CN102815751A - Method for smelting and preparing manganese sulfate from braunite - Google Patents
Method for smelting and preparing manganese sulfate from braunite Download PDFInfo
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- CN102815751A CN102815751A CN2012103512055A CN201210351205A CN102815751A CN 102815751 A CN102815751 A CN 102815751A CN 2012103512055 A CN2012103512055 A CN 2012103512055A CN 201210351205 A CN201210351205 A CN 201210351205A CN 102815751 A CN102815751 A CN 102815751A
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Abstract
The invention discloses a method for smelting and preparing manganese sulfate from braunite, which comprises the following steps: by using braunite as a raw material and natural gas as a reducer, sufficiently reducing the braunite with the natural gas in a reactor at the temperature of 800-900 DEG C for 0.5-2 hours, thereby obtaining a reduction product mainly comprising manganese monoxide; selectively leaching out the reduction product with dilute sulfuric acid, wherein the pH value in the leaching process and at the end point is controlled at 2.0-2.5; and neutralizing the ore slurry at the leaching end point with ammonia water to hydrolyze leached impurities in the ore slurry, filtering, and adding sodium dimethylaminosulfonate into the filtrate to remove heavy metals, thereby obtaining the manganese sulfate solution. The method disclosed by the invention has the advantages of high reduction efficiency, high leaching rate, high yield, low cost, environmental protection and the like.
Description
Technical field
The invention belongs to the black metal smelting technology field, relating in particular to a kind of is the method for feedstock production manganous sulfate with the brunite.
Background technology
The manganese resource of China mainly is rhodochrosite and pyrolusite, and brunite has a small amount of existence, mainly is distributed in ground such as Guangxi, Guizhou and Yunnan; The raw materials for metallurgy of manganese also mainly is rhodochrosite and pyrolusite, seldom relevant for the relevant report of the smelting technology of brunite.It is generally acknowledged that the application of brunite mainly is the rich manganese slag of pyrometallurgical smelting or ferromanganese, silicomanganese, rarely has the precedent that is used for hydrometallurgy electrowinning manganese.
Rhodochrosite is the most direct and topmost manganese raw material of electrowinning manganese, and the manganese in the rhodochrosite is mainly with MnCO
3Form exists, and manganese is Mn (II) valence state, can be directly makes manganese resource in the mineral aggregate get into solution with the form of manganous sulfate with the dilute sulphuric acid reaction and separates with impurity, realizes the extraction of valuable resource manganese in the manganese ore.
In addition, manganese oxide ore has multiple in natural existence form, and modal is pyrolusite, i.e. MnO
2, the manganese in the mineral is Mn (IV) valence state, thereby it has certain oxidisability, pyrolusite can not with directly effect and make the manganese stripping in the mineral get into solution of dilute sulphuric acid, must make Mn (IV) → Mn (II) earlier with the pyrolusite reduction.The method of reducing of pyrolusite can be divided into the fire reduction roasting and wet reducing directly leaches two kinds.The fire reduction roasting is commonly added hard coal and in 800 ℃～900 ℃ following roastings in rotary kiln, the shrend cooling that directly falls into the water of the material after the reducing roasting is leached the good manganese material of reduction with dilute sulphuric acid again and extracted manganese.Wet reducing technology is in solution, to have under reductive agent (like the pyrite etc.) existence condition directly to leach with sulfuric acid, and leaching process need be controlled at high temperature and the above extraction time of 3h more than 90 ℃, owing to need high temperature and high sulfuric acid concentration to leach; Impurity iron sial phosphorus and other can also leach with the metal species impurity of sulfuric acid reaction in the lump; The leaching cost is high, and the leach liquor foreign matter content is high, and the removal of impurities difficulty is big; The manganese yield is low; The current efficiency of electrowinning manganese is low, and energy consumption is high, is difficult for obtaining qualified electrowinning manganese product.Although above manganese smelting technology has minority electrodeposition manganese enterprise using, can't heavy industrialization.Therefore, though the manganese content of pyrolusite is generally high than rhodochrosite, it is main with rhodochrosite diluted acid extract technology still that manganese is smelted electrowinning manganese.
Brunite is another kind of oxidation class manganese ore, belongs to a kind of of oxidized form manganese resource, and the manganese in the mineral is approximately Mn (III) form, and the general formula of molecular structure of brunite is generally Mn
7SiO
12, be a kind of silicate minerals of complicacy, its structure can be regarded 3Mn as
2O
3MnSiO
3It is thus clear that, because the singularity of brunite moity will come brunite is smelted according to the reduction-acidleach condition of routine, there is big difficulty, be difficult to directly leach with sulfuric acid.Because domestic brunite reserves are less, up till now for this reason, do not see useful brunite as yet yet and carry out the relevant report that heavy industrialization is used.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art, provides that a kind of reduction efficiency is high, leaching yield is high, productive rate is high, cost is low, environmental protection, operational path are succinct is that raw material is smelted the method for preparing manganous sulfate with the brunite.
