CN104876192A - Process for reducing chroma of industrial sulfuric acid by air-hydrogen peroxide combined oxidation method - Google Patents
Process for reducing chroma of industrial sulfuric acid by air-hydrogen peroxide combined oxidation method Download PDFInfo
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- CN104876192A CN104876192A CN201510248073.7A CN201510248073A CN104876192A CN 104876192 A CN104876192 A CN 104876192A CN 201510248073 A CN201510248073 A CN 201510248073A CN 104876192 A CN104876192 A CN 104876192A
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Abstract
The invention provides a process for reducing the chromaticity of industrial sulfuric acid by an air-hydrogen peroxide combined oxidation method. The process method has the advantages of simple process, short flow, less investment, low cost, little pollution, capability of effectively removing the color of industrial sulfuric acid and the like, and overcomes the defects of large hydrogen peroxide consumption and high cost in the method for removing the color of the sulfuric acid by independently using hydrogen peroxide; can effectively reduce the chroma of the industrial sulfuric acid, ensure that the quality of the treated industrial sulfuric acid reaches the requirement of a GB/T534-2002 first-grade product, and simultaneously can obtain better economic benefit.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be specifically related to the technique that air-hydrogen peroxide co-oxidation method reduces industrial sulphuric acid colourity.
Background technology
Sulfuric acid is a kind of important basic chemical raw materials, is widely used in each industrial sector.The output of sulfuric acid is often used as the mark of a measurement National Industrial developmental level.Sulfuric acid refines, has the smelting of coloured gold Li mainly for the production of the case of chemical fertilizer, synthon, coating, washing composition, cooling agent, fodder additives and oil, and iron and steel, medicine and chemical industry.
By the end of the end of the year 2013, China's sulphuric acid output will be 8,650 ten thousand t, increase by 2.9% on a year-on-year basis, account for 36.5% of World Sulfur acid yield.Wherein, 3,967 ten thousand t are produced in Sulfur relieving haperacidity, increase by 1.6% on a year-on-year basis, account for 45.9% of sulfuric acid ultimate production; Metallurgical off-gas acid-making produces 2,473 ten thousand t, increases by 3.5% on a year-on-year basis, accounts for 28.6% of sulfuric acid ultimate production; Pyrite-based sulfuric acid production produces 2,157 ten thousand t, increases by 3.0% on a year-on-year basis, accounts for 24.9% of sulfuric acid ultimate production; 530,000 t are produced in other starting material relieving haperacidity such as phosphogypsum, hydrogen sulfide, increase by 2.2% on a year-on-year basis, account for 0.6% of sulfuric acid ultimate production.In recent years, along with the development of non-ferrous metals industry has also directly driven the development of metallurgical off-gas acid-making, " 12 " period, smelt sour production capacity by increase by 1,300 ten thousand more than t, smelting acid accounts for sulfuric acid ultimate production and will be greater than 30%.Due to flue gas during smelting complicated component, change of component fluctuation is comparatively large, causes sulfuric acid product quality unstable, affects result of use, bring adverse influence to enterprise marketing.
Flue gas during smelting sulfuric acid is that the sulfur dioxide gas produced when smelting kiln roasting by metal sulfide is produced through techniques such as dedusting, wet purification, dry suction, conversion and absorptions, the sulfuric acid product quality produced is by the impact of the factors such as metalliferous mineral raw material, smelting technology, purification process, and quality problems in various degree all appear in the sulfuric acid that many enterprises produce.
Sulfuric acid through adopting Imperial smelting process smelting technology to produce to certain Lead And Zinc Smelter domestic is black to be studied, this enterprise utilizes hard coal self-made gas for fuel, sinter fume relieving haperacidity, there is colourity unusual phenomenon in the sulfuric acid that sulfate system is produced always, main manifestations is color is sorrel, causes product price for a long time lower than GB/T534-2002 first grade price.Research shows, coal gas is that hard coal produced at producer gas generator gasification reaction, due to the reason such as local incomplete combustion of the organism in coal gas, coal gas, cause and enter flue gas system, fail to trap completely at cleaning section, thus enter in finished acid, further carbonization becomes sub-micro state carbon granules; From smelting technology angle analysis, in mineral roasting process, bring oxynitride into by air, fuel, nitrogenous beneficiation reagent etc., because oxynitride exists the reaction exacerbating iron and sulfuric acid, sulfuric acid colourity is occurred abnormal.Therefore, the partial reductive gas dissolved in sulfuric acid product, if sulfurous gas etc. and sub-micro state carbon granules and oxynitride cause sulfuric acid color to be major cause russet.
In industrial sulphuric acid decolouring technology, Chinese patent (notification number: CN102757021A) discloses the method utilizing hydrogen peroxide to decolour to sulfuric acid, and the volume ratio of sulfuric acid and superoxol is 100: 6 ~ 22.Chinese patent (notification number: CN102786036A) discloses the method utilizing potassium permanganate to decolour to sulfuric acid.
