carbonate ore |
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