For solving the problems of the technologies described above; The technical scheme that the present invention proposes be a kind of be that raw material is smelted the method for preparing manganous sulfate with the brunite; May further comprise the steps: be raw material with the brunite; As reductive agent, in reaction unit (for example fixed bed, floating bed, tubulose reduction roaster, fluidizing furnace, rotary kiln etc.), brunite is fully reduced with Sweet natural gas by Sweet natural gas, reduction temperature is controlled at 800 ℃～900 ℃; The time of reduction reaction is 0.5h～2h, and obtaining after the reduction with the manganese monoxide is main reduzate; Again reduzate is leached with dilute sulphuric acid; The pH value of control leaching process and terminal point is 2.0～2.5; Carrying out selectivity leaches; The ore pulp that leaches terminal point makes the impurity hydrolysis of leaching in the ore pulp with the ammoniacal liquor neutralization, in filtrating, adds dimethylin sodium sulfonate (being called for short SDD) after filtering and removes heavy metal, can obtain manganese sulfate solution.
Above-mentioned with the brunite is, and raw material is smelted the method that prepare manganous sulfate, is used as in the said brunite of raw material manganese element mainly with Mn
7SiO
12Form exists, and granularity preferably is controlled at-20 orders～-200 orders (accounting for more than 80%), can realize through fragmentation, dry type magnetic separation, ball milling, fine grinding etc.
Above-mentioned is that raw material is smelted the method for preparing manganous sulfate with the brunite, and the concentration of said dilute sulphuric acid is preferably 1.0N～4.0N (equivalent concentration), and the time of agitation leach is preferably 0.5h～2h.
Above-mentioned with the brunite is, and raw material is smelted the method that prepare manganous sulfate, and the concentration of said ammoniacal liquor is preferably 10%～15% (mass concentration), in the ammoniacal liquor and after the pH value preferably be controlled at 6.5～6.8.
Above-mentioned is that raw material is smelted the method for preparing manganous sulfate with the brunite, preferred, only adds the dimethylin sodium sulfonate when removing heavy metal, preferably places 24h again behind the interpolation dimethylin sodium sulfonate.
Technique scheme of the present invention is with the raw material of the higher brunite of a kind of manganese content as the preparation manganous sulfate; And with the high Sweet natural gas of reducing activity as reductive agent efficient, cleaning; It can be in reactor drum or Reaktionsofen the fast restore brunite, and reduzate is mainly green manganese monoxide (with Mn
2O
3In+Mn of 3 valence states is reduced to+MnO of divalent attitude) and, the reduction transformation efficiency of manganese reaches more than 99%; Leach with dilute sulphuric acid normal temperature again; Through acidity and the time etc. of control leaching process, can the good leaching ore pulp of output strainability, the leaching yield that contains the manganese reduzate can reach more than 98%; By contrast, the leaching yield of the reducing roasting technology manganese of conventional pyrolusite has only about 78%.In addition; The foreign matter content of leach liquor of the present invention is low; Only need to make the hydrolysis such as impurity silicon, aluminium, iron, arsenic of leaching with the weak ammonia neutralization to leaching the terminal point ore pulp; Need not to add the preliminary removing heavy metals of ammonium sulfide, filtrate filtered is directly added SDD can remove heavy metals such as a spot of Cu, Co, Ni, Zn, obtains qualified purification of manganese sulfate liquid at last.
Compared with prior art, the invention has the advantages that:
(1) existing optional reductive agent kind and method of reducing are a lot; But for brunite; The reduction effect of existing method of reducing is all not ideal enough; The present invention has adopted the reductive agent of the Sweet natural gas that reducing activity is high, attribute cleans as brunite, and not only reduction rate is fast, utilization ratio is high, has guaranteed the high reduction ratio of manganese in the brunite; And adopt the Sweet natural gas reduction, and it is remaining can in leached mud, not increase solid, and it is few to leach the quantity of slag, and technology is succinct, does not produce secondary pollution;
(2) the present invention adopts the selective control leaching-out technique (promptly through control vitriolic addition to above-mentioned reduzate; The pH value stabilization that makes leaching process is 2.0～2.5; Prevent the excessive stripping of impurity ferrosilicoaluminum etc., and the manganese monoxide that reduction forms very easily with the sulfuric acid reaction stripping) leach, not only beavy metal impurity content is few in the leaching ore pulp of acquisition; And it is low to purify cost, and leaching yield is high;
(3) higher reduction efficiency of the present invention and higher leaching efficiency; The manganese sulfate solution that has guaranteed the present invention's preparation has higher manganese yield; And the leaching of manganese element of the present invention acid consumption is merely about 50% of conventional electrowinning preparation of manganese, and the technology cost is low, and energy consumption and resource consumption are few; The qualified manganese sulfate solution that makes can be used as the raw material of smelting electrowinning manganese, at the electrowinning manganese industry extraordinary popularizing application prospect is arranged.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Below in conjunction with Figure of description and specific embodiment the present invention is further described.
