CN102815751B - Method for smelting and preparing manganese sulfate from braunite - Google Patents
Method for smelting and preparing manganese sulfate from braunite Download PDFInfo
- Publication number
- CN102815751B CN102815751B CN201210351205.5A CN201210351205A CN102815751B CN 102815751 B CN102815751 B CN 102815751B CN 201210351205 A CN201210351205 A CN 201210351205A CN 102815751 B CN102815751 B CN 102815751B
- Authority
- CN
- China
- Prior art keywords
- brunite
- manganese
- raw material
- taking
- smelting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
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 black metal smelting technology field, relate in particular to a kind of method of preparing manganous sulfate taking brunite as raw material.
Background technology
The manganese resource of China is mainly rhodochrosite and pyrolusite, and brunite has a small amount of existence, is mainly distributed in the ground such as Guangxi, Guizhou and Yunnan; The raw materials for metallurgy of manganese is mainly also rhodochrosite and pyrolusite, seldom has the relevant report about the smelting technology of brunite.It is generally acknowledged, the application of brunite is mainly the rich manganese slag of pyrometallurgical smelting or ferromanganese, silicomanganese, rarely has the precedent for hydrometallurgy electrowinning manganese.
Rhodochrosite is the most direct and topmost manganese raw material of electrowinning manganese, and the manganese in rhodochrosite is mainly with MnCO
3form exists, and manganese is Mn(II) valence state, can directly make the manganese resource in mineral aggregate enter solution and separate with impurity with the form of manganous sulfate with dilute sulphuric acid reaction, realize the extraction of valuable resource manganese in manganese ore.
In addition, manganese oxide ore has multiple in natural existence form, and modal is pyrolusite, i.e. MnO
2, the manganese in mineral is Mn(IV) and valence state, thereby it has certain oxidisability, and pyrolusite can not make the manganese in mineral be extracted into solution with dilute sulphuric acid direct effect, must, first by pyrolusite reduction, make Mn(IV) → Mn(II).The method of reducing of pyrolusite can be divided into fire reduction roasting and wet reducing directly leaches two kinds.Hard coal roasting at 800 DEG C～900 DEG C are commonly added in fire reduction roasting in rotary kiln, and the shrend that directly falls into the water of the material after reducing roasting is cooling, then leach with dilute sulphuric acid the manganese material having reduced and extract manganese.Wet reducing technique is in solution, to have under reductive agent (as pyrite etc.) existence condition directly to leach with sulfuric acid, leaching process need to be controlled at more than 90 DEG C high temperature and extraction time more than 3h, due to needs high temperature and the leaching of high sulfuric acid concentration, impurity iron sial phosphorus and other can also leach in the lump with the metal species impurity of sulfuric acid reaction, leaching cost is high, leach liquor foreign matter content is high, removal of impurities difficulty is large, manganese yield is low, the current efficiency of electrowinning manganese is low, 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,, although the manganese content of pyrolusite is generally high than rhodochrosite, manganese is smelted electrowinning manganese still taking rhodochrosite diluted acid leaching technique as main.
Brunite is another kind of oxidation class manganese ore, belongs to the one of oxidized form manganese resource, and the manganese in mineral is approximately Mn(III) form, the general formula of molecular structure of brunite is generally Mn
7siO
12, be a kind of silicate minerals of complexity, its structure can be regarded 3Mn as
2o
3mnSiO
3.Visible, due to the singularity of brunite moiety, smelt brunite according to conventional reduction-acidleach condition, there is larger difficulty, be difficult to directly leach with sulfuric acid.Because domestic brunite reserves are less, up till now for this reason, the relevant report that also there is not yet useful brunite and carry out heavy industrialization application.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the 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 smelts the method for preparing manganous sulfate taking brunite as raw material.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of method of preparing manganous sulfate of smelting taking brunite as raw material, comprise the following steps: taking brunite as raw material, using Sweet natural gas as reductive agent, such as, in reaction unit (fixed bed, floating bed, tubulose reduction roaster, fluidizing furnace, rotary kiln etc.) brunite is fully reduced by Sweet natural gas, reduction temperature is controlled at 800 DEG C～900 DEG C, the time of reduction reaction is 0.5h～2h, obtains taking manganese monoxide as main reduzate after reduction; Again reduzate is leached with dilute sulphuric acid, the pH value of controlling leaching process and terminal is 2.0～2.5, carry out selectivity leaching, the ore pulp ammonia neutralization that leaches terminal makes to leach the impurity hydrolysis in ore pulp, filter in backward filtrate and add dimethylin sodium sulfonate (being called for short SDD) removal heavy metal, can obtain manganese sulfate solution.
