CN101837959A - Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace - Google Patents
Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace Download PDFInfo
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- CN101837959A CN101837959A CN201010171938A CN201010171938A CN101837959A CN 101837959 A CN101837959 A CN 101837959A CN 201010171938 A CN201010171938 A CN 201010171938A CN 201010171938 A CN201010171938 A CN 201010171938A CN 101837959 A CN101837959 A CN 101837959A
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- sulfuric acid
- pyrolusite
- fluidizing furnace
- sulphur
- manganese
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Abstract
The invention discloses a method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in a fluidized bed furnace, which comprises the following steps of: blending the sulfur and the pyrolusite in a certain ratio, conveying the mixture into the fluidized bed furnace, reducing manganese dioxide in the pyrolusite into manganese oxide by using the sulfur and sulfur dioxide generated by combustion, discharging the manganese oxide into sulfuric acid solution or electrolytic manganese anode solution, slurrying and leaching manganese sulfate; and blowing air into the fluidized bed furnace from the upper section thereof, making sublimed sulfur fully combusted, performing temperature reduction and dedusting on sulfur dioxide generated by reaction, conveying the sulfur dioxide to a purification process, and producing the sulfuric acid by a sulfuric acid production process. By utilizing the conventional sulfuric acid producing fluidized bed furnace equipment, the production method can reduce the pyrolusite into the manganese sulfate, also can produce a great deal of sulfuric acid, greatly reduces equipment investment, saves investment, and reduces cost; meanwhile, in the reaction process, waste gas such as CO2, CO and SO2 and dust cannot be discharged, the operating conditions are good, and the environment is not influenced.
Description
Technical field
The present invention relates to a kind of method of utilizing the sulphur reducing pyrolusite, particularly relate to a kind of method of in fluidizing furnace, utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid.
Background technology
Manganous sulfate is the main raw material of manganese products such as preparation industrial manganic sulfate and electrolytic manganese, is widely used in chemical field such as medicine, papermaking, catalyzer, fodder additives and produces field of metallurgy such as electrolytic manganese and produce other manganese salt etc.Along with falling sharply of the manganese carbonate ore of divalence, the pyrolusite of occurring in nature tetravalence manganese (mainly being Manganse Dioxide) is more with its ore deposit amount, manganese content height, the low new resources that substitute manganese carbonate ore that become of price.But utilize pyrolusite to prepare in the process of manganous sulfate,, must be reduced into manganese monoxide (MnO) ability and sulfuric acid reaction generation manganous sulfate to it by reduction reaction because Manganse Dioxide is insoluble to sulfuric acid.
The method that existing pyrolusite reduction prepares manganous sulfate mainly contains two kinds: (1) coal reducing roasting-sulfuric acid leaching: this method is traditional production technique, the history of existing nearly half a century, technology is ripe, and the manganese sulfate solution quality of gained is good after sulfuric acid leaching, the removal of impurities.But the SO that it produces
2, serious dust pollution of the environment, coal consumption amount is big, labour intensity is big, reduction cost height.(2) two ore deposit roasting methods: with pyrolusite and sulfurous iron ore separated pulverizing, mix, 500 ℃-800 ℃ roasting temperature 0.5-1 hour, then with clear water leaching, separate, obtain manganese sulfate solution after the removal of impurities.This method equally also can produce SO
2And dust, contaminate environment, labour intensity is big.Above-mentioned pyrolusite roasting reduction technology need consume a large amount of fine coal as reductive agent, production process energy consumption height, long flow path, and produce a large amount of CO
2, CO and SO
2Waste gas and dust, operational condition is poor, and environmental pollution is more serious.
Summary of the invention
The object of the present invention is to provide a kind of method of in fluidizing furnace, utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid, this method has overcome the deficiency that prior art exists, use this kind method and can effectively reduce energy-output ratio, reduce environmental pollution, and can in reducing pyrolusite, realize co-producing sulfuric acid.
The object of the present invention is achieved like this, and it comprises the steps:
(a) sulphur and pyrolusite blending are according to a certain ratio sent in the fluidizing furnace, blasted air, make material in fluidizing furnace, seethe with excitement, burn, temperature in the stove of control fluidizing furnace at the fluidizing furnace hypomere;
The mixing proportion scope of described sulphur and pyrolusite is 1: (0-20); Temperature is controlled at 500-1000 ℃ in the stove of described fluidizing furnace;
(b) sulfurous gas of sulphur and generation is reduced to manganese monoxide with the Manganse Dioxide in the pyrolusite;
(c) manganese monoxide that produces is discharged from the discharge port of fluidizing furnace, the secluding air cooling directly enters it pulp in sulphuric acid soln or the electrolytic manganese anolyte then, leaches manganous sulfate;
(d) epimere from fluidizing furnace blasts air, and sublimed sulphur is fully burnt, and regulates the fluidizing furnace temperature out, and the sulfurous gas that reaction produces send cleaning section after cooling, dedusting, presses sulfuric acid production process then and produces sulfuric acid.
