CN101100341A - Environmental protection utilization method for stainless steel pickling waste liquid - Google Patents
Environmental protection utilization method for stainless steel pickling waste liquid Download PDFInfo
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- CN101100341A CN101100341A CNA2007100241737A CN200710024173A CN101100341A CN 101100341 A CN101100341 A CN 101100341A CN A2007100241737 A CNA2007100241737 A CN A2007100241737A CN 200710024173 A CN200710024173 A CN 200710024173A CN 101100341 A CN101100341 A CN 101100341A
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- stainless steel
- waste liquid
- ammonia
- filtrate
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Abstract
This invention discloses an environmental-protection reutilization of waste-liquid from acid pickling of stainless steel. Said waste-liquid is fed into a vessel, and passing ammonia into the vessel for reaction; the produced mixture is then filtered; the filtrate containing nickel-ammonia complex is added with hydrogen sulfide to produce nickel sulfide precipitate and mixed solution containing ammonium fluoride and ammonium nitrate and free ammonia. The precipitate after filtration is washed to produce nickel sulfide as product. Said filtrate is added with calcium hydroxide to produce calcium fluoride precipitate and calcium nitrate. This invention has advantages of: environmental protection treatment of waste-water with no pollution, recovering valuable components from waste-liquid, obtaining high economic benefit and social benefit.
Description
Technical field
The present invention relates to the environment-friendly treatment method of trade effluent, especially the treatment process of the spent pickle liquor that produces in the stainless steel product production process.
Background technology
Generally can use pickling in the stainless steel product production process, remove grey black etc. such as the tempering rear surface, after the pickling in the waste liquid except that containing a large amount of hydrofluoric acid, nitric acid, iron, chromium, also contain the higher nickel of a certain amount of utility value.Processing to stainless steel acid-washing waste liquid mainly is to adopt lime that heavy metal precipitation is got off simply at present, and ignored in the waste liquid ammonia nitrogen to the pollution of water body, thereby stainless steel acid-washing waste liquid is failed to obtain preferably environmental protection treatment and the severe contamination water body environment for a long time, the Taihu Lake blue-green algae wreaked havoc and caused Wuxi urbanite water consumption difficulty last stage, because of the stainless steel production in several small towns in Wuxi, the Changzhou in ring Taihu Lake very flourishing, as Wuxi Luo She town, Luoyang, Changzhou town etc., stainless steel acid-washing waste liquid also is one of pollution factor of wherein outbalance.
Summary of the invention
The objective of the invention is the spent pickle liquor that produces in the stainless steel product production, provide a kind of pollution-free and can also reclaim and wherein have the environmental protection of the stainless steel acid-washing waste liquid that utilizes the composition that is worth to utilize method.
The technical scheme that realizes above-mentioned purpose is as follows:
The environmental protection of stainless steel acid-washing waste liquid utilizes method, comprises the steps:
A. stainless steel acid-washing waste liquid is dropped into and feeds ammonia in the reaction vessel, to pH value between 8-9, reacted mixed solution filtered obtains ferrochrome precipitation of hydroxide and nickel ammonia chromium complex filtrate;
B. in the nickel ammine filtrate that preceding step produces, feed hydrogen sulfide, generate nickel sulphide precipitation and Neutral ammonium fluoride, ammonium nitrate mixed solution and free ammonia, the sedimentation and filtration washing is obtained the nickelous sulfide product;
C. the b step is filtered out and drop into calcium hydroxide in the filtrate of post precipitation and slowly be heated to the 60-80 degree, under this temperature, will distill out ammonia, and reaction generates Calcium Fluoride (Fluorspan) precipitation and nitrocalcite, dry after filtering again the Calcium Fluoride (Fluorspan) product, filtrate technology is routinely made the nitrocalcite product.
Stir and to add again that sulfuric acid stirs and adding water in the ferrochrome precipitation of hydroxide that produces in the aforesaid a step to PH3.5 ± 0.1, and be heated to more than 80 degree, again filter residue is carried out filtration washing, filter residue is an ironic hydroxide, can get iron oxide product to its heating, the filtrate condensing crystal can be got the basic chromium sulfate product.
The ammonia that distills out in the aforementioned c step can feed recycle in the stainless steel acid-washing waste liquid.
For ease of understanding technical solution of the present invention, sketch principle below in conjunction with reaction equation.
