CN104003490A - Method for treating stainless steel acid pickling waste liquid and recovering metal with addition of [beta]-ferric fluoride trihydrate seed crystal - Google Patents
Method for treating stainless steel acid pickling waste liquid and recovering metal with addition of [beta]-ferric fluoride trihydrate seed crystal Download PDFInfo
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- CN104003490A CN104003490A CN201410210539.XA CN201410210539A CN104003490A CN 104003490 A CN104003490 A CN 104003490A CN 201410210539 A CN201410210539 A CN 201410210539A CN 104003490 A CN104003490 A CN 104003490A
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- waste liquid
- acid
- acid pickling
- stainless steel
- ferric fluoride
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Abstract
The invention relates to a method for recycling stainless steel acid pickling waste liquid and recovering valuable metal in the acid pickling waste liquid and belongs to the technical field of waste liquid treatment. The methods in the invention mainly includes steps of: furthest precipitating metal ions in the acid pickling waste liquid by controlling a temperature and an addition amount of seed crystals; carrying out a solid-liquid separation process; according to components of the acid pickling waste liquid, supplying fresh HNO3 and HF to the acid pickling waste liquid after being precipitated to enable the acid pickling waste liquid to reach a concentration capable of being used for an acid pickling process; and then precipitating metal again. With recycle of the acid pickling waste liquid, not only is waste of acid reduced but also cost during subsequent treatment steps of waste acid is reduced. In addition, generation of stainless steel acid pickling sludge is reduced.
Description
Technical field
The present invention relates to the treatment process that stainless steel acid-washing waste liquid reclaims metal, belong to industrial waste acid manipulation of regeneration technical field.
Background technology
Stainless steel product is with a long history, can trace back to the earliest 1910 before and after, by Germany, UK and USA almost succeeds in developing stainless steel simultaneously.But in this short development course, stainless steel is through invention to initial stage industrialization and the large production of modern industrialization, and its output and production technology have had increase and the development of advancing by leaps and bounds.In stainless later stage cold-rolling production process, will carry out surface treatment to stainless steel product, be generally with 1 ~ 3molL
-1hNO
3with 1 ~ 3molL
-1hF mix, at 40 ~ 60 DEG C by its surface passivating treatment.In this surface treatment process, acid solution can penetrate into from the zone of oxidation gap of stainless steel surface the inside, the metal of simultaneous oxidation the inside.In the process of oxidized metal, can generate NO
xgas, the gas of generation will fall the zone of oxidation punching that is attached to stainless steel surface.In whole acid cleaning process, acid is constantly to consume, so acid is depleted to when a certain amount of and need to adds eo-acid to it in pickle solution, to keep the concentration of acid in whole acid cleaning process roughly constant.But the concentration of metal ions dissolving in pickle solution can constantly raise along with the increase of pickling number of times.Therefore, before metal fluoride generation crystalline deposit, pickle solution must be changed to cleaning pickling tank.The acid that is mixing metal ion changing has just become spent pickle liquor.
Owing to containing strong acid and toxic metal ion in stainless steel acid-washing waste liquid, so needed its harmless treatment before discharge.At present, the method for processing stainless steel acid-washing waste liquid has a variety of, comprising: flotation process, microbial method, ion exchange method, membrane separation process and neutralization precipitation method.Wherein the action principle of flotation process is exactly first to pressure air-dissolving in waste water, with the unexpected step-down of the waste water that relief contains supersaturated air makes air produce micro-bubble and overflows from water, pollutent just adheres to bubble floating and reaches the object of purifying liquid waste to the water surface.The application of flotation process has certain actual value, still can form mud after flotation, though but heavy metal be removed and be difficult to reclaim, and water outlet pH cannot regulate in flotation process; Microbial method mainly relies on the function yeast of artificial culture, utilizes electrostatic adsorption, the catalyzed conversion effect of enzyme, complexing action, throwing out, the co-precipitation of microorganism to remove the metal ion in waste water.Because each production needs to cultivate new bacterial classification, cost up, and the reproduction speed of function yeast is slower, and also the food source that in fact heavy metal is taken as microorganism consumes, and there is no in essence the advantage that reclaims metal; Ion exchange method is the exchangable ion (H utilizing on ion exchange resin or ion-exchange fiber active group
+, Na
+, OH
-deng) remove the yin, yang ion in waste water.The performance counterweight metal removal of resin has considerable influence, and conventional ion exchange resin has Zeo-karb, anionite-exchange resin, chelate resin and humic acid resin etc.Ion-exchange-resin process is applicable to processing low concentration heavy metal water, and resin through after the absorption of 7 ~ 8 times again the ability of adsorbed ion will reduce, linearly downtrending, now must change resin, total cost is higher; Membrane separation process is to utilize selectivity that polymer has to carry out the technology of separating substances, and reaching its maturity of membrane separation technique, makes modern investigators more tend to the combination research to multiple film technology.The research of association area is still in the starting stage at home, and membrane separation process complex procedures, and cost is higher, and concentration ratio is limited, and the quality of film has much room for improvement, and administrative skill requires strictlyer, also needs just can obtain industrial application through a large amount of research practices.Neutralisation is simple and easy to do, but have following point: manage loaded down with trivial detailsly, wayward, wastewater treatment capacity is restricted; The metals such as acid in waste water, water, Fe, Cr, Ni, Cu fail to utilize, and cause significant wastage; Sludge landfill percolate still contains a large amount of pollutents, and in treating processes, generates the diffusion of gas, causes secondary pollution; Sludge quantity is large, remaining salt residue treatment difficulty, and cost is higher.Chinese most enterprises all adopt neutralization precipitation method to process spent pickle liquor at present, and therefore, the method for research and development less energy-consumption, eco-friendly processing stainless steel acid-washing waste liquid is imperative.