Described fluidizing furnace temperature out is controlled at 600-900 ℃;
Its reaction equation is as follows:
S+O
2→ SO
2(sulfurous gas) ... (1)
S+2MnO
2→ SO
2+ 2MnO (manganese monoxide) ... (2)
SO
2+ MnO
2→ MnO+SO
3(sulphur trioxide) ... (3)
2SO
2+ O
2→ 2SO
3(sulphur trioxide) ... (4)
SO
3+ H
2O → H
2SO
4(sulfuric acid) ... (5)
Beneficial effect of the present invention is:
(1) the existing gas washing in SA production fluidizing furnace equipment of production method utilization of the present invention can be reduced to manganous sulfate with pyrolusite, can produce a large amount of sulfuric acid again, has significantly reduced facility investment, economizes on the use of funds, and reduces cost;
(2) the present invention utilize sulphur purity in the existing gas washing in SA production be sulphur 99.5% or more as reductive agent and heating thermal source, burning can not produce other impurity, does not influence the utilization ratio of manganese; Necessary temperature condition (500-1000 ℃) also can be provided for the reduction of Manganse Dioxide, save fuel greatly, have very big economic benefit;
(3) with add colliery roasting reduction technology relatively, can not discharge CO
2, CO and SO
2Waste gas and dust, operational condition is good, does not influence environment.
Embodiment
Embodiment 1:
With sulphur and pyrolusite in proportion blending in 1: 3 send in the fluidizing furnace, blast air at the fluidizing furnace hypomere, make material under the strength effect of furnace bottom air-flow and furnace roof negative pressure, boiling in fluidizing furnace, burning, 850-950 ℃ of control fluidized layer temperature, the sulfur burning of blending in pyrolusite generates sulfurous gas, produces a large amount of heats; The sulfurous gas of sulphur and generation is reduced to manganese monoxide with the Manganse Dioxide in the pyrolusite.The manganese monoxide that the fluidizing furnace discharge port the is discharged secluding air cooling that falls into the water prevents that manganese monoxide is oxidized to Manganse Dioxide, also manganese monoxide directly can be entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leach manganous sulfate.Anoxic in the hypomere furnace gas contains sublimed sulphur, blasts air at the fluidizing furnace epimere, delivery of supplemental oxygen, and the sublimed sulphur that fully burns, reaction generates sulfurous gas; 850-900 ℃ of fluidizing furnace temperature out, the concentration of fluidizing furnace outlet sulfurous gas is 10-13%.The furnace gas that contains sulfurous gas send cleaning section after dedusting, press sulfuric acid production process then and produce sulfuric acid.
Embodiment 2:
Repeat embodiment 1 by above-mentioned same steps as, with sulphur and pyrolusite in proportion blending in 1: 7 send in the fluidizing furnace, 800-900 ℃ of control fluidized layer temperature, 800-900 ℃ of fluidizing furnace temperature out, the concentration of fluidizing furnace outlet sulfurous gas is 10-12%.
Embodiment 3:
Repeat embodiment 1 by above-mentioned same steps as, with sulphur and pyrolusite in proportion blending in 1: 15 send in the fluidizing furnace, 750-850 ℃ of control fluidized layer temperature, 800-850 ℃ of fluidizing furnace temperature out, the concentration of fluidizing furnace outlet sulfurous gas is 8-10%.
Claims (4)
1. a method of utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid in fluidizing furnace comprises the steps:
(a) sulphur and pyrolusite blending are according to a certain ratio sent in the fluidizing furnace, blasted air, make material in fluidizing furnace, seethe with excitement, burn, produce a large amount of sulfurous gas, temperature in the stove of control fluidizing furnace at the fluidizing furnace hypomere;
(b) sulfurous gas of sulphur and generation is reduced to manganese monoxide with the Manganse Dioxide in the pyrolusite;
(c) manganese monoxide that produces is discharged from the discharge port of fluidizing furnace, the secluding air cooling directly enters it pulp in sulphuric acid soln or the electrolytic manganese anolyte then, leaches manganous sulfate;
(d) epimere from fluidizing furnace blasts air, and sublimed sulphur is fully burnt, and regulates the fluidizing furnace temperature out, and the sulfurous gas that reaction produces send cleaning section after cooling, dedusting, presses sulfuric acid production process then and produces sulfuric acid.
2. a kind of method of utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid in fluidizing furnace according to claim 1 is characterized in that: described sulphur and pyrolusite are by 1: proportioning blending (0-20).
3. a kind of method of utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid in fluidizing furnace according to claim 1 is characterized in that: temperature is controlled at 500-1000 ℃ in the stove of described fluidizing furnace.
