CN113003545A - Method for recycling and treating iron-containing mixed acid waste liquid in steel industry - Google Patents
Method for recycling and treating iron-containing mixed acid waste liquid in steel industry Download PDFInfo
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- CN113003545A CN113003545A CN202110200097.0A CN202110200097A CN113003545A CN 113003545 A CN113003545 A CN 113003545A CN 202110200097 A CN202110200097 A CN 202110200097A CN 113003545 A CN113003545 A CN 113003545A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Abstract
The invention discloses a method for recovering and treating iron-containing mixed acid waste liquid in the steel industry, which comprises the following steps of firstly precipitating and filtering the mixed acid waste liquid; then carrying out excessive sulfuric acid replacement, cooling crystallization and crystal liquid separation to obtain a coarse salt of ferric sulfate dodecahydrate and a mixed acid filtrate; then carrying out reduced pressure distillation on the mixed acid filtrate, recycling the distillate, and cooling and crystallizing the residual liquid; and finally, transferring the residual liquid crystal to a filter press, and performing filter pressing and separation by using the filter press to obtain the dodecahydrate ferric sulfate crude salt and the high-concentration sulfuric acid, wherein the high-concentration sulfuric acid is recycled. The invention adopts low-cost sulfuric acid to replace high-value nitric acid and hydrofluoric acid, has low cost, adopts a reduced pressure distillation process, ensures that the operation temperature of equipment is lower than 75 ℃, has long service life and is safe and reliable to operate. The method for treating the pickling waste liquid in the steel industry can be used for carrying out reduced pressure distillation on the high-concentration iron-containing mixed acid waste liquid, the process is simple, the treated waste acid is completely recycled, alkali neutralization is not needed, no waste water is discharged, and the environmental pollution is small.
Description
Technical Field
The invention relates to the technical field of waste liquid recycling treatment, in particular to a method for recycling and treating iron-containing mixed acid waste liquid in the steel industry.
Background
China is a large stainless steel production country, and the production capacity of various types of stainless steel is huge. When producing stainless steel strips of AISI200 series and AISI300 series, the stainless steel strips need to be annealed and pickled, and oxide scales on the surface of the stainless steel strips are removed by various strong acids. Sulfuric acid, nitric acid, hydrofluoric acid are used in the stainless steel pickling process. Nitric acid and hydrofluoric acid are typically co-proportioned in an acid bath to remove scale from the surface of stainless steel and are referred to as a mixed acid bath (nitric acid and hydrofluoric acid mixed). In the actual production process, after nitric acid and hydrofluoric acid are used for a period of time, because the concentration of ferric ions in the acid mixing tank rises, although the concentration of acid in the acid mixing tank is higher, the acid cannot wash down oxides (mainly ferric oxide) and iron simple substances on the surface of stainless steel, and the main reason is that the concentration of the ferric ions in the acid mixing tank is too high, so that the rust removal reaction is inhibited from proceeding to the positive direction, and at the moment, if the concentration of the ferric ions in waste acid is reduced, the rust removal reaction can continue to proceed to the positive direction, and the acid in the acid mixing tank can still be used continuously.
Various methods have been developed over the years to reduce the ferric ion concentration in the used mixed acid and reuse it. There are various methods such as a spray roasting method, an ion membrane method, a resin exchange method, a vacuum distillation method, and the like of anderlez. The spray roasting method is a full acid recovery process, has huge investment, is difficult to bear by common small and medium-sized enterprises, and is only adopted by some large-sized enterprises. The ion membrane method has the problems that the ion membrane is easy to block, and the ion membrane is frequently replaced with high cost. The resin exchange method has the problems that residual liquid still needs to be neutralized by alkali liquor and the waste liquid is not reduced.
The existing reduced pressure distillation method, the process shown in fig. 2, is only suitable for treating waste acid with very low ferric ion concentration, but the waste acid discharged from the acid mixing tank in actual production, if the waste acid mixing tank is forcibly subjected to reduced pressure distillation, part of ferric ions can generate part of polymeric ferric sulfate under the conditions of temperature and the existence of nitric acid due to the overhigh ferric ion concentration, the boiling point temperature in the evaporation kettle is increased, only a very small amount of water and a very small amount of nitric acid and hydrofluoric acid can be evaporated, and the residual liquid can become very viscous and has very poor fluidity. If the distillation time is longer, the heater is blocked by the residual liquid, and the machine needs to be stopped for cleaning. Because the concentration of ferric ions in the mixed acid waste liquid discharged from the mixed acid tank is higher, the mixed acid can not be treated by the conventional reduced pressure distillation process technology.