Because siderochrome and hydrofluoric acid can form more stable chromium complex in the waste liquid, be difficult to destroy their stability according to a conventional method, they are separated from solution effectively, we find FeF according to experiment
6 3-, CrF
6 3-Under alkaline condition, can complete hydrolysis also generate the difficult chromium hydroxide polymkeric substance that is deeper than water, and be easy to filtering separation, selecting for use ammonia environment decline nickel to generate nickel ammonia chromium complex soluble in water separates with siderochrome, in filtrate, feed hydrogen sulfide then, make nickel generate the nickel sulphide precipitation that is insoluble in water, the mother liquor that separates after sulfuration is pinched adds calcium hydroxide again and distills out the ammonia recycle utilization that reaction generates; In PH3.5 ± 0.1, ferric ion does not react, and chromium ion reacts, thereby can realize the separation with siderochrome oxyhydroxide, thereby has realized that each effective constituent ground effectively utilizes.
Chemical equation can be expressed as follows:
FeF
6 3+NH
3—→Fe(OH)
3↓+NH
4F
CrF
6 3-+NH
3—→Cr(OH)
3↓+NH
4F
Ni(NO
3)
2+NH
3—→Ni(NH
3)
4NO
3
Ni(NH
3)
4NO
3+H
2S—→NiS↓+NH
4NO
3+NH
3
NH
4NO
3+ NH
4F+Cr (OH)
3-→ CaF
2↓+Ca (NO
3)
2+ NH
3↑ area
Cr (OH)
3+ H
2SO
4-→ Cr (OH) SO
4(pH value 3.5 ± 0.1)
Fe(OH)
3—→Fe
2O
3+H
2O
Advantage of the present invention is effectively to handle the spent pickle liquor that forms in the stainless steel product Industrial processes, can the waste liquid environmental protection treatment is free from environmental pollution, but valuable ingredients in the efficient recovery waste liquid again has higher society and economy benefit.
Description of drawings
Fig. 1 is the process flow sheet in the specific embodiment of the invention.
Embodiment
Below in conjunction with description of drawings the specific embodiment of the present invention:
Stainless steel acid-washing waste liquid dropped into feeds ammonia in the reaction vessel, to pH value 8, reacted mixed solution filtered obtains ferrochrome precipitation of hydroxide and nickel ammonia chromium complex filtrate; In nickel ammine filtrate, feed hydrogen sulfide, generate nickel sulphide precipitation and Neutral ammonium fluoride, ammonium nitrate mixed solution and free ammonia, the sedimentation and filtration washing is obtained the nickelous sulfide product; In filtrate, drops into calcium hydroxide and slowly be heated to 70 degree, under this temperature, will distill out ammonia, and reaction generates Calcium Fluoride (Fluorspan) precipitation and nitrocalcite, dry after filtering again the Calcium Fluoride (Fluorspan) product, filtrate is made the nitrocalcite product by condensing crystal.Ammonia is by recycle in the squirt pump suction stainless steel acid-washing waste liquid.
Adding water in the ferrochrome precipitation of hydroxide stirs and to add that sulfuric acid stirs and to PH3.5 again, and be heated to 90 the degree, again remaining filter residue is carried out filtration washing, filter residue is not for participating in the ironic hydroxide of reaction under this sour environment, can get iron oxide product to its heating, the filtrate condensing crystal can be got the basic chromium sulfate product.
Claims (3)
1, the environmental protection of stainless steel acid-washing waste liquid utilizes method, it is characterized in that: comprise the steps:
A. stainless steel acid-washing waste liquid is dropped into and feeds ammonia in the reaction vessel, to pH value between 8-9, reacted mixed solution filtered obtains ferrochrome precipitation of hydroxide and nickel ammonia chromium complex filtrate;
B. in the nickel ammine filtrate that preceding step produces, feed hydrogen sulfide, generate nickel sulphide precipitation and Neutral ammonium fluoride, ammonium nitrate mixed solution and free ammonia, the sedimentation and filtration washing is obtained the nickelous sulfide product;
C. the b step is filtered out and drop into calcium hydroxide in the filtrate of post precipitation and slowly be heated to the 60-80 degree, under this temperature, will distill out ammonia, and reaction generates Calcium Fluoride (Fluorspan) precipitation and nitrocalcite, dry after filtering again the Calcium Fluoride (Fluorspan) product, filtrate technology is routinely made the nitrocalcite product.
2, the environmental protection of stainless steel acid-washing waste liquid according to claim 1 utilizes method, it is characterized in that: add water in the ferrochrome precipitation of hydroxide that produces in the described a step and stir and to add again that sulfuric acid stirs and to PH3.5 ± 0.1, and be heated to more than 80 degree, again filter residue is carried out filtration washing, filter residue is an ironic hydroxide, can get iron oxide product to its heating, the filtrate condensing crystal can be got the basic chromium sulfate product.
