CN104294038A - Technology for preparing manganese carbonate from silver-manganese ores - Google Patents
Technology for preparing manganese carbonate from silver-manganese ores Download PDFInfo
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- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 15
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 15
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 15
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 13
- RQCJDSANJOCRMV-UHFFFAOYSA-N [Mn].[Ag] Chemical compound [Mn].[Ag] RQCJDSANJOCRMV-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000005516 engineering process Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 74
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 73
- 239000011572 manganese Substances 0.000 claims abstract description 73
- 238000002386 leaching Methods 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 27
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 230000003472 neutralizing effect Effects 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 229940116901 diethyldithiocarbamate Drugs 0.000 claims description 7
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 241000233805 Phoenix Species 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 229910052598 goethite Inorganic materials 0.000 abstract 1
- 235000012054 meals Nutrition 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001254 electrum Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- -1 kustelite Chemical compound 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001739 silver mineral Inorganic materials 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a technology for preparing manganese carbonate from silver-manganese ores. The manganese leaching rate of the technology is greater than 98%, and the later stage silver leaching rate can reach 95%; Fe in a manganese leaching liquid can be completely removed through pre-oxidation and an E.Z. goethite process, and the Fe content in the iron removed liquid is less than 1mg/L, so the iron removal rate reaches 99.99%; heavy meal impurities in the manganese leaching liquid can be removed through a sulfuration process, and the removal rates of Co, Ni and Zn reach 97.19%, 99.84% and 72.10% respectively, so the purifying effect is good; and a manganese carbonate product is successfully prepared, and the quality of the product reaches requirements of one-grade products.
Description
Technical field
The present invention relates to manganous carbonate and produce field, be specifically related to a kind of technique producing manganous carbonate from silver-colored manganese ore.
Background technology
In recent years, divide all in succession found silver-colored manganese ore deposit in many provinces of China, the Fe content in these mineral deposits is generally at 10%-30%, and the grade of silver is at 150g/t to a few kg/t.The silver-colored manganese ore reserves that China is verified have reached thousands of tons of (in argent), but not yet solve due to selecting and smelting technology problem, and this kind of ore of China not yet obtains effective development and utilization.Manganese in silver-manganese ore is the oxide mineral such as pyrolusite, psilomelane mainly, main existence form is MnO2, MnS, the silver mineral of its association mainly exists with forms such as native silver, kustelite, electrum, composing in isomorph mode in fine particle is stored in manganese ore lattice, both the mode being difficult to be sorted by machinery obtains high-grade silver preparation concentrate, also be difficult to obtain silver preferably by single cyanide process and leach index, be acknowledged as unmanageable containing one of silver ore, silver-colored manganese ore treatment process research is also subject to domestic and international common concern.
The process of current stage to silver-colored manganese ore mainly contains pyrogenic process and the large class of wet method two.Pyrogenic process mainly contains blast-furnace smelting method and reducing roasting lixiviation process.Wet method can be divided into again two-step approach, single stage method and Bioleaching method three major types.The two-step approach of report is wherein had to have using sulfur dioxide reduction method, two-control region, ferrous sulfate method, aniline process etc.Single stage method has thiosulfate technique, sour sulfur pulpating method, hydrogen peroxide method etc.
In actual applications thermal process because energy consumption is high, environmental pollution is serious and metal recovery rate is low is not widely adopted.Manganese, silver can leach in solution by the single stage method in wet processing simultaneously, the shortcomings such as technical process is short, but there is operational condition harshness, poor stability, and later separation is complicated, oneself rests on experimental stage, the domestic report there are no industrial application by the document of report mostly.Bioleaching method is the novel method that external silver-colored manganese is separated, and has the advantage that reagent consumption amount is few, free from environmental pollution, but also there is the defect that leaching velocity is slow, the operational cycle is long.Current stage silver manganese ore main methods be two-step approach, wherein comparative maturity is sulfurous gas method and two-control region.