4. a kind of method of utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid in fluidizing furnace according to claim 1 is characterized in that: described fluidizing furnace temperature out is controlled at 600-900 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101719381A CN101837959B (en) | 2010-05-14 | 2010-05-14 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101719381A CN101837959B (en) | 2010-05-14 | 2010-05-14 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
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| Publication Number | Publication Date |
|---|---|
| CN101837959A true CN101837959A (en) | 2010-09-22 |
| CN101837959B CN101837959B (en) | 2012-11-07 |
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|---|---|---|---|
| CN2010101719381A Expired - Fee Related CN101837959B (en) | 2010-05-14 | 2010-05-14 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320665A (en) * | 2011-07-27 | 2012-01-18 | 姚茂君 | Application of secondary air to process for reducing pyrolusite and producing sulfuric acid in fluidized bed furnace |
| CN102390867A (en) * | 2011-07-27 | 2012-03-28 | 刘芳 | Diatomite purification and impurity removal method for manganese sulfate solution |
| CN102424365A (en) * | 2011-07-27 | 2012-04-25 | 刘集贵 | Recycling method of tail gas from pyrolusite reduction and sulfuric acid coproduction in fluidized bed furnace |
| CN107098393A (en) * | 2017-06-23 | 2017-08-29 | 中南大学 | The preparation method of high-purity manganese monoxide |
| CN108892109A (en) * | 2018-08-03 | 2018-11-27 | 禄丰天宝磷化工有限公司 | A kind of oxide boiling roasting device of production of sulfur from pyrite acid |
| CN112551589A (en) * | 2020-11-24 | 2021-03-26 | 湘西蒙成科技有限责任公司 | Energy-saving reduction method of manganese dioxide, manganese dioxide and application |
| CN114457235A (en) * | 2022-01-26 | 2022-05-10 | 贵州金瑞新材料有限责任公司 | Application method of high-iron reduced ore in electrolytic manganese production process |
| CN115159470A (en) * | 2022-08-02 | 2022-10-11 | 广西埃索凯新材料科技有限公司 | Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur |
Citations (3)
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|---|---|---|---|---|
| US3348912A (en) * | 1963-09-23 | 1967-10-24 | Utah Construction & Mining Co | Method of preparing manganese sulfate from pyrite reduced manganese dioxide ores |
| CN101157481A (en) * | 2007-07-24 | 2008-04-09 | 汪云华 | Method for preparing manganese sulfate by manganese oxide ore |
| CN101413056A (en) * | 2008-11-25 | 2009-04-22 | 朱军 | Manganese ore reduction calcination method and apparatus |
-
2010
- 2010-05-14 CN CN2010101719381A patent/CN101837959B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3348912A (en) * | 1963-09-23 | 1967-10-24 | Utah Construction & Mining Co | Method of preparing manganese sulfate from pyrite reduced manganese dioxide ores |
| CN101157481A (en) * | 2007-07-24 | 2008-04-09 | 汪云华 | Method for preparing manganese sulfate by manganese oxide ore |
| CN101413056A (en) * | 2008-11-25 | 2009-04-22 | 朱军 | Manganese ore reduction calcination method and apparatus |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320665A (en) * | 2011-07-27 | 2012-01-18 | 姚茂君 | Application of secondary air to process for reducing pyrolusite and producing sulfuric acid in fluidized bed furnace |
| CN102390867A (en) * | 2011-07-27 | 2012-03-28 | 刘芳 | Diatomite purification and impurity removal method for manganese sulfate solution |
| CN102424365A (en) * | 2011-07-27 | 2012-04-25 | 刘集贵 | Recycling method of tail gas from pyrolusite reduction and sulfuric acid coproduction in fluidized bed furnace |
| CN102424365B (en) * | 2011-07-27 | 2013-07-24 | 湖南省泸溪县金旭治化有限责任公司 | Recycling method of tail gas from pyrolusite reduction and sulfuric acid coproduction in fluidized bed furnace |
| CN107098393A (en) * | 2017-06-23 | 2017-08-29 | 中南大学 | The preparation method of high-purity manganese monoxide |
| CN107098393B (en) * | 2017-06-23 | 2019-06-18 | 中南大学 | The preparation method of high-purity manganese monoxide |
| CN108892109A (en) * | 2018-08-03 | 2018-11-27 | 禄丰天宝磷化工有限公司 | A kind of oxide boiling roasting device of production of sulfur from pyrite acid |
| CN112551589A (en) * | 2020-11-24 | 2021-03-26 | 湘西蒙成科技有限责任公司 | Energy-saving reduction method of manganese dioxide, manganese dioxide and application |
| CN114457235A (en) * | 2022-01-26 | 2022-05-10 | 贵州金瑞新材料有限责任公司 | Application method of high-iron reduced ore in electrolytic manganese production process |
| CN115159470A (en) * | 2022-08-02 | 2022-10-11 | 广西埃索凯新材料科技有限公司 | Method for preparing sulfuric acid and manganese sulfate in linkage manner by adopting sulfur |
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| Publication number | Publication date |
|---|---|
| CN101837959B (en) | 2012-11-07 |
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Granted publication date: 20121107 Termination date: 20160514 |