Due to the difference of gas washing in SA production raw material, the reason causing sulfuric acid painted is also many-sided, solve sulfuric acid decolouring technology, what key was oxygenant chooses with on decoloration process, the decolorizing effect that suitable oxygenant and rational decoloration process just can reach, and make decolouring cost lower, the economic benefit obtained.
Summary of the invention
Object of the present invention will provide a kind of air-hydrogen peroxide co-oxidation method to reduce the processing method of industrial sulphuric acid colourity exactly, this processing method adopts air-hydrogen peroxide co-oxidation removal of impurities principle, have that technique is simple, flow process is short, less investment, cost are low, it is little to pollute and can the plurality of advantages such as effective elimination industrial sulphuric acid color, compensate for and be used alone hydrogen peroxide and remove the deficiency that in the method for sulfuric acid color, hydrogen peroxide consumption is large, cost is high; Can effectively reduce industrial sulphuric acid colourity, make the industrial sulphuric acid quality after processing reach GB/T534-2002 first grade requirement, good economic benefit can be obtained simultaneously.
To achieve these goals, the present invention is achieved through the following technical solutions:
Air-hydrogen peroxide co-oxidation method reduces the technique of industrial sulphuric acid colourity, and this technique is carried out according to following step:
(1) by mass concentration be 93% industrial sulphuric acid load have in the reactor of heating function, pass into dry air, by process 1 ton of sulphur acid meter, air flow control is at 40 ~ 60L/min, and pressure-controlling, at 0.2MPa, is preheating to 40 DEG C;
(2) by mass concentration be 27.5 ~ 30% hydrogen peroxide be slowly added drop-wise in reactor, by process 1 ton of sulphur acid meter, hydrogen peroxide rate of addition is 0.15 ~ 0.2Lmin
-1, the mass ratio of hydrogen peroxide and industrial sulphuric acid is 0.5 ~ 0.7: 100, controls temperature of reaction at 45 ~ 50 DEG C; After hydrogen peroxide dropwises, under 45 ~ 50 DEG C of conditions, keep reaction 0.5h; Under 60 DEG C of conditions, keep reaction 1.5h, reaction terminates;
(3) start cooling, when temperature is down to 20 ~ 25 DEG C, stops passing into air, both obtained finished product sulfuric acid.
Wherein, the industrial sulphuric acid described in above-mentioned steps (1) is obtained by flue gas during smelting, and outward appearance is chocolate.
Wherein, the reactor described in above-mentioned steps (1) is the enamel reactor with chuck.
Wherein, be prepared in the compressed-air filter and moisture eliminator of routine at the filtration described in above-mentioned steps (1), dry air.
Compared with prior art, beneficial effect of the present invention is:
This processing method adopts air-hydrogen peroxide co-oxidation removal of impurities principle, have that technique is simple, flow process is short, less investment, cost are low, it is little to pollute and can the plurality of advantages such as effective elimination industrial sulphuric acid color, compensate for and be used alone hydrogen peroxide and remove the deficiency that in the method for sulfuric acid color, hydrogen peroxide consumption is large, cost is high; Can effectively reduce industrial sulphuric acid colourity, make the industrial sulphuric acid quality after processing reach GB/T534-2002 first grade requirement, good economic benefit can be obtained simultaneously.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention.
Embodiment
Below the present invention is described further:
Embodiment one
Certain Lead And Zinc Smelter domestic adopts Imperial smelting process smelting technology, utilize hard coal self-made gas for fuel, sinter fume relieving haperacidity, there is colourity unusual phenomenon in the sulfuric acid that sulfate system is produced always, main manifestations is color is sorrel, causes product price for a long time lower than GB/T534-2002 first grade price.Research shows, coal gas is that hard coal produced at producer gas generator gasification reaction, due to the reason such as local incomplete combustion of the organism in coal gas, coal gas, cause and enter flue gas system, fail to trap completely at cleaning section, thus enter in finished acid, further carbonization becomes sub-micro state carbon granules; From smelting technology angle analysis, in mineral roasting process, bring oxynitride into by air, fuel, nitrogenous beneficiation reagent etc., because oxynitride exists the reaction exacerbating iron and sulfuric acid, sulfuric acid colourity is occurred abnormal.Therefore, the partial reductive gas dissolved in sulfuric acid product, if sulfurous gas etc. and sub-micro state carbon granules and oxynitride cause sulfuric acid color to be major cause russet.
As shown in Figure 1, air-hydrogen peroxide co-oxidation method reduces sulfuric acid colourity technique and comprises the steps:
(1) air passes into and sulfuric acid preheating:
The painted sulfuric acid of 1t industry is loaded the 1m with heating function
3in reactor, pass into after filtration, dry air, air passes under pipeline should be inserted in sulfuric acid liquid level, and apart from reactor bottom 200 ~ 250mm, air flow control is at 40 ~ 60L/min, and pressure-controlling is at 0.2MPa; Open reactor heating unit, be preheating to 40 DEG C.