China studies for manganese oxide ore (MnO2), is also all used to Processing Ag manganese oxide ore in the treatment process of above-mentioned silver-colored manganese ore.And the method that the silver-colored manganese ore that the major ingredient of silver-colored manganese is sulphide ores produces silver-colored manganese ore leaching manganese liquid document at home and abroad does not all also have similar report.
Manganous carbonate is a kind of general material of having many uses, and it may be used for: (1) manufactures soft magnetic ferrite.Manganous carbonate was once the main raw material that soft magnetic ferrite is produced, but nearly ten years, the production of soft magnetic ferrite progressively adopts trimanganese tetroxide to substitute manganous carbonate, and manganous carbonate has the trend be eliminated in this field; (2) manufacture the raw material of other manganese salt, be mainly used for producing chemical mno2; (3) pigment of coating and paint; (4) production of mangal and manganese-silicon; (5) fertilizer and fodder additives; (6) paint drier; (7) the multiple material of welding electrode; (8) pharmacy etc.
The production of China's manganous carbonate be mostly with rhodochrosite and pyrolusite for raw material, prepare manganous carbonate with the leaching manganese liquid of silver-colored manganese ore as raw material and also do not seen same process report.
Therefore, the major ingredient that the present invention is directed to silver-colored manganese is that the method that the silver-colored manganese ore of sulphide ores produces silver-colored manganese ore leaching manganese liquid is studied, and prepared manganous carbonate by the leaching manganese liquid of silver-colored manganese ore as raw material, being conducive to is utilization and the exploitation of the silver-colored manganese ore of sulphide ores to the major ingredient of silver-colored manganese.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of technique producing manganous carbonate from silver-colored manganese ore.The leaching yield of described technique manganese is greater than 98%, and the leaching yield of later stage silver can reach 95%; Can the Fe in leaching manganese liquid be removed clean by preoxidation and E.Z. separation of iron in goethite form, the Fe after deironing in liquid
t<1mg/L, deironing rate is up to 99.99%; Adopt sulfuration method can remove beavy metal impurity in leaching manganese liquid, wherein the purification rate of Co, Ni, Zn reaches 97.19%, 99.84%, 72.10% respectively, and decontamination effect improving is good; Successfully prepared manganese carbonate product, quality product reaches the requirement of first grade.
Present invention employs following technical scheme:
From silver-colored manganese ore, produce a technique for manganous carbonate, it comprises the following steps:
Producing of silver manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 3.5-4.5N, catalyzer 0.35-0.45N, liquid-solid ratio L/S=2.5-3.5, pyrolusite amount is the 35-45% of silver-colored manganic concerntrate, temperature 85-95 DEG C, leaches under the condition of time 1.5-2.5h;
Neutralization: adopt rhodochrosite (MnCO3) to make neutralizing agent, the sulfuric acid at 75-85 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1;
E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 75-85 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=5-6, is incubated 0.5-1 hour after reaction is reached home;
Sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 55-65 DEG C;
Produce manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 75-85g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control at about 6.5-7.5.
Wherein preferred technique is:
Producing of silver manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 4N, catalyzer 0.4N, liquid-solid ratio L/S=3, pyrolusite amount is 40% of silver-colored manganic concerntrate, and temperature 90 DEG C, leaches under the condition of time 2h;
Neutralization: adopt rhodochrosite (MnCO3) to make neutralizing agent, the sulfuric acid at 80 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1.
E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 80 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=5.5, is incubated 45min after reaction is reached home.
Sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 60 DEG C.
Produce manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 79g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control about 7.
Wherein, described silver-colored manganese ore is the silver floatation manganese ore concentrate of Guangxi phoenix silver ore.
Wherein, the Chemical Composition of described silver-colored manganese ore comprises (wt%): 0.796Ag, 4.31Pb, 3.08Zn, 0.24Cu, 10.97As, 23.46S, 18.09Fe, 17.29Mn.