Summary of the invention
Object of the present invention is mainly a kind of crystal seed of preparation, reclaims valuable metal in Iron And Steel Industry stainless steel acid-washing waste liquid in order to deposition, and meanwhile, remaining acid solution is added, configuration eo-acid, and then continues a kind of method of recycle.
For achieving the above object, the present invention takes following technical scheme
By a method of adding β-tri-water ferric fluoride crystal seed processing stainless steel acid-washing waste liquid recovery metal, it is characterized in that thering is following process and step:
A. preparation simulation stainless steel acid-washing waste liquid, its moiety is: HNO
315.1%, HF 3%, Fe (NO
3)
313%, Cr (NO
3)
34.6%, Ni (NO
3)
21.6%, H
2o 62.7%(quality percentage composition);
B. the preparation of β-tri-water ferric fluoride crystal seed: by FeCl
36H
2o and (NH
4)
2cO
3become solution by the proportional arrangement of 1:3, and by titration apparatus by (NH
4)
2cO
3solution splashes into FeCl
3in solution, use electromagnetic mixing apparatus even to ensure crystallization simultaneously, generate flocks Fe (OH)
3, add appropriate ethanol to stir in order to avoid precipitation is reunited, reach the effect of discrete particles; Then, alternately wash solid phase precipitation thing three times with distilled water and alcohol, after vacuum unit suction filtration, put into loft drier, 40 DEG C obtain dry Fe (OH) after dry
3; By join (the tetrafluoroethylene material) in beaker obtaining, then be the hydrofluoric acid of 20wt% to adding concentration in beaker gradually, treat Fe (OH)
3after dissolving completely, beaker is placed in to the water bath with thermostatic control evaporative crystallization of 50 DEG C, obtains peach β-tri-water ferric fluoride, the crystal grain generating due to evaporative crystallization is larger, need to be ground to and very carefully just can be used as crystal seed;
C. the processing of stainless steel acid-washing waste liquid: at 30 DEG C ~ 50 DEG C temperature, process in the ratio of per kilogram waste liquid configuration 20g β-tri-water ferric fluoride crystal seed; Crystalline deposit condition: precipitation temperature is 30 DEG C, crystal seed is β-tri-water ferric fluoride; Employing water bath with thermostatic control insulation, induction stirring, stirring velocity is 300 revs/min; At interval of 100 minutes with in advance at 30 DEG C preheated injector draw in the centrifuge tube that 5mL spent acid joins preheating at 30 DEG C in advance, centrifugation 30 minutes, centrifuge speed is 4000 revs/min; Centrifugal settling finishes rear removal supernatant liquor and does ICP(ICP-AES) detect Fe, Cr, the concentration of Ni in spent pickle liquor, this sampling-centrifugation-testing process repeats once for every 100 minutes; Obtain thus concentration of metal ions relation over time in spent pickle liquor.
Advantage and disadvantage of the present invention is: utilize the method for adding crystal seed to make the form precipitate and separate of most metal ions with metal fluoride; And spent pickle liquor can be by adding HNO
3carry out cycling and reutilization with the method for HF eo-acid, so not only saved resource and also reduced the generation of waste, protected environment, obtain byproduct metal fluoride simultaneously.
Brief description of the drawings
Fig. 1 is recycle spent pickle liquor reclaim the schematic flow sheet of metal in the present invention.
Fig. 2 is concentration of metal ions graph of a relation over time in the spent pickle liquor obtaining in embodiment A.
Fig. 3 is concentration of metal ions graph of a relation over time in the spent pickle liquor obtaining in Embodiment B.
Fig. 4 is concentration of metal ions graph of a relation over time in the spent pickle liquor obtaining in Embodiment C.
Fig. 5 is the XRD figure spectrum that in embodiment, precipitation obtains.