(2) oxidative decoloration reaction:
Slowly be added drop-wise in reactor by hydrogen peroxide, rate of addition controls at 0.15 ~ 0.2Lmin
-1, the mass ratio of hydrogen peroxide and industrial sulphuric acid is 0.5 ~ 0.7: 100, controls temperature of reaction at 45 ~ 50 DEG C; Hydrogen peroxide dropwises, and keeps reaction 0.5h under 45 ~ 50 DEG C of conditions; Under 60 DEG C of conditions, keep reaction 1.5h, reaction terminates.
(3) lower the temperature:
Oxidative decoloration starts cooling after reacting and terminating, and the air natural cooling passed into is taked in cooling, when temperature is down to 20 ~ 25 DEG C, stops passing into air, both obtains finished product sulfuric acid.
(4) sampling analysis chemical examination:
The finished product sulfuric acid sampling analysis of aforesaid method desolventing technology is chemically examined, the results are shown in Table 1.Result shows, adopt air-hydrogen peroxide co-oxidation method to reduce sulfuric acid colourity technique, the finished product sulfuric acid quality after decolouring reaches industrial sulphuric acid standard GB/T/T534-2002 first grade index request.
Claims (4)
1. air-hydrogen peroxide co-oxidation method reduces the technique of industrial sulphuric acid colourity, it is characterized in that: this technique is carried out according to following step:
(1) by mass concentration be 93% industrial sulphuric acid load have in the reactor of heating function, pass into dry air, by process 1 ton of sulphur acid meter, air flow control is at 40 ~ 60L/min, and pressure-controlling, at 0.2MPa, is preheating to 40 DEG C;
(2) by mass concentration be 27.5 ~ 30% hydrogen peroxide be slowly added drop-wise in reactor; By process 1 ton of sulphur acid meter, hydrogen peroxide rate of addition is 0.15 ~ 0.2Lmin
-1; The mass ratio of hydrogen peroxide and industrial sulphuric acid is 0.5 ~ 0.7: 100, controls temperature of reaction at 45 ~ 50 DEG C; After hydrogen peroxide dropwises, under 45 ~ 50 DEG C of conditions, keep reaction 0.5h; Under 60 DEG C of conditions, keep reaction 1.5h, reaction terminates;
(3) start cooling, when temperature is down to 20 ~ 25 DEG C, stops passing into air, both obtained finished product sulfuric acid.
2. air-hydrogen peroxide co-oxidation method as claimed in claim 1 reduces the technique of industrial sulphuric acid colourity, it is characterized in that: the industrial sulphuric acid described in above-mentioned steps (1) is obtained by flue gas during smelting, and outward appearance is chocolate.
3. air-hydrogen peroxide co-oxidation method as claimed in claim 1 reduces the technique of industrial sulphuric acid colourity, it is characterized in that: the reactor described in above-mentioned steps (1) is the enamel reactor with chuck.
4. air as claimed in claim 1-hydrogen peroxide co-oxidation method reduces the technique of industrial sulphuric acid colourity, it is characterized in that: be prepared in the compressed-air filter and moisture eliminator of routine at the filtration described in above-mentioned steps (1), dry air.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460905A (en) * | 2016-01-07 | 2016-04-06 | 长沙有色冶金设计研究院有限公司 | Technology for preparing high-quality sulfuric acid from non-ferrous metal smelting flue gas |
| CN109534302A (en) * | 2018-11-13 | 2019-03-29 | 乳源东阳光电化厂 | A kind of method and its application for removing dimethyl sulfate in sulfuric acid |
| CN113735069A (en) * | 2021-08-18 | 2021-12-03 | 西北矿冶研究院 | Process method for reducing chromaticity of industrial sulfuric acid by flue gas method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757021A (en) * | 2012-08-08 | 2012-10-31 | 刘立文 | Method for decolorizing sulfuric acid by using hydrogen peroxide |
| CN103172033A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757021A (en) * | 2012-08-08 | 2012-10-31 | 刘立文 | Method for decolorizing sulfuric acid by using hydrogen peroxide |
| CN103172033A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid |
Non-Patent Citations (1)
| Title |
|---|
| 杨鼎文: ""石化工业废硫酸的净化处理及回收利用"", 《化工环保》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460905A (en) * | 2016-01-07 | 2016-04-06 | 长沙有色冶金设计研究院有限公司 | Technology for preparing high-quality sulfuric acid from non-ferrous metal smelting flue gas |
| CN109534302A (en) * | 2018-11-13 | 2019-03-29 | 乳源东阳光电化厂 | A kind of method and its application for removing dimethyl sulfate in sulfuric acid |
| CN113735069A (en) * | 2021-08-18 | 2021-12-03 | 西北矿冶研究院 | Process method for reducing chromaticity of industrial sulfuric acid by flue gas method |
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