CN100556831C - The environmental protection of stainless steel acid-washing waste liquid utilizes method - Google Patents
The environmental protection of stainless steel acid-washing waste liquid utilizes method Download PDFInfo
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- CN100556831C CN100556831C CNB2007100241737A CN200710024173A CN100556831C CN 100556831 C CN100556831 C CN 100556831C CN B2007100241737 A CNB2007100241737 A CN B2007100241737A CN 200710024173 A CN200710024173 A CN 200710024173A CN 100556831 C CN100556831 C CN 100556831C
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Abstract
The environmental protection of stainless steel acid-washing waste liquid utilizes method, waste liquid is dropped into feed ammonia in the reaction vessel, and reacted mixed solution filters; In the nickel ammine filtrate that 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; In filtrate, drop into calcium hydroxide and generate Calcium Fluoride (Fluorspan) precipitation and nitrocalcite.Advantage of the present invention is 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
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.
Goal 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 drops into stainless steel acid-washing waste liquid and feeds ammonia in the reaction vessel, to pH value between 8-9, reacted mixed solution filtered obtains ferrochrome precipitation of hydroxide and nickel ammine filtrate;
B feeds hydrogen sulfide in the nickel ammine filtrate that preceding step produces, generate nickel sulphide precipitation and Neutral ammonium fluoride, ammonium nitrate mixed solution and free ammonia, and the sedimentation and filtration washing is obtained the nickelous sulfide product;
C, the b step is filtered out 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 complex compound 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 ironic hydroxide and the chromium hydroxide polymkeric substance that is insoluble in water, and be easy to filtering separation, select for use under the ammonia environment and nickel to be generated nickel ammine soluble in water and separate with siderochrome and in filtrate, lead to hydrogen sulfide then, make nickel generate the nickel sulphide precipitation that is insoluble in water, the mother liquor behind the separation nickelous sulfide 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 effective utilization of each effective constituent.
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↑
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 ammine 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 drops into stainless steel acid-washing waste liquid and feeds ammonia in the reaction vessel, to the pH value between 8-9, reacted mixed solution is filtered the filtrate that obtains the ferrochrome precipitation of hydroxide and contain nickel ammine;
B feeds hydrogen sulfide in the filtrate of containing nickel ammine that preceding step produces, generate nickel sulphide precipitation and Neutral ammonium fluoride, ammonium nitrate mixed solution and free ammonia, and the sedimentation and filtration washing is obtained the nickelous sulfide product;
C, the b step is filtered out 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, to its heat iron oxide product, the filtrate condensing crystal is 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 feeds recycle in the stainless steel acid-washing waste liquid.
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| CN100556831C true CN100556831C (en) | 2009-11-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020076315A1 (en) * | 2018-10-10 | 2020-04-16 | Lixivia, Inc. | Compositions and methods for purification of metals from steel making waste streams |
Families Citing this family (9)
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| 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 |
| 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 |
| 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 |
| CN109554718B (en) * | 2019-01-25 | 2020-11-13 | 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 |
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- 2007-07-18 CN CNB2007100241737A patent/CN100556831C/en not_active Expired - Fee Related
Non-Patent Citations (2)
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| 硝氟酸酸洗废液的治理. 稀有金属材料与工程，第6期. 1979 * |
| 钢铁酸洗废液的处理技术及其评价. 郑隆鳌，刘文夫.钢铁研究，第1期. 1997 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020076315A1 (en) * | 2018-10-10 | 2020-04-16 | Lixivia, Inc. | Compositions and methods for purification of metals from steel making waste streams |
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