CN112875964A - Treatment and recycling method of pickling wastewater containing metal iron, chromium and nickel - Google Patents
Treatment and recycling method of pickling wastewater containing metal iron, chromium and nickel Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/42—Preparation from nitrates
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a method for treating and recycling pickling wastewater containing metal, iron, chromium and nickel, which comprises the following steps of oil separation regulation, neutralization reaction, advection precipitation, nickel precipitation, waste liquid concentration and nitric acid preparation, wherein the pickling wastewater containing metal, iron, chromium and nickel is treated to obtain clear water, gypsum and nitric acid after sequentially passing through an oil separation regulation tank, a neutralization reaction tank, a flocculation tank, a nickel precipitation reaction tank, an MVR + MED evaporator and a reaction tank. Can treat the acid wastewater efficiently, can be recycled, improves the economic benefit and is more environment-friendly.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for treating and recycling pickling wastewater containing metal iron, chromium and nickel.
Background
Stainless steel is widely used in various fields because of its excellent corrosion resistance and good appearance. Although stainless steel products are various and smelting processes are different, the stainless steel products with good corrosion resistance and oxidation resistance need to be subjected to a pickling and passivation process flow. During the pickling process, the metal oxide is continuously dissolved and enters the pickling solution. The hydrogen ions in the ortho-acid washing liquor are gradually replaced by the metal salt, so that the concentration of the acid is gradually reduced, the concentration of the metal salt is increased, the speed of the acid washing liquor for dissolving the oxide is gradually reduced, therefore, the waste liquor needs to be continuously discharged, new acid washing liquor needs to be supplied, and the discharged waste liquor with poor acid washing effect becomes acid washing wastewater. The stainless steel pickling wastewater has high acidity and high toxicity, comprises toxic pollutants such as nickel, chromium, iron and the like, has high integral yield and is very difficult to treat, and has great threat to the environment and the human health. The traditional stainless steel pickling wastewater treatment technology has the advantages of high medicament cost, heavy secondary pollution, waste of a large amount of valuable inorganic acid and high-value heavy metal resources, and high treatment requirement and high cost due to the fact that the generated neutralized sludge belongs to dangerous waste. And the problems of separation, recovery and comprehensive utilization of the treated products can not be effectively solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating and recycling pickling wastewater containing metal iron, chromium and nickel, which can efficiently treat acidic wastewater and simultaneously can be recycled, thereby improving economic benefits and being more environment-friendly.
In order to achieve the aim, the invention provides a method for treating and recycling pickling wastewater containing metallic iron, chromium and nickel, which comprises the following steps,
step 1, oil removal adjustment, namely collecting pickling wastewater, separating the pickling wastewater through a PE (polyethylene) grid, and homogenizing in an oil removal tank;
step 2, performing primary neutralization reaction, namely introducing the homogenized acid washing wastewater into a primary neutralization reaction tank, neutralizing the acid washing wastewater with lime emulsion until the pH value is 3.0 +/-0.5, controlling the reaction time to be 0.5-2.0 hours, obtaining a calcium fluoride product and a neutralization filtrate, allowing the calcium fluoride product to enter a primary advection tank for precipitation, and allowing the neutralization filtrate to enter a secondary neutralization reaction tank;
step 3, performing secondary neutralization reaction, namely adding lime emulsion into a secondary neutralization reaction tank, standing for 3-5 hours, controlling the pH value of the secondary neutralization reaction tank to be 5.6-5.8, introducing acid washing wastewater subjected to the neutralization reaction into a flocculation tank, adding PAM (polyacrylamide) for sludge precipitation, staying for 22-26 hours to obtain Fe/Cr/Ni sludge, introducing a first supernatant into a nickel precipitation tank, performing filter pressing on the Fe/Cr/Ni sludge to obtain a first filtrate, and introducing the first filtrate into the nickel precipitation tank;
step 4, nickel precipitation, namely adding a vulcanizing agent or calcium hydroxide slurry into a nickel precipitation tank, filtering to obtain nickel precipitation and treatment liquid, treating the treatment liquid to obtain pretreated wastewater, and introducing the pretreated wastewater into a transition tank;
step 5, concentrating the waste liquid, namely introducing the pretreated waste water in the transition tank into an MED falling film evaporator to perform MVR evaporation concentration to obtain a concentrated solution;
and 6, preparing nitric acid, namely introducing the concentrated solution into a first reaction tank, adding 98% concentrated sulfuric acid with half of the total reaction metered amount into the first reaction tank, reacting for 10-15 min, carrying out solid-liquid separation to obtain first separated liquid and first slurry, adding the first separated liquid into a second reaction tank, adding 98% concentrated sulfuric acid with half of the reaction metered amount into the second reaction tank, reacting for 10-15 min, carrying out solid-liquid separation to obtain second separated liquid and second slurry, and placing the second separated liquid into a nitric acid storage tank for storage.
