CN101514033A - Environment friendly processing method of waste acid containing ferrous sulphate - Google Patents
Environment friendly processing method of waste acid containing ferrous sulphate Download PDFInfo
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- CN101514033A CN101514033A CNA2009100198810A CN200910019881A CN101514033A CN 101514033 A CN101514033 A CN 101514033A CN A2009100198810 A CNA2009100198810 A CN A2009100198810A CN 200910019881 A CN200910019881 A CN 200910019881A CN 101514033 A CN101514033 A CN 101514033A
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Abstract
The invention discloses an environment friendly processing method of waste acid containing ferrous sulphate, mainly comprising the following steps: the waste acid containing ferrous sulphate is oxidized by hydrogen peroxide and neutralized and displaced by magnesium oxide to generate ferric hydroxide deposit and magnesium sulphate by reaction, and fine powder of ferric oxide is obtained after the generated ferric hydroxide deposit is filtered, washed by water and dried while hot. In the whole processing course, no three wastes are discharged; the fine powder products of ferric oxide and magnesium sulphate products obtained through processing can be sold and the obtained magnesium sulphate products can also be reused; the treated water discharged during production can be recycled as primary water, thus radically solving nuisanceless disposal of the waste acid containing ferrous sulphate, greatly saving the processing cost of waste acid and obtaining by-products to be sold, therefore, the comprehensive benefits are high.
Description
Technical field
The present invention relates to the spent acid treatment process.
Background technology
At present, in the production process of special steel and titanium white, need to consume a large amount of sulfuric acid, produce one ton of titanium dioxide and need discharge about 8 tons and contain H
2SO
420% dilute sulphuric acid contains a large amount of ferrous sulfate in the acid.This useless vitriolic treatment process is at present: adopt unslaked lime to neutralize, the neutralization back generates contains lot of F e
2O
3Gypsum owing to contain Fe
2O
3The gypsum usability of discharge is limited to, generally it is stored up as industrial residue, so fundamentally do not solve problem of environmental pollution, just be exchanged into another kind of pollution mode.Become current special steel, titanium powder industry problem demanding prompt solution so invent a kind of environment-friendly treatment method of spent acid.
Summary of the invention
The purpose of this invention is to provide a kind of environment-friendly treatment method that contains the ferrous sulfate spent acid, this treatment process has not only solved existing treatment process and has caused secondary pollution problem easily, and the chemical substance recycle again that obtains after handling.
For achieving the above object, spent acid treatment process of the present invention is as follows:
The first step: the spent acid that will contain ferrous sulfate is delivered in the oxidation tank, constantly adds hydrogen peroxide oxidant when stirring, and makes the ferrous sulfate complete oxidation in the spent acid generate ferric sulfate, and chemical equation is
Second step: the spent acid behind the complete oxidation is sent in the neutralization tank, adding magnesium oxide in neutralization tank stirs, during spent acid carried out and replacement(metathesis)reaction, magnesium oxide elder generation and sulfuric acid reaction, then with spent acid in the ferric sulfate reaction generate sorrel ferric hydroxide precipitate and sal epsom; Question response stops to add magnesium oxide during to PH=4-5, and neutralization finishes, and the ferro element in this moment spent acid all generates the ferric hydroxide precipitate of indissoluble, and this moment, the spent acid temperature of reaction reached more than 80 ℃.Chemical equation is:
H
2SO
4+MgO＝MgSO
4+H
2O
MgO+H
2O＝Mg(OH)
2
3Mg(OH)
2+Fe
2(SO
4)
3＝3MgSO
4+2Fe(OH)
3
The 3rd step: the solution that contains a large amount of ferric hydroxide precipitate of above-mentioned second step neutralization reaction generation is sent into filter while hot filter, obtain Fe (OH)
3Filter cake is used the clear water washing leaching cake again, with the sal epsom washes clean in the filter cake, and send in the dryer and does, and obtains the iron oxide fine powder after the oven dry.
The 4th step: filtrate and washing water that the 3rd step filter was discharged filter through activated charcoal filter, remove the organic impurity in the solution, and the solution after will filtering then enters membrane separation unit and carries densely, and the fresh water of membrane sepn is discharged the back and continued use as a water; The dope of membrane sepn is the saturated solution of magnesium sulfate of concentration more than 40%.
The 5th step: saturated solution of magnesium sulfate is pumped in the vaporizer, and heating concentrates, the dope crystallization, and the solution of advantages of good crystallization enters whizzer and separates the sal epsom (MgSO that obtains containing n hydrate
4.nH
2O), regulate the sal epsom that Tc obtains containing different hydrates, the centrifugate that whizzer is discharged enters vaporizer again and carries out the circulating and evaporating crystallization; The water of condensation that vaporizer produces turns back in the system and continues to use as a water.
It is low to utilize the present invention to handle the sal epsom impurity that spent acid obtains, and can be used as feed grade sal epsom and sells.Or send and calcine production sulfuric acid in the calcining furnace.The magnesium oxide reuse again that calcining obtains.The flue gas that calcining furnace produces is removed dust in flue gas through purification system, but the magnesia powder reuse again that cyclonic separation is discharged.
Positively effect of the present invention is, in the entire treatment process, no waste discharge, treatedly obtain iron oxide fine powder product and the sal epsom product can be sold, the sal epsom product that obtains can carry out reuse again, and the treating water of discharging in the production process can be used as a water cycle and uses, so fundamentally solved the nuisanceless handling problem of the ferrous spent acid of sulfur acid, and saved the spent acid processing cost greatly, and can obtain by-product sale again, comprehensive benefit is higher.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a process flow diagram of the present invention.