The above-mentioned method of preparing manganous sulfate of smelting taking brunite as raw material, as manganese element in the described brunite of raw material mainly with Mn
7siO
12form exists, and granularity is preferably controlled at-20 order～-200 orders (accounting for more than 80%), can realize by fragmentation, dry type magnetic separation, ball milling, fine grinding etc.
The method of manganous sulfate is prepared in the above-mentioned smelting taking brunite as raw material, and the concentration of described dilute sulphuric acid is preferably 1.0N～4.0N(equivalent concentration), the time of agitation leach is preferably 0.5h～2h.
The method of manganous sulfate is prepared in the above-mentioned smelting taking brunite as raw material, and the concentration of described ammoniacal liquor is preferably 10%～15%(mass concentration), the pH value after ammonia neutralization is preferably controlled at 6.5～6.8.
The method of manganous sulfate is prepared in the above-mentioned smelting taking brunite as raw material, preferred, only adds dimethylin sodium sulfonate when removal heavy metal, after interpolation dimethylin sodium sulfonate, preferably places 24h again.
Technique scheme of the present invention is using the higher brunite of a kind of manganese content as the raw material of preparing manganous sulfate, and using the high Sweet natural gas of reducing activity as efficient, clean reductive agent, its can be in reactor or Reaktionsofen fast restore brunite, and reduzate is mainly green manganese monoxide (by Mn
2o
3in+MnO of be reduced to+divalent of the Mn state of 3 valence states), the reduction transformation efficiency of manganese reaches more than 99%; Leach with dilute sulphuric acid normal temperature again, by controlling acidity and time etc. of leaching process, can the good leaching ore pulp of output strainability, can reach more than 98% containing the leaching yield of manganese reduzate, by contrast, the leaching yield of the reducing roasting technique manganese of conventional pyrolusite only has 78% left and right.In addition, the foreign matter content of leach liquor of the present invention is low, only need be to leaching the hydrolysis such as impurity silicon that terminal ore pulp makes to leach with weak ammonia neutralization, aluminium, iron, arsenic, without adding the preliminary removing heavy metals of ammonium sulfide, filtrate after filtration is directly added SDD can remove the heavy metals such as a small amount of Cu, Co, Ni, Zn, finally obtains qualified purification of manganese sulfate liquid.
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 reducing activity is high, attribute the is clean Sweet natural gas reductive agent as brunite, not only reduction rate is fast, utilization ratio is high, has ensured the high reduction ratio of manganese in brunite; And adopt Sweet natural gas reduction, and can in leached mud, not increase solid remnants, leach the quantity of slag few, technique is succinct, does not produce secondary pollution;
(2) the present invention adopts selective control leaching-out technique (by controlling the addition of sulfuric acid to above-mentioned reduzate, make the pH value stabilization of leaching process 2.0～2.5, prevent the excessive stripping of impurity ferrosilicoaluminum etc., and reduction form manganese monoxide very easily with sulfuric acid reaction stripping) leach, in the leaching ore pulp obtaining, not only beavy metal impurity content is few, and it is low to purify cost, leaching yield is high;
(3) reduction efficiency that the present invention is higher and higher leaching efficiency, ensure that manganese sulfate solution prepared by the present invention has higher manganese yield, and the leaching of manganese element of the present invention acid consumption is only 50% left and right of conventional electrowinning preparation of manganese, process costs is low, energy consumption and resource consumption are few, the qualified manganese sulfate solution making can be used as the raw material of smelting electrowinning manganese, has extraordinary popularizing application prospect at electrowinning manganese industry.