Embodiment 1:
Algeria's somewhere brunite, the raw ore chemical ingredients mainly comprises Mn 43.8%, SiO
212.3%, Al
2O
31.79%, P 1.12%, and Fe 0.34%; CaO 4.33% and MgO 1.87% are raw material with this brunite, adopt method of the present invention as shown in Figure 1 to prepare manganous sulfate; May further comprise the steps:, pair roller broken through jaw, ball milling make the granularity of this brunite account for 80% for-100 orders, get 100g after levigate the brunite material and place in the corundum boat, put into the tube furnace of closed at both ends then; Electrically heated is warmed up to 800 ℃～900 ℃, and feeding nitrogen (or other protective gas) feeds Sweet natural gas continuously and carries out reducing roasting after discharging the interior air of burner hearth; Insulation reduction 0.5h (0.5～2h all can) stops insulation, stops to feed Sweet natural gas; Change feeding nitrogen protection cooling, be cooled to the material (the manganese material that contains behind the roasting reduction is green) after reduction is taken out in back below 100 ℃, the dilute sulphuric acid that with concentration is 2.3N then is by solid-to-liquid ratio (ml/g) agitation leach in 8: 1; The pH value of control leaching process and terminal point is 2.0～2.5, and extraction time is 1h; The ore pulp that leaches terminal point adds 15% ammoniacal liquor makes pH value of slurry transfer to 6.5～6.8, filters (taking out silicon, aluminium, iron, phosphorus, arsenic etc.) at last, and through measuring, the leaching yield of manganese reaches 98.3% in the filtrating; Add SDD removing heavy metals (Cu, Co, Ni, Zn etc.) in the filtrating again, leave standstill the 24h after-filtration, filtrating is the manganese sulfate solution that foreign matter content closes the requirement of symbol electrowinning manganese, and it can be used for electrowinning manganese.Through detecting, the composition of the manganese sulfate solution of present embodiment preparation is following:
Mn53.81g/L，Fe0.56mg/L，SiO
23.8?mg/L，Al
2O
34.0?mg/L，As0.2?mg/L，P0.28mg/L，Sb3.31mg/L，Ni0.86mg/L、Co0.45mg/L、Cu0.23mg/L、Zn0.51mg/L。
Embodiment 2:
Somewhere, Guizhou brunite, the raw ore main chemical compositions comprises Mn 28.65%, SiO
223.28%, Al
2O
37.35%, P 0.35%, and Fe 3.39%; CaO 2.83%, and MgO 1.31%, is raw material with this brunite 100g; Adopt method of the present invention as shown in Figure 1 to prepare manganous sulfate, may further comprise the steps:, pair roller broken through jaw, ball milling make the granularity of this brunite account for 80% for-60 orders, then in the rotary kiln of closed at both ends; Electrically heated is warmed up to 820 ℃～880 ℃, begins to add continuously brunite, after feeding nitrogen (or other protective gas) is discharged the interior air of burner hearth; Feed Sweet natural gas continuously and carry out reducing roasting, the motor speed of adjustment rotary kiln guarantees that the high-temperature material residence time is 1h (guaranteeing that promptly the high temperature reduction time is 1h); Discharging after the reduction chilling that directly falls into the water takes out the material after the reduction, then with the 1.9N dilute sulphuric acid by solid-to-liquid ratio (ml/g) agitation leach in 5: 1; The pH value of control leaching process and terminal point is 2.0～2.5, and extraction time is 0.5h; The ore pulp that leaches terminal point adds 12% ammoniacal liquor makes pH value of slurry transfer to 6.5～6.8, filters (taking out silicon, aluminium, iron, phosphorus, arsenic etc.) at last, and through measuring, the leaching yield of manganese reaches 98.7% in the filtrating; Add SDD removing heavy metals (Cu, Co, Ni, Zn etc.) in the filtrating again, leave standstill the 24h after-filtration, filtrating is the manganese sulfate solution that foreign matter content closes the requirement of symbol electrowinning manganese, and it can be used for electrowinning manganese.Through detecting, the composition of the manganese sulfate solution of present embodiment preparation is following:
Mn53.01g/L，Fe1.45mg/L，SiO
25.8?mg/L，Al
2O
36.0?mg/L，As0.3?mg/L，P0.31mg/L，?Sb2.21mg/L，Ni0.58mg/L、Co0.38mg/L、Cu0.34mg/L、Zn0.42mg/L。
Claims (5)
1. one kind is that raw material is smelted the method for preparing manganous sulfate with the brunite; May further comprise the steps: be raw material with the brunite; As reductive agent, brunite is fully reduced with Sweet natural gas by Sweet natural gas, reduction temperature is controlled at 800 ℃～900 ℃; The time of reduction reaction is 0.5h～2h, and obtaining after the reduction with the manganese monoxide is main reduzate; Again reduzate is leached with dilute sulphuric acid; The pH value of control leaching process and terminal point is 2.0～2.5; Carrying out selectivity leaches; The ore pulp that leaches terminal point makes the impurity hydrolysis of leaching in the ore pulp with the ammoniacal liquor neutralization, in filtrating, adds the dimethylin sodium sulfonate after filtering and removes heavy metal, can obtain manganese sulfate solution.