Disclosure of Invention
The invention aims to provide a method for recovering and treating iron-containing mixed acid waste liquid in the steel industry aiming at the defects in the prior art, which can be used for carrying out reduced pressure distillation on high-concentration ferric ion-containing mixed acid waste liquid.
The purpose of the invention is realized by the following technical scheme: a method for recovering and treating iron-containing mixed acid waste liquid in the steel industry comprises the following steps:
(1) precipitating and filtering
Settling and filtering the mixed acid waste liquid containing ferric ions discharged from the mixed acid tank to obtain mixed acid clear liquid;
(2) replacing excessive sulfuric acid, cooling and crystallizing
Introducing the clear mixed acid solution obtained in the step (1) into a cooling crystallization tank for stirring and cooling, adding concentrated sulfuric acid into the cooling crystallization tank while stirring and cooling to obtain a mixed acid solution, continuing cooling and stirring, and crystallizing and separating ferric sulfate dodecahydrate;
(3) liquid crystal separation
Transferring the mixed acid solution containing the ferric sulfate dodecahydrate crystals obtained in the step (2) to a filter press, and carrying out filter-pressing separation on the ferric sulfate dodecahydrate crystals and the mixed acid solution to obtain coarse ferric sulfate dodecahydrate salts and mixed acid filtrate;
(4) distillation under reduced pressure
Transferring the mixed acid filtrate obtained in the step (3) into a distillation still, carrying out reduced pressure distillation until the concentration of ferric ions reaches 75g/L, stopping reduced pressure distillation, condensing the distillate to obtain mixed acid distillate, and cooling and crystallizing residual liquid in the distillation still;
(5) filter pressing of filter press
And (3) transferring the residual liquid crystals in the distillation kettle in the step (4) to a filter press, and performing filter pressing by using the filter press to obtain the coarse salt of ferric sulfate dodecahydrate and high-concentration sulfuric acid, wherein the high-concentration sulfuric acid can be added into the step (2) for recycling.
Further, the mixed acid clear solution obtained in the step (1) contains hydrofluoric acid and nitric acid.
Further, the cooling temperature in the step (2) is less than or equal to 45 ℃.
Further, when the concentration of sulfate ions in the mixed acid liquid in the step (2) reaches 5.0-6.0mol/L, adding concentrated sulfuric acid is stopped, and stirring and cooling are continued for 8-12 h.
Further, the temperature of reduced pressure distillation in the step (4) is 70-75 ℃, and the pressure is-0.08-0.085 MPa.
Further, the mixed acid filtrate obtained in the step (3) contains hydrofluoric acid, nitric acid and sulfuric acid.
Further, the mixed acid distillate obtained in the step (4) contains hydrofluoric acid and nitric acid.
Further, the residual liquid in the distillation kettle in the step (4) contains high-concentration ferric ions and sulfuric acid.
The invention has the following effective effects:
1. the method can be used for carrying out reduced pressure distillation on the high-concentration iron-containing mixed acid waste liquid, and has high recovery efficiency and simple process;
2. high-value nitric acid and hydrofluoric acid are replaced by low-cost sulfuric acid, so that the cost is low;
3. the reduced pressure distillation process is adopted, so that the operation temperature of the equipment is lower than 75 ℃, the service life of the equipment is long, and the operation is safe and reliable;
4. the treated waste acid is completely recycled, alkali is not needed for neutralization, no waste water is discharged, and the environmental pollution is small.
Drawings
FIG. 1 is a process flow diagram of the present invention;
figure 2 is a prior art process flow diagram.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
A method for recovering and treating iron-containing mixed acid waste liquid in the steel industry comprises the following steps:
(1) precipitating and filtering
Mixed acid waste liquid with ferric ion concentration of 100g/L discharged from 100kg of mixed acid tank passes through a sedimentation tank, and precipitates are precipitated and filtered in the sedimentation tank to obtain mixed acid clear liquid with specific gravity of 1450 g/L. The mixed acid clear solution contains hydrofluoric acid and nitric acid.
(2) Replacing excessive sulfuric acid, cooling and crystallizing
And (2) introducing the clear mixed acid liquid obtained in the step (1) into a cooling crystallization tank for stirring and cooling, adding concentrated sulfuric acid into the cooling crystallization tank while stirring and cooling, and stirring and cooling while adding the concentrated sulfuric acid to prevent the mixed acid liquid from generating nitrogen dioxide due to temperature rise. In order to avoid the generation of nitrogen dioxide, the adding speed of concentrated sulfuric acid is controlled, and the temperature of mixed acid in the cooling tank is controlled to be less than or equal to 45 ℃.
