CN104003490B - Utilize the method for adding β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift - Google Patents
Utilize the method for adding β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift Download PDFInfo
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- CN104003490B CN104003490B CN201410210539.XA CN201410210539A CN104003490B CN 104003490 B CN104003490 B CN 104003490B CN 201410210539 A CN201410210539 A CN 201410210539A CN 104003490 B CN104003490 B CN 104003490B
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- acid
- stainless steel
- crystal seed
- waste liquid
- ferric fluoride
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- Removal Of Specific Substances (AREA)
Abstract
The present invention relates to a kind of valuable metal recovery method in recycle of stainless steel acid-washing waste liquid and spent acid solution, belong to liquid waste disposal technique field.The main content of the present invention is: by control temperature and seed load, the metal ion in spent pickle liquor is farthest precipitated, carry out solid-liquid separation afterwards; With reference to the composition of pickle solution, in the spent pickle liquor after precipitation, supplement HNO
3with HF eo-acid, make it to reach and can carry out the concentration of pickling and again precipitate metal.The present invention is to the recycle of pickle solution, and the processing costs when waste that not only can reduce acid can also reduce subsequent disposal spent acid, reduces the generation of acid-washing stainless steel mud simultaneously.
Description
Technical field
The present invention relates to the treatment process of stainless steel acid-washing waste liquid Footwall drift, belong to industrial waste acid manipulation of regeneration technical field.
Background technology
Stainless steel product is with a long history, can trace back to before and after 1910 the earliest, almost succeeds in developing stainless steel by Germany, UK and USA simultaneously.But in the development course that this is short, stainless steel is through invention to initial stage industrialization and the large production of modern industrialization, and its output and production technology have had the increase and 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 mixing, by its surface passivating treatment at 40 ~ 60 DEG C.In this surface treatment process, acid solution can penetrate into the inside from the zone of oxidation gap of stainless steel surface, the metal inside simultaneous oxidation.NO can be generated in the process of oxidized metal
xgas, the gas of generation will fall the zone of oxidation punching being attached to stainless steel surface.In whole acid cleaning process, acid constantly consumes, so need when in pickle solution, acid is depleted to a certain amount of to add eo-acid to it, to keep the concentration of acid in whole acid cleaning process roughly constant.But the concentration of metal ions dissolved in pickle solution constantly can raise along with the increase of pickling number of times.Therefore, pickle solution must be changed before metal fluoride generation crystalline deposit, cleaning pickling tank.The acid mixing metal ion changed just has become spent pickle liquor.
Owing to containing strong acid and toxic metal ions in stainless steel acid-washing waste liquid, so need before discharge its harmless treatment.At present, the method for process stainless steel acid-washing waste liquid has a variety of, comprising: flotation process, microbial method, ion exchange method, membrane separation process and moderate water-cut stage.Wherein the action principle of flotation process is exactly first to pressure air-dissolving in waste water, with relief contains the unexpected step-down of waste water of supersaturated air, make air produce micro-bubble and overflow 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 the electrostatic adsorption of microorganism, the catalyzed conversion effect of enzyme, complexing action, throwing out, co-precipitation to remove the metal ion in waste water.Need cultivate new bacterial classification, cost up owing to producing at every turn, and the reproduction speed of function yeast is comparatively slow, and the food source that in fact heavy metal is taken as microorganism consumes, and there is no the advantage of Footwall drift in essence; Ion exchange method utilizes the exchangable ion (H on ion exchange resin or ion-exchange fiber active group
+, Na
+, OH
-deng) remove anions and canons in waste water.The performance heavy metal of resin is removed considerable influence, and conventional ion exchange resin has Zeo-karb, anionite-exchange resin, chelate resin and humic acid resin etc.Ion-exchange-resin process be applicable to process low concentration heavy metal water, and resin 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 be utilize polymer to have selectivity to carry out the technology of separating substances, reaching its maturity of membrane separation technique, makes the combination research that modern investigators tend to multiple film technology more.The research of association area is still in the starting stage at home, and membrane separation process complex procedures, cost is higher, and concentration ratio is limited, and the quality of film has much room for improvement, and administrative skill requires relatively stricter, also needs just can obtain industrial application through a large amount of research practices.Neutralisation is simple and easy to do, but there is following point: manage loaded down with trivial details, and wayward, wastewater treatment capacity is restricted; The metal such as the acid in waste water, water, Fe, Cr, Ni, Cu fails to utilize, and causes significant wastage; Sludge landfill percolate still containing a large amount of pollutent, and generates the diffusion of gas in treating processes, cause secondary pollution; Sludge quantity is large, and remaining salt residue treatment difficulty, cost is higher.Most enterprise of current China all adopts moderate water-cut stage process spent pickle liquor, and therefore, the method for research and development less energy-consumption, eco-friendly process stainless steel acid-washing waste liquid is imperative.