The present invention has the following advantages:
(1) pyrolusite (MnO2) is adopted to make oxygenant, at sulfuric acid 4N, catalyzer 0.4N, liquid-solid ratio L/S=3, pyrolusite amount is 40% of silver-colored manganic concerntrate, temperature 90 DEG C, under the condition of time 2h, in silver-colored manganese ore, the leaching yield of manganese is greater than 98%, and the leaching yield of later stage silver can reach 95%.
(2) soaking sulfuric acid content higher (83.17g/L) in manganese liquid adopts rhodochrosite (MnCO3) to make neutralizing agent, and the sulfuric acid at 80 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1.
(3) systematic research has been carried out to the technique of E.Z. separation of iron in goethite form, can the Fe in leaching manganese liquid removed clean by preoxidation and E.Z. separation of iron in goethite form.Fe after deironing in liquid
t<1mg/L, deironing rate is up to 99.99%.
(4) sulfuration method is adopted can to remove beavy metal impurity in leaching manganese liquid.Wherein the purification rate of Co, Ni, Zn reaches 97.19%, 99.84%, 72.10% respectively, and decontamination effect improving is good.
(5) successfully prepared manganese carbonate product, quality product reaches the requirement of first grade.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment one
From silver-colored manganese ore, produce a technique for manganous carbonate, it comprises the following steps:
Producing of silver manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 4N, catalyzer 0.4N, liquid-solid ratio L/S=3, pyrolusite amount is 40% of silver-colored manganic concerntrate, and temperature 90 DEG C, leaches under the condition of time 2h;
Neutralization: adopt rhodochrosite (MnCO3) to make neutralizing agent, the sulfuric acid at 80 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1.
E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 80 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=5.5, is incubated 45min after reaction is reached home.
Sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 60 DEG C.
Produce manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 79g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control about 7.
Wherein, the Chemical Composition of described silver-colored manganese ore comprises (wt%): 0.796Ag, 4.31Pb, 3.08Zn, 0.24Cu, 10.97As, 23.46S, 18.09Fe, 17.29Mn.
Embodiment two
From silver-colored manganese ore, produce a technique for manganous carbonate, it comprises the following steps:
Producing of silver manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 3.5N, catalyzer 0.35N, liquid-solid ratio L/S=2.5, pyrolusite amount is 35% of silver-colored manganic concerntrate, and temperature 85 DEG C, leaches under the condition of time 1.5h;
Neutralization: adopt rhodochrosite (MnCO3) to make neutralizing agent, the sulfuric acid at 75 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1;
E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 75 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=5, after reaction is reached home, be incubated 0.5 hour;
Sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 55 DEG C;
Produce manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 75g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control about 6.5.
Wherein, the Chemical Composition of described silver-colored manganese ore comprises (wt%): 0.796Ag, 4.31Pb, 3.08Zn, 0.24Cu, 10.97As, 23.46S, 18.09Fe, 17.29Mn.
Embodiment three
From silver-colored manganese ore, produce a technique for manganous carbonate, it comprises the following steps:
Producing of silver manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 4.5N, catalyzer 0.45N, liquid-solid ratio L/S=3.5, pyrolusite amount is 45% of silver-colored manganic concerntrate, and temperature 95 DEG C, leaches under the condition of time 2.5h;
Neutralization: adopt rhodochrosite (MnCO3) to make neutralizing agent, the sulfuric acid at 85 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1;
E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 85 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=6, after reaction is reached home, be incubated 1 hour;
Sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 65 DEG C;
Produce manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 85g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control about 7.5.