2. according to claim 1 is that raw material is smelted method prepare manganous sulfate with the brunite, it is characterized in that: be used as in the said brunite of raw material manganese element mainly with Mn
7SiO
12Form exists, and granularity is controlled at-20 orders～-200 orders, the manganese content 20%～55% in the brunite.
3. according to claim 1 is that raw material is smelted the method for preparing manganous sulfate with the brunite, and it is characterized in that: the concentration of said dilute sulphuric acid is 1.0～4.0N, and the time of agitation leach is 0.5h～2h.
4. according to claim 1 is that raw material is smelted method prepare manganous sulfate with the brunite, and it is characterized in that: the concentration of said ammoniacal liquor is 10%～15%, in the ammoniacal liquor and after the pH value be controlled at 6.5～6.8.
5. according to claim 1 is that raw material is smelted the method for preparing manganous sulfate with the brunite, it is characterized in that: only add the dimethylin sodium sulfonate when removing heavy metal, place 24h again behind the interpolation dimethylin sodium sulfonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609753A (en) * | 2019-01-08 | 2019-04-12 | 重庆大学 | A method of standby manganese carbonate is soaked by additive ammonia of ammonium acid fluoride |
| CN109628739A (en) * | 2019-01-08 | 2019-04-16 | 重庆大学 | A method of manganese ore ammonia leaching rate is improved by additive of nitrilotriacetic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341777A (en) * | 2000-09-04 | 2002-03-27 | 肖峥 | High-purity high-activity electrolytic magnese dioxide |
| CN1390265A (en) * | 1999-09-20 | 2003-01-08 | 尤尼瑟驰有限公司 | Solid state reduction of oxides |
| CN101591731A (en) * | 2009-06-30 | 2009-12-02 | 长沙矿冶研究院 | Reduction roasting method and device for high-valence manganese ores |
| CN101914676A (en) * | 2010-09-08 | 2010-12-15 | 中南大学 | Manganese oxide mineral sulfur-based fire reduction method |
| CN102674464A (en) * | 2012-03-30 | 2012-09-19 | 梧州三和新材料科技有限公司 | Preparation method of manganous oxide with ultralow calcium, magnesium and heavy metal impurity concentrations |
-
2012
- 2012-09-20 CN CN201210351205.5A patent/CN102815751B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390265A (en) * | 1999-09-20 | 2003-01-08 | 尤尼瑟驰有限公司 | Solid state reduction of oxides |
| CN1341777A (en) * | 2000-09-04 | 2002-03-27 | 肖峥 | High-purity high-activity electrolytic magnese dioxide |
| CN101591731A (en) * | 2009-06-30 | 2009-12-02 | 长沙矿冶研究院 | Reduction roasting method and device for high-valence manganese ores |
| CN101914676A (en) * | 2010-09-08 | 2010-12-15 | 中南大学 | Manganese oxide mineral sulfur-based fire reduction method |
| CN102674464A (en) * | 2012-03-30 | 2012-09-19 | 梧州三和新材料科技有限公司 | Preparation method of manganous oxide with ultralow calcium, magnesium and heavy metal impurity concentrations |
Non-Patent Citations (1)
| Title |
|---|
| 尹文新等: "电解二氧化锰制备技术的研究进展", 《金属矿山》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609753A (en) * | 2019-01-08 | 2019-04-12 | 重庆大学 | A method of standby manganese carbonate is soaked by additive ammonia of ammonium acid fluoride |
| CN109628739A (en) * | 2019-01-08 | 2019-04-16 | 重庆大学 | A method of manganese ore ammonia leaching rate is improved by additive of nitrilotriacetic acid |
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| CN102815751B (en) | 2014-07-23 |
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