The formation of the ferric sulfate dodecahydrate crystal is related to the addition of concentrated sulfuric acid, the addition of the concentrated sulfuric acid is low, the crystallization speed is low, the crystal particles are large, and the filtration is easy; the adding amount of concentrated sulfuric acid is high, the crystallization speed is high, the crystal particles are fine, and the filtration is difficult. But the adding amount of the concentrated sulfuric acid is too low, the crystallization of the ferric sulfate dodecahydrate can not occur, and the adding amount of the concentrated sulfuric acid is that the concentration of sulfate ions in the mixed acid solution added with the concentrated sulfuric acid reaches 5.0-6.0 mol/L.
Under the condition that the temperature is less than or equal to 45 ℃, when the concentration of sulfate ions in the mixed acid liquor reaches 5.0-6.0mol/L, ferric sulfate dodecahydrate crystals appear in about 8-12h, and ferric ions in the solution can be crystallized out of the mixed acid liquor in the form of ferric sulfate dodecahydrate.
In the embodiment, the sulfate ion concentration in the mixed acid solution is 5.4mol/L, and the adding amount of concentrated sulfuric acid is 50 kg. The stirring and cooling time of the cooling crystallization tank is set to be 10 hours, the sulfate ion concentration in the mixed acid solution can be 5.0mol/L, 5.8mol/L or 6.0mol/L in other embodiments, and the stirring and cooling time of the cooling crystallization tank can also be set to be 8 hours, 9 hours, 11 hours or 12 hours.
The cooling temperature of the cooling crystallization tank in the embodiment is set to 35 ℃, and the cooling temperature of the cooling crystallization tank in other embodiments can be set to 25 ℃ and 45 ℃. The step replaces high-value nitric acid and hydrofluoric acid by low-cost sulfuric acid, and has low operation cost and low cost.
(3) Liquid crystal separation
And (3) transferring the mixed acid solution containing the ferric sulfate dodecahydrate crystal obtained in the step (2) to a filter press, and carrying out filter-pressing separation on the ferric sulfate dodecahydrate crystal and the mixed acid solution to obtain a coarse salt of ferric sulfate dodecahydrate and a mixed acid filtrate, wherein the mixed acid filtrate contains hydrofluoric acid, nitric acid and sulfuric acid, and the mixed acid filtrate is subjected to the next reduced pressure distillation.
57.7 liters of mixed acid filtrate is obtained after the mixed acid liquid is subjected to filter press separation of ferric sulfate dodecahydrate crystals, and the mixed acid filtrate enters a reduced pressure distillation process, wherein the concentration of ferric ions in the mixed acid filtrate is 24 g/L.
(4) Distillation under reduced pressure
And (4) transferring the mixed acid filtrate obtained in the step (3) into a distillation kettle, vacuumizing and distilling under reduced pressure. As the boiling points of the nitric acid and the hydrofluoric acid are lower than the boiling point of water, and the nitric acid and the hydrofluoric acid belong to volatile acids, the pressure in the distillation kettle is controlled to be-0.08-0.085 MPa, the boiling point of water is reduced to 70-75 ℃, the free nitric acid and the hydrofluoric acid in the mixed acid can volatilize together with water vapor, and the mixed nitric acid and the hydrofluoric acid can be condensed to form mixed distillate of the nitric acid and the hydrofluoric acid for recycling. Sulfuric acid is difficult to evaporate due to its high boiling point and remains in the still.
After a period of evaporation, the concentration of ferric ions in the distillation kettle gradually increases, and when the concentration of ferric ions reaches 75g/L, reduced pressure distillation is stopped. The distillate volume was 38.47 liters and the raffinate volume was 19.23 liters.
Discharging residual liquid in the distillation kettle, adding new mixed acid filtrate into the distillation kettle again, and continuing to perform reduced pressure distillation. The raffinate in the still, which now contains high concentrations of ferric ions and sulphuric acid, is cooled at room temperature to form raffinate crystals. The step adopts a reduced pressure distillation process, so that the operation temperature of the equipment is lower than 75 ℃, the service life of the equipment is long, the operation is safe and reliable, and the maintenance cost is low.
(5) Filter pressing of filter press
And (3) transferring the residual liquid crystals in the distillation kettle in the step (4) to a filter press, and performing filter pressing by using the filter press to obtain the dodecahydrate ferric sulfate crude salt and the high-concentration sulfuric acid, wherein the high-concentration sulfuric acid can be added into the step (2) for recycling.