Summary of the invention
Object of the present invention mainly prepares a kind of crystal seed, 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
Add a method for β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift, it is characterized in that there 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%(mass percentage);
B. the preparation of β-three water ferric fluoride crystal seed: by FeCl
36H
2o and (NH
4)
2cO
3solution is become by the proportional arrangement of 1:3, and by titration apparatus by (NH
4)
2cO
3solution instillation FeCl
3in solution, use electromagnetic mixing apparatus to ensure that crystallization is even simultaneously, generate flocks Fe (OH)
3, add ethanol in proper amount and 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, after 40 DEG C of dryings, obtain dry Fe (OH)
3; Join (tetrafluoroethylene material) in beaker by what obtain, then in beaker, add the hydrofluoric acid that concentration is 20wt% gradually, treat Fe (OH)
3after dissolving completely, beaker is placed in the water bath with thermostatic control evaporative crystallization of 50 DEG C, obtains peach β-three water ferric fluoride, the crystal grain generated due to evaporative crystallization is comparatively large, needs to be ground to very carefully just to can be used as crystal seed;
C. the process of stainless steel acid-washing waste liquid: at 30 DEG C ~ 50 DEG C temperature, processes in the ratio of per kilogram waste liquid configuration 20g β-three water ferric fluoride crystal seed; Crystalline deposit condition: precipitation temperature is 30 DEG C, crystal seed is β-three water ferric fluoride; Employing water bath with thermostatic control is incubated, induction stirring, and stirring velocity is 300 revs/min; At interval of 100 minutes with prior at 30 DEG C preheated injector draw 5mL spent acid and join in centrifuge tube preheated at 30 DEG C in advance, centrifugation 30 minutes, centrifuge speed is 4000 revs/min; Centrifugal settling terminates rear removal supernatant liquor and does ICP(ICP-AES) detect Fe, Cr, Ni concentration in spent pickle liquor, this sampling-centrifugation-testing process repeats once in every 100 minutes; Obtain concentration of metal ions relation over time in spent pickle liquor thus.
Advantage and disadvantage of the present invention is: utilize the method for adding crystal seed to make most metal ion with the form precipitate and separate of metal fluoride; And spent pickle liquor can by adding HNO
3carry out cycling and reutilization with the method for HF eo-acid, so not only saved the generation that resource decreases waste, protected environment, obtained byproduct metal fluoride simultaneously.
Accompanying drawing explanation
Fig. 1 is recycle spent pickle liquor the schematic flow sheet of Footwall drift in the present invention.
Fig. 2 is concentration of metal ions graph of a relation over time in the spent pickle liquor obtained in embodiment A.
Fig. 3 is concentration of metal ions graph of a relation over time in the spent pickle liquor obtained in Embodiment B.
Fig. 4 is concentration of metal ions graph of a relation over time in the spent pickle liquor obtained in Embodiment C.
Fig. 5 precipitates the XRD figure spectrum obtained in embodiment.
Fig. 6 precipitates the SEM figure obtained in embodiment.
Embodiment
Implementation step of the present invention is as follows:
1. the preparation of β-three water ferric fluoride crystal seed
By FeCl
36H
2o and (NH
4)
2cO
3solution is become by the proportional arrangement of 1:3, and by titration apparatus by (NH
4)
2cO
3solution instillation FeCl
3in solution, use electromagnetic mixing apparatus to ensure that crystallization is even simultaneously, generate flocks Fe (OH)
3, add ethanol in proper amount and 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, after 40 DEG C of dryings, obtain dry Fe (OH)
3.Join (tetrafluoroethylene material) in beaker by what obtain, then in beaker, add the hydrofluoric acid that concentration is 20wt% gradually, treat Fe (OH)
3after dissolving completely, beaker is placed in the water bath with thermostatic control evaporative crystallization of 50 DEG C, obtains peach β-FeF
33H
2o, the crystal grain generated due to evaporative crystallization is comparatively large, needs to be ground to very carefully just to can be used as crystal seed.