Fig. 6 is the SEM figure that in embodiment, precipitation obtains.
Embodiment
Implementation step of the present invention is as follows:
1. the preparation of β-tri-water ferric fluoride crystal seed
By FeCl
36H
2o and (NH
4)
2cO
3become solution by the proportional arrangement of 1:3, and by titration apparatus by (NH
4)
2cO
3solution splashes into FeCl
3in solution, use electromagnetic mixing apparatus even to ensure crystallization simultaneously, generate flocks Fe (OH)
3, add appropriate ethanol to stir in order to avoid precipitation is reunited, reach the effect of discrete particles.Then, alternately wash solid phase precipitation thing three times with distilled water and alcohol, after vacuum unit suction filtration, put into loft drier, 40 DEG C obtain dry Fe (OH) after dry
3.By join (the tetrafluoroethylene material) in beaker obtaining, then be the hydrofluoric acid of 20wt% to adding concentration in beaker gradually, treat Fe (OH)
3after dissolving completely, beaker is placed in to the water bath with thermostatic control evaporative crystallization of 50 DEG C, obtains peach β-FeF
33H
2o, the crystal grain generating due to evaporative crystallization is larger, need to be ground to and very carefully just can be used as crystal seed.
2. the preparation of simulation spent pickle liquor
Use HNO
3(65w%), HF(40w%), Fe (NO
3)
39H
2o, Cr (NO
3)
39H
2o, Ni (NO
3)
29H
2o and deionized water proportionally configure simulation spent pickle liquor, and prepared simulation spent pickle liquor result is as shown in table 1.
Table 1 is joined spent pickle liquor result (g/kg)
| HNO 3 | HF | Fe | Cr | Ni |
| 150.6 | 30 | 30.4 | 9.4 | 4.78 |
3. the processing of stainless steel acid-washing waste liquid
A. the sedimentation effect at 30 DEG C
Crystalline deposit condition: precipitation temperature is 30 DEG C, crystal seed is β-tri-water ferric fluoride.Employing water bath with thermostatic control insulation, induction stirring, stirring velocity is 300 revs/min.At interval of 100 minutes with in advance at 30 DEG C preheated injector draw in the centrifuge tube that 5mL waste liquid joins preheating at 30 DEG C in advance, centrifugation 30 minutes, centrifuge speed is 4000 revs/min.Centrifugal settling finishes rear removal supernatant liquor and does ICP(ICP-AES) detect Fe, Cr, the concentration of Ni in spent pickle liquor, this sampling-centrifugation-testing process repeats once for every 100 minutes.Obtain thus concentration of metal ions relation over time in spent pickle liquor.
B. the sedimentation effect at 40 DEG C
Crystalline deposit condition: precipitation temperature is 40 DEG C, crystal seed is β-tri-water ferric fluoride.Other steps are as embodiment A.
C. the sedimentation effect at 50 DEG C
Crystalline deposit condition: precipitation temperature is 50 DEG C, crystal seed is β-tri-water ferric fluoride.Other steps are as embodiment A.
By the contrast of A, B, tri-kinds of situations of C, find that optimum situation is C, its component list is as shown in table 2.
Spent pickle liquor recycling capable of circulation in the present invention
Spent pickle liquor in the present invention adds eo-acid HNO rear to it
3after HF, make its be able to pickling again concentration, and precipitate allocation processing.Pickle solution composition after interpolation eo-acid is as shown in table 3.