Comparative example
The method for recovering and treating the iron-containing mixed acid waste liquid in the steel industry in the prior art comprises the following steps:
(1) precipitating and filtering
Mixed acid waste liquid with ferric ion concentration of 100g/L discharged from 100kg of mixed acid tank passes through a sedimentation tank, and precipitates are precipitated and filtered in the sedimentation tank to obtain mixed acid clear liquid with specific gravity of 1450 g/L. The mixed acid clear solution contains hydrofluoric acid and nitric acid.
(2) Replacement by sulfuric acid
And (2) introducing the clear mixed acid liquid obtained in the step (1) into a cooling tank for stirring and cooling, adding concentrated sulfuric acid into the cooling crystallization tank while stirring and cooling, and cooling while stirring when adding the concentrated sulfuric acid to prevent the temperature of the mixed acid liquid from rising to generate nitrogen dioxide yellow smoke when adding the sulfuric acid. In order to avoid nitrogen dioxide yellow smoke, the adding speed of the sulfuric acid is controlled, and the temperature of the mixed acid in the cooling tank is controlled below 45 ℃.
The adding amount of the sulfuric acid is based on the condition that the sulfuric acid is matched with ferric ions in the mixed acid instead of the ferric ions. According to the condition that the concentration of ferric ions is 100g/L, 98X 100X 100000X 3/1450X 56X 2-18103 g of concentrated sulfuric acid is added. After 18.1kg of concentrated sulfuric acid is added, the condition that sulfate ions replace nitrate ions and ferric ions in the mixed acid are paired is met. Under the condition of adding 18.1kg of concentrated sulfuric acid, the crystallization of the ferric sulfate dodecahydrate can not occur when the temperature is reduced and the ferric sulfate is cooled. Adding 18.1kg of concentrated sulfuric acid to obtain 78.8 liters of mixed acid solution, and then carrying out reduced pressure distillation in the step (3), wherein the concentration of ferric ions in the mixed acid solution is 87.5 g/L.
(3) Distillation under reduced pressure
And (3) transferring the mixed acid liquid obtained in the step (2) into a distillation kettle, and carrying out reduced pressure distillation. As the boiling points of the nitric acid and the hydrofluoric acid are lower than the boiling point of water, and the nitric acid and the hydrofluoric acid belong to volatile acids, the pressure in the reduced pressure distillation kettle is negative pressure, the pressure is controlled to be-0.08-0.085 MPa, the boiling point of water is reduced to 70-75 ℃, free nitric acid and hydrofluoric acid in the mixed acid and water vapor are volatilized together, and the mixed distillate of the nitric acid and the hydrofluoric acid is obtained after condensation and is recycled. Sulfuric acid is difficult to evaporate due to its high boiling point and remains in the still. After a period of evaporation, the concentration of ferric ions in the distillation still gradually increases, and when the concentration of ferric ions reaches 110g/L, the reduced pressure distillation is stopped. The volume of distillate was 16.1 liters and the volume of raffinate was 62.7 liters.
When the concentration of ferric ions in the mixed acid liquid reaches 110g/L, the reduced pressure distillation must be stopped, otherwise, the phenomenon of blocking a heater in a reduced pressure distillation system can be caused, and the system is shut down.
Discharging residual liquid in the distillation kettle, adding new mixed acid liquid into the distillation kettle again, and continuing to perform reduced pressure distillation.
(4) Residual alkali neutralization
The residual liquid in the distillation still contains high-concentration ferric ions, sulfuric acid and nitric acid, and the residual liquid does not reach the crystallization condition of the dodecahydrate ferric sulfate, so that sodium hydroxide is still added to the residual liquid for alkali neutralization, and the acid sludge and the salt-containing wastewater are obtained after filter pressing and separation by a filter press. Drying and reducing the acid sludge, then performing harmless treatment, and performing harmless treatment on the salt-containing wastewater.
The above examples and comparative examples show that the method can be used for carrying out reduced pressure distillation on the high-concentration iron-containing mixed acid waste liquid, and the method has high recovery efficiency and simple process.
As can be seen from the above examples and comparative examples, the present invention combines salting out with proper cooling to replace high-value nitric acid and hydrofluoric acid with low-cost sulfuric acid, thereby reducing the cost.
As can be seen from the above examples and comparative examples, the present invention adopts the reduced pressure distillation process, so that the operation temperature of the equipment is lower than 75 ℃, the service life of the equipment is long, and the operation is safe and reliable.
The embodiment and the comparative example show that the recycling method provided by the invention is used for treating the pickling waste liquid in the steel industry, the treated waste acid is completely recycled, alkali neutralization is not needed, no waste water is discharged, and the environmental pollution is small.
