CN102776370B - Technological method for leaching manganese ore with high spent acid - Google Patents
Technological method for leaching manganese ore with high spent acid Download PDFInfo
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- CN102776370B CN102776370B CN201210307235.6A CN201210307235A CN102776370B CN 102776370 B CN102776370 B CN 102776370B CN 201210307235 A CN201210307235 A CN 201210307235A CN 102776370 B CN102776370 B CN 102776370B
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- manganese
- acid
- ore
- sulfuric acid
- manganese ore
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 37
- 239000011572 manganese Substances 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 238000002386 leaching Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 46
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 42
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 8
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 8
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 8
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 8
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 235000013312 flour Nutrition 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 5
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 5
- 239000002893 slag Substances 0.000 abstract description 5
- 229940099596 manganese sulfate Drugs 0.000 abstract description 4
- 239000011702 manganese sulphate Substances 0.000 abstract description 4
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003978 infusion fluid Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 iron ion Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a technological method for leaching manganese ore with high spent acid, which comprise the steps: (1) according to the technological requirements, adding sulfuric acid into manganese ore powder, so as to obtain manganese sulfate leachate after reaction; in the leachate, keeping the concentration of the sulfuric acid be (3-10)g/l; (2) adding an oxidant into the leachate for oxidation treatment; and (3) adding calcium carbonate into the leachate to react with the sulfuric acid until the pH value is within a range of 6.4 plus or minus 0.2, so as to obtain manganese ore leachate. According to the method, the concentration of leached spend acid is increased so that the manganese carbonate ore and the acid react relatively thoroughly, the leaching rate is improved, the manganese content in slag is reduced, not only is the utilization rate of resources increased, but also the pollution to the environment is effectively reduced; calcium carbonate is used for substituting for all or part ammonia water for neutralizing the spent acid, so that the problem that ammonium sulfate which is produced by using the ammonia water and the excessive spent acid is supersaturated in a circulation system is effectively solved; and the neutralization cost is greatly lowered, and obvious economic benefits are obtained.
Description
Technical field
The present invention relates to manganese ore in a kind of electrolytic manganese production and dissolve the method that is produced into soluble manganese salt, especially high spent acid leaching of manganese ore technology method.
Background technology
In electrolytic manganese production, be first that manganese ore is dissolved, normally in sulfuric acid, dissolve, generate soluble manganese sulfate solution.The manganese carbonate ore extract technology flow process of prior art, as shown in Figure 1, according to processing requirement, adds sulfuric acid in manganese ore powder, carries out chemical reaction, generates soluble manganese sulfate solution; Leach liquor is carried out to oxide treatment, is mainly to add oxygenant (as Manganse Dioxide, oxygen etc.), and its effect is to make Fe2+ be oxidized to Fe3+, and formation precipitates and removes the iron ion in solution, reduces to greatest extent the iron ion content in solution; Finally add ammoniacal liquor to carry out neutralization reaction, the acid in neutralization solution, makes the pH value of solution reach processing requirement.This cover extract technology method, has continued to use many decades, is to be born under the background that sulphuric acid cost was higher and manganese carbonate ore grade is relatively high at that time.But along with the manganese carbonate ore lasting reduction of grade in recent years and the decline of sulphuric acid cost, this cover technique be difficult to have adapted to electrolytic manganese enterprise and has pursued that cost is maximized have been required; The second, the leaching yield of manganese ore is relatively on the low side, and in slag, the content of manganese is still relatively plain high, has reduced the utilization ratio of resource, and the high slag of manganese content exists larger pollution to environment.The 3rd, adopt the too high spent acid of ammonia neutralization, the supersaturation problem of the ammonium sulfate bringing in circulating system; The 4th, use a large amount of ammoniacal liquor, in also having increased and cost.
Summary of the invention
The manganese carbonate ore extract technology above shortcomings of pin prior art of the present invention, the leaching yield that a kind of manganese ore is provided compared with high, in and cost compared with low, do not adopt or significantly reduce ammonia volume neutralization and avoid ammonium sulfate in circulating system problem, the problem includes: the high spent acid leaching of manganese ore technology method of supersaturation problem.