Embodiment
From Fig. 1 process flow diagram as can be seen, technological process of the present invention is as follows:
The chemical industry sulfur waste acid of discharging from the production process of special steel and titanium white is delivered in the oxidation tank, adds continuous stirring of hydrogen peroxide oxidant simultaneously and carries out oxidizing reaction, and the complete reaction under the oxygenant effect of hydrogen peroxide of the ferrous sulfate in the sulfur waste acid generates ferric sulfate; Spent acid behind the complete oxidation is sent in the neutralization tank, add simultaneously magnesium oxide sulfur waste acid is carried out in and replacement(metathesis)reaction, in reaction process, magnesium oxide elder generation and sulfuric acid generation neutralization reaction, then with spent acid in ferric sulfate reaction generate sorrel ferric hydroxide precipitate and sal epsom, question response stops to add magnesium oxide during to PH=4-5, and neutralization finishes; The solution that will contain ferric hydroxide precipitate is sent into filter while hot and is filtered, and obtains Fe (OH)
3Filter cake and filtrate are sent after with the sal epsom washes clean in the filter cake in the dryer with clear water and to be done, and obtain the iron oxide fine powder; Filtrate and washing water enter membrane separation unit and carry densely after activated charcoal filter filters, the fresh water of membrane sepn is discharged the back and continued to use as a water; The dope of membrane sepn is that the saturated solution of magnesium sulfate of concentration more than 40% is pumped in the vaporizer, and heating concentrates, crystallization, and the solution of advantages of good crystallization enters whizzer and separates the sal epsom (MgSO that obtains containing n hydrate
4.nH
2O), regulate the sal epsom that Tc obtains containing different hydrates, the centrifugate that whizzer is discharged enters vaporizer again and carries out the circulating and evaporating crystallization; The water of condensation that vaporizer produces turns back in the system and continues to use as a water.
Claims (1)
1, a kind of environment-friendly treatment method that contains the ferrous sulfate spent acid is characterized in that it may further comprise the steps:
The first step: the spent acid that will contain ferrous sulfate is delivered in the oxidation tank, constantly adds hydrogen peroxide oxidant when stirring, and makes the ferrous sulfate complete oxidation in the spent acid generate ferric sulfate;
Second step: the spent acid behind the complete oxidation is sent in the neutralization tank, adding magnesium oxide in neutralization tank stirs, during spent acid carried out and replacement(metathesis)reaction, magnesium oxide elder generation and sulfuric acid reaction, then with spent acid in the ferric sulfate reaction generate sorrel ferric hydroxide precipitate and sal epsom; Question response stops to add magnesium oxide during to PH=4-5, and neutralization finishes, and the ferro element in this moment spent acid all generates the ferric hydroxide precipitate of indissoluble, and this moment, the spent acid temperature of reaction reached more than 80 ℃;
The 3rd step: the solution that contains a large amount of ferric hydroxide precipitate of above-mentioned second step neutralization reaction generation is sent into filter while hot filter, obtain Fe (OH)
3Filter cake is used the clear water washing leaching cake again, will obtain the iron oxide fine powder after the sal epsom washes clean in the filter cake, the oven dry;
The 4th step: filtrate and washing water that the 3rd step filter was discharged filter through activated charcoal filter, remove the organic impurity in the solution, and the solution after will filtering then enters membrane separation unit and carries densely, and the fresh water of membrane sepn is discharged the back and continued use as a water; The dope of membrane sepn is the saturated solution of magnesium sulfate of concentration more than 40%;
The 5th step: saturated solution of magnesium sulfate is pumped in the vaporizer, and heating concentrates, crystallization, and the solution of advantages of good crystallization enters whizzer and separates the sal epsom MgSO that obtains containing n hydrate
4.nH
2O regulates the sal epsom that Tc obtains containing different hydrates, and the centrifugate that whizzer is discharged enters vaporizer again and carries out the circulating and evaporating crystallization; The water of condensation that vaporizer produces turns back in the system and continues to use as a water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100198810A CN101514033A (en) | 2009-03-21 | 2009-03-21 | Environment friendly processing method of waste acid containing ferrous sulphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100198810A CN101514033A (en) | 2009-03-21 | 2009-03-21 | Environment friendly processing method of waste acid containing ferrous sulphate |
Publications (1)
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|---|---|
| CN101514033A true CN101514033A (en) | 2009-08-26 |
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ID=41038668
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|---|---|---|---|
| CNA2009100198810A Pending CN101514033A (en) | 2009-03-21 | 2009-03-21 | Environment friendly processing method of waste acid containing ferrous sulphate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107911A (en) * | 2011-03-04 | 2011-06-29 | 大连海事大学 | Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma |
| CN109836002A (en) * | 2017-11-24 | 2019-06-04 | 常州第六元素材料科技股份有限公司 | The hierarchical processing method of the spent acid containing manganese |
-
2009
- 2009-03-21 CN CNA2009100198810A patent/CN101514033A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107911A (en) * | 2011-03-04 | 2011-06-29 | 大连海事大学 | Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma |
| CN102107911B (en) * | 2011-03-04 | 2012-07-04 | 大连海事大学 | Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma |
| CN109836002A (en) * | 2017-11-24 | 2019-06-04 | 常州第六元素材料科技股份有限公司 | The hierarchical processing method of the spent acid containing manganese |
| CN109836002B (en) * | 2017-11-24 | 2021-12-03 | 常州第六元素材料科技股份有限公司 | Grading treatment method for manganese-containing waste acid |
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Open date: 20090826 |