Brief description of the drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the invention will be further described.
embodiment 1:
Algeria's somewhere brunite, raw ore chemical composition mainly comprises Mn 43.8%, SiO
212.3%, Al
2o
31.79%, P 1.12%, Fe 0.34%, CaO 4.33% and MgO 1.87%, taking this brunite as raw material, adopt method of the present invention as shown in Figure 1 to prepare manganous sulfate, comprise the following steps: broken through jaw, pair roller, ball milling makes the granularity of this brunite account for 80% for-100 orders, get the brunite material of 100g after levigate and be placed in corundum boat, then put into the tube furnace of closed at both ends, electrically heated is warmed up to 800 DEG C～900 DEG C, passing into nitrogen (or other protective gas) discharges after the interior air of burner hearth, pass into continuously Sweet natural gas and carry out reducing roasting, insulation reduction 0.5h(0.5～2h all can), stop insulation, stop passing into Sweet natural gas, change that to pass into nitrogen protection cooling, be cooled to 100 DEG C of following rear materials (the manganese material that contains after roasting reduction is green) that take out after reduction, then the dilute sulphuric acid taking concentration as 2.3N is by solid-to-liquid ratio 8: 1(ml/g) agitation leach, control the pH value of leaching process and terminal 2.0～2.5, extraction time is 1h, leach the ore pulp of terminal and add 15% ammoniacal liquor and make the pH value of slurry be adjusted to 6.5～6.8, finally filter (taking-up silicon, aluminium, iron, phosphorus, arsenic etc.), after measured, in filtrate, the leaching yield of manganese reaches 98.3%, in filtrate, add SDD removing heavy metals (Cu, Co, Ni, Zn etc.) again, after standing 24h, filter, filtrate is foreign matter content and closes the manganese sulfate solution of symbol electrowinning manganese requirement, and it can be used for electrowinning manganese.The composition of the manganese sulfate solution that after testing, prepared by the present embodiment is as follows:
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, raw ore main chemical compositions comprises Mn 28.65%, SiO
223.28%, Al
2o
37.35%, P 0.35%, Fe 3.39%, CaO 2.83%, MgO 1.31%, taking this brunite 100g as raw material, adopt method of the present invention as shown in Figure 1 to prepare manganous sulfate, comprise the following steps: broken through jaw, pair roller, ball milling makes 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 DEG C～880 DEG C, start to add continuously brunite, passing into nitrogen (or other protective gas) discharges after the interior air of burner hearth, pass into continuously Sweet natural gas and carry out reducing roasting, adjust the motor speed of rotary kiln, ensure that the high-temperature material residence time is that 1h(ensures that the high temperature reduction time is 1h), discharging after the reduction chilling that directly falls into the water, take out the material after reduction, then press solid-to-liquid ratio 5: 1(ml/g with 1.9N dilute sulphuric acid) agitation leach, control the pH value of leaching process and terminal 2.0～2.5, extraction time is 0.5h, leach the ore pulp of terminal and add 12% ammoniacal liquor and make the pH value of slurry be adjusted to 6.5～6.8, finally filter (taking-up silicon, aluminium, iron, phosphorus, arsenic etc.), after measured, in filtrate, the leaching yield of manganese reaches 98.7%, in filtrate, add SDD removing heavy metals (Cu, Co, Ni, Zn etc.) again, after standing 24h, filter, filtrate is foreign matter content and closes the manganese sulfate solution of symbol electrowinning manganese requirement, and it can be used for electrowinning manganese.The composition of the manganese sulfate solution that after testing, prepared by the present embodiment is as follows:
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 (4)
1. smelt and prepare the method for manganous sulfate taking brunite as raw material, comprise the following steps: taking brunite as raw material, as manganese element in the brunite of raw material mainly with Mn
7siO
12form exists, and granularity is controlled at-20 order～-200 orders, the manganese content 20%～55% in brunite; Using Sweet natural gas as reductive agent, in reaction unit, make brunite fully be reduced by Sweet natural gas, reduction temperature is controlled at 800 DEG C～900 DEG C, and the time of reduction reaction is 0.5h～2h, obtains taking manganese monoxide as main reduzate after reduction; Again reduzate is leached with dilute sulphuric acid, the pH value of controlling leaching process and terminal is 2.0～2.5, carry out selectivity leaching, the ore pulp ammonia neutralization that leaches terminal makes to leach the impurity hydrolysis in ore pulp, filter in backward filtrate and add dimethylin sodium sulfonate removal heavy metal, can obtain manganese sulfate solution.
2. the method for preparing manganous sulfate of smelting taking brunite as raw material according to claim 1, is characterized in that: the concentration of described dilute sulphuric acid is 1.0～4.0N, and the time of agitation leach is 0.5h～2h.