Technical scheme of the present invention: high spent acid leaching of manganese ore technology method, is characterized in that comprising the steps:
(1) according to processing requirement, sulfuric acid is added in manganese ore stone flour, through reaction, obtain manganous sulfate leach liquor; In infusion solution, the concentration of sulfuric acid is remained on (3-10) g/l;
(2), according to processing requirement, in leach liquor, add oxygenant to carry out oxide treatment;
(3) in leach liquor, add calcium carbonate, calcium carbonate and sulfuric acid reaction, the add-on of calcium carbonate is between 0.3-3.7g/l; Carry out necessary stirring, make pH value stop adding in 6.4 ± 0.2 scopes, obtain meeting the Leaching Solution of Manganese Ore of processing requirement.
High spent acid leaching of manganese ore technology method, is characterized in that comprising the steps:
(1) according to processing requirement, sulfuric acid is added in manganese ore stone flour, through reaction, obtain manganous sulfate leach liquor; In infusion solution, the concentration of sulfuric acid is remained on (3-10) g/l;
(2), according to processing requirement, in leach liquor, add oxygenant to carry out oxide treatment;
(3) in leach liquor, add calcium carbonate, calcium carbonate and sulfuric acid reaction, the add-on of calcium carbonate is between 0.3-3.7g/l; Carry out necessary stirring, make pH value stop adding in 4-5 scopes: then, in leach liquor, add ammoniacal liquor, make pH value stop adding in 6.4 ± 0.2 scopes, obtain meeting the Leaching Solution of Manganese Ore of processing requirement.
The high spent acid leaching of manganese of the present invention ore technology method, with respect to prior art, has following features:
1, the concentration that leaches residual acid by raising makes the reaction of manganese carbonate ore and acid more thorough, has improved leaching yield, has reduced the content of manganese in slag, has not only improved the utilization ratio of resource, and has effectively reduced the pollution to environment.
2, by with calcium carbonate, substitute all or part of ammoniacal liquor come in and spent acid, efficiently solve ammonium sulfate that the too high spent acid of ammonia neutralization the brings supersaturation problem in circulating system of using.
3, significantly reduce in and cost, there is economic benefit obvious.
Accompanying drawing explanation
Fig. 1 is the manganese carbonate ore extract technology schema of prior art;
Fig. 2 is process method flow chart of the present invention.
Embodiment
As Fig. 2, the high spent acid leaching of manganese of the present invention ore technology method, is characterized in that comprising the steps:
1, according to processing requirement, sulfuric acid is added in manganese ore stone flour, through reaction, obtain manganous sulfate leach liquor; In infusion solution, make more than the concentration of sulfuric acid remains on 3g/l, generally in the scope of (3-10) g/l; This concentration is the residual concentration of sulfuric acid in manganese sulfate solution, guarantees excess sulfuric acid in infusion solution, and manganese ore and sour reaction are more thorough, and mn ion can be dissolved to greatest extent, to improve leaching yield, reduce the content of manganese in slag.
2,, according to processing requirement, in leach liquor, add oxygenant to carry out oxide treatment; The oxygenant adding, is mainly that its effect is to make Fe2+ be oxidized to Fe3+ as Manganse Dioxide, oxygen etc., and formation precipitates and removes the iron ion in solution, reduces to greatest extent the iron ion content in solution.
3, in leach liquor, add calcium carbonate, calcium carbonate and sulfuric acid reaction, the add-on of calcium carbonate is between 0.3-3.7g/l; Because calcium carbonate is solid-state, need to carry out necessary stirring, or stir while adding, make pH value stop adding in 6.4 ± 0.2 scopes, obtain meeting the Leaching Solution of Manganese Ore of processing requirement.
Or, first in leach liquor, adding part calcium carbonate, calcium carbonate and sulfuric acid reaction, make pH value stop adding in 4-5 scopes, and the add-on of calcium carbonate, at 0.3-3.7g/l, needs stir or stir while adding; Then, in leach liquor, add ammoniacal liquor, the add-on of ammoniacal liquor according to actual needs, generally makes pH value stop adding in 6.4 ± 0.2 scopes, obtains meeting the Leaching Solution of Manganese Ore of processing requirement.
More than the concentration of sulfuric acid of the present invention remains on 3g/l, generally in the scope of (3-10) g/l, as 3.2 g/l, 3.5 g/l, 3.8 g/l, 4.0 g/l, 4.2 g/l, 4.5 g/l, 4.8 g/l, 5.0 g/l, 5.5g/l, 6.0 g/l, 6.5 g/l, 7.0 g/l, 7.5 g/l, 8.0 g/l, 8.5g/l, 9.0 g/l, 9.5 g/l, can meet processing requirement, guarantee excess sulfuric acid in infusion solution, manganese ore and sour reaction are more thorough; The present invention by with calcium carbonate, substitute all or part of ammoniacal liquor come in and spent acid, efficiently solve ammonium sulfate that the too high spent acid of ammonia neutralization the brings supersaturation problem in circulating system of using.
The add-on of calcium carbonate of the present invention is between 0.3-3.7g/l, as 0.5 g/l, 0.8 g/l, 1.0 g/l, 1.2 g/l, 1.5 g/l, 1.8 g/l, 2.0 g/l, 2.2g/l, 2.5 g/l, 2.8 g/l, 3.0 g/l, 3.2 g/l, 3.5 g/l, 3.6 g/l, 3.7 g/l etc., can meet processing requirement, stop adding after meeting the requirements of pH value.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (1)
1. high spent acid leaching of manganese ore technology method, is characterized in that comprising the steps:
(1) according to processing requirement, sulfuric acid is added in manganese ore stone flour, through reaction, obtain manganous sulfate leach liquor; In leach liquor, the concentration of sulfuric acid is remained on (3-7.5) g/L;
(2), according to processing requirement, in leach liquor, add oxygenant to carry out oxide treatment;
(3) in leach liquor, add calcium carbonate, calcium carbonate and sulfuric acid reaction, the add-on of calcium carbonate is between 0.3～3.7g/L; Carry out necessary stirring, make pH value stop adding in 4～5 scopes: then, in leach liquor, add ammoniacal liquor, make pH value stop adding in 6.4 ± 0.2 scopes, obtain meeting the Leaching Solution of Manganese Ore of processing requirement;
Described manganese ore is manganese carbonate ore.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757441B (en) * | 2013-12-29 | 2015-06-17 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN105483399B (en) * | 2015-11-30 | 2017-11-17 | 长沙矿冶研究院有限责任公司 | The manganese carbonate ore leaching method for neutralizing and leaching is leached based on leading portion |
| CN108193047B (en) * | 2017-12-29 | 2019-09-06 | 四川恒泰环境技术有限责任公司 | With the method for the manganese sulfate solution of anolyte manganous dithionate low with slurries desulfurization system prepared by manganese ore |
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Non-Patent Citations (4)
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| 谢放尖，等."电解金属锰工艺清洁生产初探".《四川环境》.2008,第27卷(第2期),56. |
| 谢放尖,等."电解金属锰工艺清洁生产初探".《四川环境》.2008,第27卷(第2期),56. * |
| 陈蓉，等."低品位锰矿制备硫酸锰的研究".《武汉工程大学学报》.2008,第30卷(第1期),20-21. |
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Effective date of registration: 20220623 Address after: 554199 4th floor, Economic Development Zone Management Committee, Songtao Miao Autonomous County, Tongren City, Guizhou Province Patentee after: GUIZHOU WULING MANGANESE INDUSTRY Co.,Ltd. Address before: 409912 Chongqing Wuling Manganese Industry Co., Ltd., Rongxi Town, Xiushan Tujia and Miao Autonomous County, Chongqing Patentee before: Chongqing Wuling Manganese Industry Corp. |