Pickle solution composition (g/kg) after table 2 precipitation finishes
| HNO 3 | HF | Fe | Cr | Ni |
| 150.6 | 30 | 11.4 | 4.1 | 4.5 |
Table 3 adds the pickle solution composition (g/kg) after eo-acid
| HNO 3 | HF | Fe | Cr | Ni |
| 180 | 50 | 10.9 | 3.9 | 4.3 |
Claims (1)
1. by a method of adding β-tri-water ferric fluoride crystal seed processing stainless steel acid-washing waste liquid recovery metal, it is characterized in that thering is following process and step:
A. preparation simulation stainless steel acid-washing waste liquid, its moiety is: HNO
315.1%, HF 3%, Fe (NO
3)
313%, Cr (NO
3)
34.6%, Ni (NO
3)
21.6%, H
2o 62.7%(quality percentage composition);
B. the preparation of β-tri-water ferric fluoride crystal seed: by FeCl
36H
2o and (NH
4)
2cO
3become solution by the proportional arrangement of 1:3, and by titration apparatus by (NH
4)
2cO
3solution splashes into FeCl
3in solution, use electromagnetic mixing apparatus even to ensure crystallization simultaneously, generate flocks Fe (OH)
3, add appropriate ethanol to stir in order to avoid precipitation is reunited, reach the effect of discrete particles; Then, alternately wash solid phase precipitation thing three times with distilled water and alcohol, after vacuum unit suction filtration, put into loft drier, 40 DEG C obtain dry Fe (OH) after dry
3; By join (the tetrafluoroethylene material) in beaker obtaining, then be the hydrofluoric acid of 20wt% to adding concentration in beaker gradually, treat Fe (OH)
3after dissolving completely, beaker is placed in to the water bath with thermostatic control evaporative crystallization of 50 DEG C, obtains peach β-tri-water ferric fluoride, the crystal grain generating due to evaporative crystallization is larger, need to be ground to and very carefully just can be used as crystal seed;
C. the processing of stainless steel acid-washing waste liquid: at 30 DEG C ~ 50 DEG C temperature, process in the ratio of per kilogram waste liquid configuration 20g β-tri-water ferric fluoride crystal seed; Crystalline deposit condition: precipitation temperature is 30 DEG C, crystal seed is β-tri-water ferric fluoride; Employing water bath with thermostatic control insulation, induction stirring, stirring velocity is 300 revs/min; At interval of 100 minutes with in advance at 30 DEG C preheated injector draw in the centrifuge tube that 5mL spent acid joins preheating at 30 DEG C in advance, centrifugation 30 minutes, centrifuge speed is 4000 revs/min; Centrifugal settling finishes rear removal supernatant liquor and does ICP(ICP-AES) detect Fe, Cr, the concentration of Ni in spent pickle liquor; This sampling-centrifugation-testing process repeats once for every 100 minutes; Obtain thus concentration of metal ions relation over time in spent pickle liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410210539.XA CN104003490B (en) | 2014-05-19 | 2014-05-19 | Utilize the method for adding β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410210539.XA CN104003490B (en) | 2014-05-19 | 2014-05-19 | Utilize the method for adding β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift |
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| Publication Number | Publication Date |
|---|---|
| CN104003490A true CN104003490A (en) | 2014-08-27 |
| CN104003490B CN104003490B (en) | 2015-10-07 |
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|---|---|---|---|
| CN201410210539.XA Expired - Fee Related CN104003490B (en) | 2014-05-19 | 2014-05-19 | Utilize the method for adding β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107460493A (en) * | 2017-07-04 | 2017-12-12 | 当涂县宏宇金属炉料有限责任公司 | A kind of recovery and treatment method of secondary metal pickle liquor |
| CN116766460A (en) * | 2023-08-23 | 2023-09-19 | 河北优科斯橡胶科技有限公司 | Automatic recycling method and device for white carbon black of condom production line |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5477238A (en) * | 1977-12-01 | 1979-06-20 | Agency Of Ind Science & Technol | Stainless steel pickling tretment free of environmental pollution |
| JPS54153736A (en) * | 1978-05-25 | 1979-12-04 | Daido Kagaku Sochi | Regeneration of nitricchydrofluoric acid waste |
| CN101891259A (en) * | 2009-05-20 | 2010-11-24 | 北京紫光英力化工技术有限公司 | New process for recycling pickling waste liquid |
| CN103553256A (en) * | 2013-11-04 | 2014-02-05 | 云南农业大学 | Recycling treatment process for chlorohydric acid pickling liquid waste |
-
2014
- 2014-05-19 CN CN201410210539.XA patent/CN104003490B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5477238A (en) * | 1977-12-01 | 1979-06-20 | Agency Of Ind Science & Technol | Stainless steel pickling tretment free of environmental pollution |
| JPS54153736A (en) * | 1978-05-25 | 1979-12-04 | Daido Kagaku Sochi | Regeneration of nitricchydrofluoric acid waste |
| CN101891259A (en) * | 2009-05-20 | 2010-11-24 | 北京紫光英力化工技术有限公司 | New process for recycling pickling waste liquid |
| CN103553256A (en) * | 2013-11-04 | 2014-02-05 | 云南农业大学 | Recycling treatment process for chlorohydric acid pickling liquid waste |
Non-Patent Citations (1)
| Title |
|---|
| 赵日哲等: "用酸洗废液回收硫酸亚铁", 《环境保护科学》, vol. 15, no. 3, 31 December 1989 (1989-12-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107460493A (en) * | 2017-07-04 | 2017-12-12 | 当涂县宏宇金属炉料有限责任公司 | A kind of recovery and treatment method of secondary metal pickle liquor |
| CN116766460A (en) * | 2023-08-23 | 2023-09-19 | 河北优科斯橡胶科技有限公司 | Automatic recycling method and device for white carbon black of condom production line |
| CN116766460B (en) * | 2023-08-23 | 2023-11-14 | 河北优科斯橡胶科技有限公司 | Automatic recycling method and device for white carbon black of condom production line |
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| CN104003490B (en) | 2015-10-07 |
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