3, the environmental protection of stainless steel acid-washing waste liquid according to claim 1 and 2 utilizes method, it is characterized in that: the ammonia that distills out in the described c step can feed recycle in the stainless steel acid-washing waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100241737A CN100556831C (en) | 2007-07-18 | 2007-07-18 | The environmental protection of stainless steel acid-washing waste liquid utilizes method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100241737A CN100556831C (en) | 2007-07-18 | 2007-07-18 | The environmental protection of stainless steel acid-washing waste liquid utilizes method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101100341A true CN101100341A (en) | 2008-01-09 |
| CN100556831C CN100556831C (en) | 2009-11-04 |
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| CNB2007100241737A Expired - Fee Related CN100556831C (en) | 2007-07-18 | 2007-07-18 | The environmental protection of stainless steel acid-washing waste liquid utilizes method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376547B (en) * | 2008-10-10 | 2010-10-13 | 韩晓波 | Method for recovering and processing pickling solution of refining benzene |
| CN102115038A (en) * | 2010-12-30 | 2011-07-06 | 王莉 | Method for preparing sulfides and mixed product of sodium sulfide and strontium sulfate by manganese-containing waste liquid |
| CN102115039A (en) * | 2010-12-30 | 2011-07-06 | 王莉 | Method for preparing sulfide and mixed product of sodium sulfide and ammonium sulfate by manganese-containing waste liquid |
| CN104098148A (en) * | 2013-04-08 | 2014-10-15 | 兰州大学 | Processing method for recovering nickel, chromium and iron from stainless steel factory waste residue |
| CN104805291A (en) * | 2015-04-16 | 2015-07-29 | 南阳师范学院 | Method for treating stainless steel pickling waste liquor and recovering iron, chromium and nickel |
| CN104973745A (en) * | 2014-04-11 | 2015-10-14 | 河北建支铸造集团有限公司 | Harmless treatment method of red sludge in after-treatment liquid of cold galvanizing |
| CN108166009A (en) * | 2018-02-06 | 2018-06-15 | 北海诚德镍业有限公司 | The system and method for nickelous carbonate are extracted in a kind of waste mixed acid from acid-washing stainless steel |
| CN109554718A (en) * | 2019-01-25 | 2019-04-02 | 鲍君杰 | Treatment method of stainless steel pickling waste liquid |
| CN112520776A (en) * | 2020-11-26 | 2021-03-19 | 广沣金源（北京）科技有限公司 | Combined treatment method for fluorine-containing nitric acid waste liquid and hydrofluoric acid waste liquid |
| CN113165897A (en) * | 2018-10-10 | 2021-07-23 | 里克希维亚有限公司 | Compositions and methods for purifying metals from steelmaking waste streams |
-
2007
- 2007-07-18 CN CNB2007100241737A patent/CN100556831C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376547B (en) * | 2008-10-10 | 2010-10-13 | 韩晓波 | Method for recovering and processing pickling solution of refining benzene |
| CN102115038A (en) * | 2010-12-30 | 2011-07-06 | 王莉 | Method for preparing sulfides and mixed product of sodium sulfide and strontium sulfate by manganese-containing waste liquid |
| CN102115039A (en) * | 2010-12-30 | 2011-07-06 | 王莉 | Method for preparing sulfide and mixed product of sodium sulfide and ammonium sulfate by manganese-containing waste liquid |
| CN104098148A (en) * | 2013-04-08 | 2014-10-15 | 兰州大学 | Processing method for recovering nickel, chromium and iron from stainless steel factory waste residue |
| CN104098148B (en) * | 2013-04-08 | 2015-11-18 | 兰州大学 | A kind for the treatment of process reclaiming nickel, chromium, iron from stainless steel plant's waste residue |
| CN104973745A (en) * | 2014-04-11 | 2015-10-14 | 河北建支铸造集团有限公司 | Harmless treatment method of red sludge in after-treatment liquid of cold galvanizing |
| CN104805291A (en) * | 2015-04-16 | 2015-07-29 | 南阳师范学院 | Method for treating stainless steel pickling waste liquor and recovering iron, chromium and nickel |
| CN104805291B (en) * | 2015-04-16 | 2016-10-05 | 南阳师范学院 | The process of a kind of stainless steel acid-washing waste liquid and iron, chromium, the recovery method of nickel |
| CN108166009A (en) * | 2018-02-06 | 2018-06-15 | 北海诚德镍业有限公司 | The system and method for nickelous carbonate are extracted in a kind of waste mixed acid from acid-washing stainless steel |
| CN113165897A (en) * | 2018-10-10 | 2021-07-23 | 里克希维亚有限公司 | Compositions and methods for purifying metals from steelmaking waste streams |
| CN109554718A (en) * | 2019-01-25 | 2019-04-02 | 鲍君杰 | Treatment method of stainless steel pickling waste liquid |
| CN112520776A (en) * | 2020-11-26 | 2021-03-19 | 广沣金源（北京）科技有限公司 | Combined treatment method for fluorine-containing nitric acid waste liquid and hydrofluoric acid waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100556831C (en) | 2009-11-04 |
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