Wherein, the Chemical Composition of described silver-colored manganese ore comprises (wt%): 0.796Ag, 4.31Pb, 3.08Zn, 0.24Cu, 10.97As, 23.46S, 18.09Fe, 17.29Mn.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (8)
1. from silver-colored manganese ore, produce a technique for manganous carbonate, it comprises the following steps:
Producing of silver manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 3.5-4.5N, catalyzer 0.35-0.45N, liquid-solid ratio L/S=2.5-3.5, pyrolusite amount is the 35-45% of silver-colored manganic concerntrate, temperature 85-95 DEG C, leaches under the condition of time 1.5-2.5h;
Neutralization: adopt rhodochrosite (MnCO3) to make neutralizing agent, the sulfuric acid at 75-85 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1;
E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 75-85 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=5-6, is incubated 0.5-1 hour after reaction is reached home;
Sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 55-65 DEG C;
Produce manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 75-85g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control at about 6.5-7.5.
2. technique according to claim 1, producing of preferred silver-colored manganese ore leaching manganese liquid: adopt pyrolusite (MnO2) to make oxygenant, at sulfuric acid 4N, catalyzer 0.4N, liquid-solid ratio L/S=3, pyrolusite amount is 40% of silver-colored manganic concerntrate, temperature 90 DEG C, leaches under the condition of time 2h.
3. technique according to claim 1, preferably neutralizes: adopt rhodochrosite (MnCO3) to make neutralizing agent, and the sulfuric acid at 80 DEG C and in leaching manganese liquid, the add-on of its manganese carbonate ore, controls with terminal pH=1.
4. technique according to claim 1, preferred E.Z. separation of iron in goethite form: add pyrolusite oxidation of ferrous iron to ferric iron at 80 DEG C; Adopt lime to carry out as neutralizing agent, terminal pH=5.5, is incubated 45min after reaction is reached home.
5. technique according to claim 1, preferred sulfuration method removing heavy metals: adopt diethyldithiocarbamate to remove beavy metal impurity in leaching manganese liquid as precipitation agent sulfuration method at 60 DEG C.
6. technique according to claim 1, preferably produces manganous carbonate: adopt bicarbonate of ammonia to make precipitation agent, add the bicarbonate of ammonia of theoretical amount 1.2 times; The starting point concentration of bicarbonate of ammonia is 79g/L; Unsuitable too high about 30 DEG C of the temperature of reaction; The pH value of reaction end should control about 7.
7. technique according to claim 1, wherein, described silver-colored manganese ore is the silver floatation manganese ore concentrate of Guangxi phoenix silver ore.
8. technique according to claim 1, wherein, the Chemical Composition of described silver-colored manganese ore comprises (wt%): 0.796Ag, 4.31Pb, 3.08Zn, 0.24Cu, 10.97As, 23.46S, 18.09Fe, 17.29Mn.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106119565A (en) * | 2016-06-22 | 2016-11-16 | 湖南大学 | A kind of method that leaching of manganese and silver produce manganese sulfate and silver from manganese-silver ore |
| CN106395910A (en) * | 2016-08-29 | 2017-02-15 | 中南大学 | Method for preparation of battery grade high-purity manganese sulfate from industrial grade manganese sulfate |
| CN106367589A (en) * | 2016-09-19 | 2017-02-01 | 北京科技大学 | Short-process low-consumption high-purity manganese sulfate solution preparing method |
| CN106673066A (en) * | 2016-11-11 | 2017-05-17 | 中南大学 | Preparation method of high-purity anhydrous manganese chloride particles |
| CN107117657A (en) * | 2017-06-23 | 2017-09-01 | 中南大学 | The method that high-pure anhydrous manganese chloride is prepared using technical grade sulfuric acid manganese |
| CN108660326A (en) * | 2018-05-25 | 2018-10-16 | 东北大学 | A method of reduction acidolysis-leaching is simultaneously except iron handles manganese oxide ore |
| CN111286603A (en) * | 2020-03-25 | 2020-06-16 | 内蒙古金山矿业有限公司 | Process for recovering silver and co-producing manganese sulfate from manganese-containing silver ore |
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