2. simulate the preparation of 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 obtained simulation spent pickle liquor result is as shown in table 1.
Table 1 join spent pickle liquor result (g/kg)
| HNO 3 | HF | Fe | Cr | Ni |
| 150.6 | 30 | 30.4 | 9.4 | 4.78 |
3. the process 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-three water ferric fluoride.Employing water bath with thermostatic control is incubated, and induction stirring, stirring velocity is 300 revs/min.At interval of 100 minutes with prior at 30 DEG C preheated injector draw 5mL waste liquid and join in centrifuge tube preheated at 30 DEG C in advance, centrifugation 30 minutes, centrifuge speed is 4000 revs/min.Centrifugal settling terminates rear removal supernatant liquor and does ICP(ICP-AES) detect Fe, Cr, Ni concentration in spent pickle liquor, this sampling-centrifugation-testing process repeats once for every 100 minutes.Obtain concentration of metal ions relation over time in spent pickle liquor thus.
B. the sedimentation effect at 40 DEG C
Crystalline deposit condition: precipitation temperature is 40 DEG C, crystal seed is β-three 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-three water ferric fluoride.Other steps are as embodiment A.
By the contrast of A, B, C tri-kinds of situations, 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 reach can again pickling concentration, and carry out precipitation allocation processing.The pickle solution composition added after eo-acid is as shown in table 3.
Pickle solution composition (g/kg) after table 2 precipitation terminates
| 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-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift, it is characterized in that there is following process and step:
A. preparation simulation stainless steel acid-washing waste liquid, its composition and mass percentage are: HNO
315.1%, HF 3%, Fe (NO
3)
313%, Cr (NO
3)
34.6%, Ni (NO
3)
21.6%, H
2o 62.7%;
B. the preparation of β-three water ferric fluoride crystal seed: by FeCl
36H
2o and (NH
4)
2cO
3solution is become by the proportional arrangement of 1:3, and by titration apparatus by (NH
4)
2cO
3solution instillation FeCl
3in solution, use electromagnetic mixing apparatus to ensure that crystallization is even simultaneously, generate flocks Fe (OH)
3, add ethanol in proper amount and 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, after 40 DEG C of dryings, obtain dry Fe (OH)
3; By joining in beaker of obtaining, then in beaker, add the hydrofluoric acid that concentration is 20wt% gradually, treat Fe (OH)
3after dissolving completely, beaker is placed in the water bath with thermostatic control evaporative crystallization of 50 DEG C, obtains peach β-three water ferric fluoride, the crystal grain generated due to evaporative crystallization is comparatively large, needs to be ground to very carefully just to can be used as crystal seed;
C. the process of stainless steel acid-washing waste liquid: at 30 DEG C ~ 50 DEG C temperature, processes in the ratio of per kilogram waste liquid configuration 20g β-three water ferric fluoride crystal seed; Crystalline deposit condition: precipitation temperature is 30 DEG C, crystal seed is β-three water ferric fluoride; Employing water bath with thermostatic control is incubated, induction stirring, and stirring velocity is 300 revs/min; At interval of 100 minutes with prior at 30 DEG C preheated injector draw 5mL spent acid and join in centrifuge tube preheated at 30 DEG C in advance, centrifugation 30 minutes, centrifuge speed is 4000 revs/min; Centrifugal settling terminates rear removal supernatant liquor and is ICP-AES ICP to detect Fe, Cr, Ni concentration in spent pickle liquor; This sampling-centrifugation-testing process repeats once in every 100 minutes; Obtain concentration of metal ions relation over time in spent pickle liquor thus.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104003490A CN104003490A (en) | 2014-08-27 |
| CN104003490B true CN104003490B (en) | 2015-10-07 |
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ID=51364435
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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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Families Citing this family (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 |
| 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 |
Family Cites Families (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 |
| CN101891259B (en) * | 2009-05-20 | 2012-10-10 | 北京紫光英力化工技术有限公司 | New process for recycling pickling waste liquid |
| CN103553256B (en) * | 2013-11-04 | 2015-01-07 | 云南农业大学 | Recycling treatment process for chlorohydric acid pickling liquid waste |
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Granted publication date: 20151007 Termination date: 20200519 |