Those skilled in the art to which the present invention pertains can also make appropriate alterations and modifications to the above-described embodiments, in light of the above disclosure. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (8)
1. A method for recycling and treating iron-containing mixed acid waste liquid in the steel industry is characterized by comprising the following steps: the method comprises the following steps:
(1) precipitating and filtering
Settling and filtering the mixed acid waste liquid containing ferric ions discharged from the mixed acid tank to obtain mixed acid clear liquid;
(2) replacing excessive sulfuric acid, cooling and crystallizing
Introducing the clear mixed acid solution obtained in the step (1) into a cooling crystallization tank for stirring and cooling, adding concentrated sulfuric acid into the cooling crystallization tank while stirring and cooling to obtain a mixed acid solution, continuing cooling and stirring, and crystallizing and separating ferric sulfate dodecahydrate;
(3) liquid crystal separation
Transferring the mixed acid solution containing the ferric sulfate dodecahydrate crystal obtained in the step (2) to a filter press, and carrying out filter-pressing separation on the ferric sulfate dodecahydrate crystal and the mixed acid solution to obtain a coarse ferric sulfate dodecahydrate salt and a mixed acid filtrate;
(4) distillation under reduced pressure
Transferring the mixed acid filtrate obtained in the step (3) into a distillation still, carrying out reduced pressure distillation until the concentration of ferric ions reaches 75g/L, stopping reduced pressure distillation, condensing the distillate to obtain mixed acid distillate, and cooling and crystallizing residual liquid in the distillation still;
(5) filter pressing of filter press
And (3) transferring the residual liquid crystals in the distillation kettle in the step (4) to a filter press, and performing filter pressing by using the filter press to obtain the coarse salt of ferric sulfate dodecahydrate and high-concentration sulfuric acid, wherein the high-concentration sulfuric acid can be added into the step (2) for recycling.
2. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: the mixed acid clear solution obtained in the step (1) contains hydrofluoric acid and nitric acid.
3. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: the cooling temperature in the step (2) is less than or equal to 45 ℃.
4. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: and (3) stopping adding concentrated sulfuric acid when the concentration of sulfate ions in the mixed acid solution in the step (2) reaches 5.0-6.0mol/L, and continuing stirring and cooling for 8-12 h.
5. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: the temperature of reduced pressure distillation in the step (4) is 70-75 ℃, and the pressure is-0.08-0.085 MPa.
6. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: and (4) the mixed acid filtrate obtained in the step (3) contains hydrofluoric acid, nitric acid and sulfuric acid.
7. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: the mixed acid distillate obtained in the step (4) contains hydrofluoric acid and nitric acid.
8. The method for recycling and treating the iron-containing mixed acid waste liquid in the steel industry according to claim 1, characterized by comprising the following steps: and (4) residual liquid in the distillation kettle in the step (4) contains high-concentration ferric ions and sulfuric acid.
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| JPH0369515A (en) * | 1989-08-09 | 1991-03-25 | Tetsugen:Kk | Method for recovering high-purity iron sulfate from waste sulfuric acid pickling solution for stainless steel |
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| CN104498974A (en) * | 2015-01-23 | 2015-04-08 | 黄健 | Method for recycling mixed acid from cold-rolling stainless steel acid washing waste liquid |
| CN105601019A (en) * | 2016-03-17 | 2016-05-25 | 常州天合光能有限公司 | Device and method for recovering HNO3-HF mixed solution from crystalline silicon solar cell spent acid solution |
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2021
- 2021-02-23 CN CN202110200097.0A patent/CN113003545A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0369515A (en) * | 1989-08-09 | 1991-03-25 | Tetsugen:Kk | Method for recovering high-purity iron sulfate from waste sulfuric acid pickling solution for stainless steel |
| JP2002284509A (en) * | 2001-03-28 | 2002-10-03 | Osaka Gas Co Ltd | Treatment method of spent sulfuric acid and the treatment equipment |
| CN101294286A (en) * | 2008-05-30 | 2008-10-29 | 陈跃星 | Processing and recycling method and equipment for acid pickle of acid washing rolled steel |
| CN101935077A (en) * | 2010-08-27 | 2011-01-05 | 南通京通石墨设备有限公司 | Waste acid concentration multistage treatment method |
| CN102784491A (en) * | 2012-08-28 | 2012-11-21 | 重庆钢铁(集团)有限责任公司 | Waste acid treatment process |
| CN104498974A (en) * | 2015-01-23 | 2015-04-08 | 黄健 | Method for recycling mixed acid from cold-rolling stainless steel acid washing waste liquid |
| CN105601019A (en) * | 2016-03-17 | 2016-05-25 | 常州天合光能有限公司 | Device and method for recovering HNO3-HF mixed solution from crystalline silicon solar cell spent acid solution |
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