3. the method for preparing manganous sulfate of smelting taking brunite as raw material according to claim 1, is characterized in that: the mass concentration of described ammoniacal liquor is 10%～15%, and the pH value after ammonia neutralization is controlled at 6.5～6.8.
4. the method for preparing manganous sulfate of smelting taking brunite as raw material according to claim 1, is characterized in that: when removal heavy metal, only add dimethylin sodium sulfonate, after interpolation dimethylin sodium sulfonate, place 24h again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210351205.5A CN102815751B (en) | 2012-09-20 | 2012-09-20 | Method for smelting and preparing manganese sulfate from braunite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210351205.5A CN102815751B (en) | 2012-09-20 | 2012-09-20 | Method for smelting and preparing manganese sulfate from braunite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102815751A CN102815751A (en) | 2012-12-12 |
| CN102815751B true CN102815751B (en) | 2014-07-23 |
Family
ID=47300262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210351205.5A Active CN102815751B (en) | 2012-09-20 | 2012-09-20 | Method for smelting and preparing manganese sulfate from braunite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102815751B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609753A (en) * | 2019-01-08 | 2019-04-12 | 重庆大学 | A method for preparing manganese carbonate by ammonia leaching with ammonium bifluoride as additive |
| CN109628739A (en) * | 2019-01-08 | 2019-04-16 | 重庆大学 | A kind of method for improving ammonia leaching rate of manganese ore with ammonia triacetic acid as additive |
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 | A sulfur-based fire reduction method for manganese oxide minerals |
| 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 | A sulfur-based fire reduction method for manganese oxide minerals |
| 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 (2)
| Title |
|---|
| 尹文新等.电解二氧化锰制备技术的研究进展.《金属矿山》.2007,(第3期),第10-14页. |
| 电解二氧化锰制备技术的研究进展;尹文新等;《金属矿山》;20070331(第3期);第10-14页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102815751A (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100395354C (en) | Comprehensive recovering process of multimetal sulfide mineral | |
| CN102094128B (en) | Method for comprehensively recovering various valuable metals from germanium-containing material by wet process | |
| CN102002585B (en) | Method for producing vanadium iron with stone-like coal pickle liquor | |
| CN102234721A (en) | Treatment method of nickel-cobalt material | |
| CN103088208A (en) | Method for treating manganese-containing and phosphorus-containing hematite | |
| CN112159897A (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| CN103274471A (en) | Method for preparing electronic-grade manganese sulfate by utilizing ferro-manganese alloy furnace slag | |
| CN110117720A (en) | A kind of method of sulfate slag phosphorylation roasting-leaching-extraction comprehensive extraction of valent metal | |
| CN103555933A (en) | Method for extracting molybdenum and nickel and enriching precious metals from nickel and molybdenum ores | |
| CN102181627A (en) | Method for treating primary low-grade high-phosphorus manganese ore by acid blending curing | |
| CN103374658A (en) | Ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and method thereof | |
| CN108570555A (en) | A method of directly producing LITHIUM BATTERY nickel sulfate from nickel cobalt enriched substance | |
| CN104060106A (en) | Method for preparing bismuth oxide by extracting bismuth from bismuth-containing liquor through solvent extracting method | |
| CN103643037B (en) | A method for separating copper, lead and iron in complex copper-lead-iron mixed sulfide ore | |
| CN114318417A (en) | Method for producing electrolytic manganese by using low-grade manganese oxide three-ore method | |
| CN103060553A (en) | Method for purifying zinc from zinc concentrate | |
| CN102703694A (en) | Method for treating low-grade zinc oxide ores by wet method | |
| CN102815751B (en) | Method for smelting and preparing manganese sulfate from braunite | |
| CN104046776A (en) | Process for recovering valuable metals from high-iron alloys | |
| CN101760652B (en) | Technological method for treating refractory complex molybdenum ore by combined dressing and smelting process | |
| CN108588425A (en) | A kind of processing method of cobalt metallurgy of nickel waste water slag | |
| CN102296323B (en) | Manufacturing system for producing electrolytic manganese metal by two-ore method | |
| CN101608265B (en) | Recovering process of associated metal zinc in gold finished ore | |
| CN102826586B (en) | Method for producing high purity nanometer zinc oxide by using steel plant dust | |
| CN110273070B (en) | Iron removal method for copper sulfide concentrate oxygen pressure leaching solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |