CN105063343A - Desulphurization method for Fe-Mn ore - Google Patents
Desulphurization method for Fe-Mn ore Download PDFInfo
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- CN105063343A CN105063343A CN201510547008.4A CN201510547008A CN105063343A CN 105063343 A CN105063343 A CN 105063343A CN 201510547008 A CN201510547008 A CN 201510547008A CN 105063343 A CN105063343 A CN 105063343A
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Abstract
The invention relates to a desulphurization technology for Fe-Mn ore, in particular to a desulphurization method for Fe-Mn ore. The Fe-Mn ore is pulverized to make the particle size to reach 150-200 meshes, and ore powder is obtained after sieving; water is added into the ore powder and evenly stirred under the condition of 80-120 DEG C, and slurry is obtained; the slurry is stirred, sulfur dioxide gas is injected at the same time, auxiliaries are added and stirred for 30 min after 30-40 min of stirring and 10-20 min of still standing, the adding quantity of the auxiliaries is 1/30 to 1/20 of the size of the slurry, and intermediate materials are obtained; and cellulose is added into the intermediate materials and stirred for 20-50 min, and then separation is carried out to obtain flake flocks, solid and sulphate solutions. The desulphurization method has a good desulphurization effect, is low in cost, free of pollution and capable of removing a part of harmful ions such as lead and cadmium.
Description
Technical field
The present invention relates to the desulfurization technology of Ferromanganese Ore, be specifically related to a kind of sulfur method of Ferromanganese Ore.
Background technology
Ferromanganese Ore is important raw mineral materials, be mainly used in metallurgy industry, particularly smelting iron and steel, but moieties can cause disadvantageous effect to smelting in Ferromanganese Ore, such as, sulphur content is larger to smelting fluctuation, the solubleness of sulphur in iron is minimum, part is present in steel with the form of FeS, on the one hand, steel brittleness is increased, on the other hand, FeS and Fe can form the eutectic of low melting point (985 DEG C), be distributed on austenitic crystal boundary, carry out thermal pressure add man-hour when steel is heated to about 1200 DEG C, eutectic on crystal boundary dissolves, intercrystalline combines destroyed, and then make steel in the course of processing along grain boundary separation, so, for ensureing the quality of smelting, need to carry out desulfurization process in advance to Ferromanganese Ore.
In the prior art, the desulfurization of general employing sintering process, technique is skillful, but hear rate is large, cost is high, and the sulphur removed enters air with gas form, causes atmospheric pollution; The patent No. be 201310242967.6 " a kind of to high-sulfur rhodochrosite " disclose a kind of Vanadium Pentoxide in FLAKES and 2.6-anthraquinone disulfonic acid or Vanadium Pentoxide in FLAKES and tannin extract of utilizing and coordinate the sweetening agent formed to carry out desulfurization process to rhodochrosite, this method sweetening effectiveness is good, energy consumption is less, but the time is long, reagent dosage is large, and this law is simple based on rhodochrosite self component, mainly containing manganese, iron, calcium, zinc, and crystal belongs to trigonal system, therefore desulfurization process is easier to; And Ferromanganese Ore complicated component, the harmful substance contents such as lead, silver, cadmium, arsenic is high, and crystal belongs to tetragonal system, therefore Ferromanganese Ore desulfurization intractability is comparatively large, and therefore, the sulfur method of Ferromanganese Ore still needs large quantity research.
For this reason, the present inventor studies Ferromanganese Ore and desulfurization technology for many years, and the sulfur method for Ferromanganese Ore provides new approaches.
Summary of the invention
The present invention for solving the problems of the technologies described above, provide a kind of pollution-free, consume less, low, the effective Ferromanganese Ore sulfur method of cost.
Be achieved especially by following scheme:
A sulfur method for Ferromanganese Ore, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 150-200 order, sieves, and obtains breeze;
(2) under 80-120 DEG C of condition, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 30-40min, after leaving standstill 10-20min, add auxiliary agent and stir 30s, wherein, promoter addition is the 1/30-1/20 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 20-50min, be separated, obtain flock, solid and sulfate liquor.
In described step (2), amount of water is 2-3 times of breeze weight.
In described step (3), stirring velocity is 60-120r/min.
Described step adds sulfur dioxide gas in (3), and its add-on is the 1/10-1/5 of slip volume.
In described step (3), auxiliary agent is that 1:1-3:2-5 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
Stirring velocity in described step (3) and (4) is 30-60r/min.
In described step (4), cellulosic add-on is the 1/70-1/50 of slip volume.
Beneficial effect of the present invention
The present invention by being filled with sulfur dioxide gas in slurry, and combine stirring, make slip sulfur dioxide absorption and in acid, further, add the auxiliary agent of preparation, in conjunction with rational proportioning raw materials, make the low price sulphur in breeze be oxidized to the solubility sulphur of high-valence state, then add Mierocrystalline cellulose, make the heavy metal ion in intermediate material and its generation complex reaction, further, due to S
2-electronics first transit to ground state by excited state, transit to excited state again, wherein, give off energy when transitting to ground state, this energy is the required energy absorbed of providing chemical bond rupture just in time, when heavy metal and Mierocrystalline cellulose generation complex reaction, be bonded to and give off energy, this portion of energy supplies again transition of electron to excited state institute energy requirement; By to carrying out manganese, sulphur content determination experiment before and after the process of ferrimanganic breeze, obtain, desulfurization degree is up to 93%, and the sulphur content of Ferromanganese Ore is after treatment lower than 1.5%, higher than sintering process desulfurization degree 1.3-1.7 doubly; In summary: the present invention has good sweetening effectiveness, cost low, pollution-free, also can remove lead, every etc. part harmful ion.
Embodiment
Below in conjunction with concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Embodiment 1
A sulfur method for Ferromanganese Ore, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 200 orders, sieves, and obtains breeze;
(2) under 90 DEG C of conditions, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 35min, after leaving standstill 15min, add auxiliary agent and stir 30s, wherein, promoter addition is 1/28 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 30min, be separated, obtain flock, solid and sulfate liquor.
In described step (2), amount of water is 2.5 times of breeze weight.
In described step (3), stirring velocity is 120r/min.
Described step adds sulfur dioxide gas in (3), and its add-on is 1/10 of slip volume.
In described step (3), auxiliary agent is that 1:3:2 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
Stirring velocity in described step (3) and (4) is 50r/min.
In described step (4), cellulosic add-on is 1/70 of slip volume.
Embodiment 2
A sulfur method for Ferromanganese Ore, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 150 orders, sieves, and obtains breeze;
(2) under 85 DEG C of conditions, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 32min, after leaving standstill 15min, add auxiliary agent and stir 30s, wherein, promoter addition is 1/25 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 30min, be separated, obtain flock, solid and sulfate liquor.
In described step (2), amount of water is 2 times of breeze weight.
In described step (3), stirring velocity is 100r/min.
Described step adds sulfur dioxide gas in (3), and its add-on is 1/12 of slip volume.
In described step (3), auxiliary agent is that 1:1:1 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
Stirring velocity in described step (3) and (4) is 40r/min.
In described step (4), cellulosic add-on is 1/68 of slip volume.
Embodiment 3
A sulfur method for Ferromanganese Ore, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 170 orders, sieves, and obtains breeze;
(2) under 96 DEG C of conditions, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 34min, after leaving standstill 12min, add auxiliary agent and stir 30s, wherein, promoter addition is 1/28 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 30min, be separated, obtain flock, solid and sulfate liquor.
In described step (2), amount of water is 2.5 times of breeze weight.
In described step (3), stirring velocity is 120r/min.
Described step adds sulfur dioxide gas in (3), and its add-on is 1/10 of slip volume.
In described step (3), auxiliary agent is that 1:4:2 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
Stirring velocity in described step (3) and (4) is 45r/min.
In described step (4), cellulosic add-on is 1/50 of slip volume.
Embodiment 4
A sulfur method for Ferromanganese Ore, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 200 orders, sieves, and obtains breeze;
(2) under 130 DEG C of conditions, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 35min, after leaving standstill 15min, add auxiliary agent and stir 30s, wherein, promoter addition is 1/25 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 50min, be separated, obtain flock, solid and sulfate liquor.
In described step (2), amount of water is 1.5 times of breeze weight.
In described step (3), stirring velocity is 100r/min.
Described step adds sulfur dioxide gas in (3), and its add-on is 1/8 of slip volume.
In described step (3), auxiliary agent is that 1:1:5 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
Stirring velocity in described step (3) and (4) is 60r/min.
In described step (4), cellulosic add-on is 1/45 of slip volume.
Embodiment 5
A sulfur method for Ferromanganese Ore, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 150 orders, sieves, and obtains breeze;
(2) under 78 DEG C of conditions, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 35min, after leaving standstill 15min, add auxiliary agent and stir 30s, wherein, promoter addition is 1/15 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 30min, be separated, obtain flock, solid and sulfate liquor.
In described step (2), amount of water is 2 times of breeze weight.
In described step (3), stirring velocity is 180r/min.
Described step adds sulfur dioxide gas in (3), and its add-on is 1/12 of slip volume.
In described step (3), auxiliary agent is that 1:2:3 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
Stirring velocity in described step (3) and (4) is 60r/min.
In described step (4), cellulosic add-on is 1/65 of slip volume.
Test example 1
The solid powder obtained by embodiment 1-5 is broken to ferrimanganic breeze one-size, GB/T14949.9-94 " the mensuration barium sulfategravimetry of manganese ore chemical analysis sulfur content and burning iodometry " is adopted to measure sulphur content, simultaneously, adopt GB/T1506-2002 " the mensuration potentiometric titration of manganese ore Fe content and sulfuric acid imonium volumetry " to measure Fe content, its result is as following table 1
Table 1
As can be known from the above table, desulfurization degree of the present invention is higher, and it is up to 93%, sulphur content in Ferromanganese Ore can be reduced to less than 1.5%, and then improve Fe content, and then improve the quality of smelting.
Claims (7)
1. a sulfur method for Ferromanganese Ore, is characterized in that, comprises the following steps:
(1) Ferromanganese Ore being crushed to granularity is 150-200 order, sieves, and obtains breeze;
(2) under 80-120 DEG C of condition, in breeze, add water stir, obtain slurry;
(3) stir slurry, be filled with sulfur dioxide gas simultaneously, after stirring 30-40min, after leaving standstill 10-20min, add auxiliary agent and stir 30s, wherein, promoter addition is the 1/30-1/20 of slip volume, obtains intermediate material;
(4) Mierocrystalline cellulose is added in intermediate material, after stirring 20-50min, be separated, obtain flock, solid and sulfate liquor.
2. the sulfur method of Ferromanganese Ore as claimed in claim 1, is characterized in that, in described step (2), amount of water is 2-3 times of breeze weight.
3. the sulfur method of Ferromanganese Ore as claimed in claim 1, is characterized in that, in described step (3), stirring velocity is 60-120r/min.
4. the sulfur method of Ferromanganese Ore as claimed in claim 1, it is characterized in that, described step adds sulfur dioxide gas in (3), and its add-on is the 1/10-1/5 of slip volume.
5. the sulfur method of Ferromanganese Ore as claimed in claim 1, is characterized in that, in described step (3), auxiliary agent is that 1:1-3:2-5 mixes by the mass ratio of peroxyacetic acid, sodium bismuthate, Na2Fe04.
6. the sulfur method of Ferromanganese Ore as claimed in claim 1, is characterized in that, the stirring velocity in described step (3) and (4) is 30-60r/min.
7. the sulfur method of Ferromanganese Ore as claimed in claim 1, it is characterized in that, in described step (4), cellulosic add-on is the 1/70-1/50 of slip volume.
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Citations (6)
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|---|---|---|---|---|
| WO2005116169A1 (en) * | 2004-05-31 | 2005-12-08 | Agency For Science, Technology And Research | Novel process for removing sulfur from fuels |
| CN101798625A (en) * | 2010-04-14 | 2010-08-11 | 北京科技大学 | Method for removing sulfur from fuel before sintering iron ores |
| CN102230088A (en) * | 2011-07-10 | 2011-11-02 | 重庆大学 | Method for extracting manganese from manganese-enriched slag |
| CN102732718A (en) * | 2012-06-15 | 2012-10-17 | 浙江华友钴业股份有限公司 | Method for low temperature treatment of sulfide ore by using air and sulfur dioxide mixed gas |
| CN103131847A (en) * | 2013-03-16 | 2013-06-05 | 重庆大学 | Method for desulphurizing high-sulphur rhodochrosite |
| CN103276228A (en) * | 2013-06-19 | 2013-09-04 | 重庆大学 | Desulfurizing method for high-sulfur rhodochrosite |
-
2015
- 2015-08-31 CN CN201510547008.4A patent/CN105063343B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005116169A1 (en) * | 2004-05-31 | 2005-12-08 | Agency For Science, Technology And Research | Novel process for removing sulfur from fuels |
| CN101798625A (en) * | 2010-04-14 | 2010-08-11 | 北京科技大学 | Method for removing sulfur from fuel before sintering iron ores |
| CN102230088A (en) * | 2011-07-10 | 2011-11-02 | 重庆大学 | Method for extracting manganese from manganese-enriched slag |
| CN102732718A (en) * | 2012-06-15 | 2012-10-17 | 浙江华友钴业股份有限公司 | Method for low temperature treatment of sulfide ore by using air and sulfur dioxide mixed gas |
| CN103131847A (en) * | 2013-03-16 | 2013-06-05 | 重庆大学 | Method for desulphurizing high-sulphur rhodochrosite |
| CN103276228A (en) * | 2013-06-19 | 2013-09-04 | 重庆大学 | Desulfurizing method for high-sulfur rhodochrosite |
Non-Patent Citations (1)
| Title |
|---|
| 梁月荣主编: "《茶资源综合利用》", 30 November 2013, 浙江大学出版社 * |
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Effective date of registration: 20200709 Address after: 3 / F, building 2, economic development zone, Wanshan District, Tongren City, Guizhou Province Patentee after: Tongren Guizhou Hecheng Manganese Industry Co.,Ltd. Address before: Xi Xiang prosperous village 554200 Guizhou area of Tongren province Wanshan District Patentee before: GUIZHOU WANSHAN XINGLONG MANGANESE INDUSTRY Co.,Ltd. |
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Address after: 554299 floor 3, building 2, economic development zone, Wanshan District, Tongren City, Guizhou Province Patentee after: Guizhou Tongren Hecheng Manganese Alloy Co.,Ltd. Address before: 554299 floor 3, building 2, economic development zone, Wanshan District, Tongren City, Guizhou Province Patentee before: Tongren Guizhou Hecheng Manganese Industry Co.,Ltd. |
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