According to the further arrangement of the method, 5% calcium hydroxide slurry is added in the step 4, Ni ions are precipitated into nickel hydroxide, the pH value of a nickel sedimentation tank is controlled to be 8.5-9.5, the nickel hydroxide stays for 1.5-2.5 hours, third supernatant is obtained, the precipitated nickel hydroxide is introduced into an inclined tube sedimentation tank and is subjected to filter pressing to obtain third filtrate, and the third filtrate and the third supernatant are combined to form the treatment liquid.
As a further arrangement of the invention, the step 4 further comprises treating the treatment solution, introducing the treatment solution into a manganese sedimentation tank, adding sodium sulfide into the manganese sedimentation tank and aerating, wherein the aeration time is controlled to be 0.5-2.0 h to obtain manganous hydroxide or manganese sulfide sediment, introducing a fourth supernatant into a transition tank, performing filter pressing on the sediment to obtain a fourth filtrate, introducing the fourth filtrate into the transition tank, and combining the fourth filtrate and the fourth supernatant to obtain the pretreated wastewater.
According to the further arrangement of the invention, the vulcanizing agent added in the step 4 is one or more of hydrogen sulfide, sodium hydrosulfide, sodium sulfide, barium sulfide and calcium sulfide, and the pH range during vulcanization is 3.50-5.50.
As a further arrangement of the invention, in the step 6, the first slurry is introduced into a filter press for filter pressing to form a first filter cake and a first pressure filtrate, and the first pressure filtrate is added into a second reaction tank; the method comprises the steps of introducing the second slurry into a filter press for filter pressing to form a second filter cake and a second pressure filtrate, and adding the second pressure filtrate into a nitric acid storage tank for storage.
In a further configuration of the present invention, in the step 6, the method further comprises introducing high-pressure water into the second filter cake in a filter press for washing to obtain washing wastewater, and introducing the washing wastewater into the neutralization reaction tank.
As a further arrangement of the invention, the high pressure water is from a MED falling film evaporator.
In a further configuration of the present invention, in the step 6, compressed air is introduced into the second filter cake in the filter press, and the blown-out liquid is introduced into the nitric acid storage tank for storage.
According to the further arrangement of the invention, the blow-off gas of the compressed air after passing through the filter cake is introduced into an acid mist tower for treatment, an alkaline solution is sprayed in the acid mist tower, and the blow-off gas is discharged out of the acid mist tower after being fully contacted with the alkaline solution.
As a further configuration of the present invention, in the step 6, dry air is further introduced into the first filter cake and the second filter cake.
The advantage of this arrangement is that in this way the stainless steel pickling waste water is mainly obtained by using mixed acid (IF and HNO)3) After the surface of the stainless steel pipe is subjected to acid pickling, wastewater containing stainless steel constituent elements and mixed acid components, which is generated by washing the acid-pickled stainless steel pipe, is formed. The main solute component in the stainless steel pickling wastewater is Fe through test analysis3+、Cr3+、Ni2+、NO3-、Mn2+、Co2+And F. Wherein Fe, Cr, Mn and Ni are a large amount of constituent elements of stainless steel, NO3-And F is the main component of the acid-washing mixed acid, wherein Cr is trivalent chromium. According to Fe2+、Cr+And Ni2+The pH of the plasma precipitation was varied, as shown in table 1,
| metal ion | Fe3+ | Cr3+ | Ni2+ |
| Initial precipitation pH | 1.50 | 4.0 | 6.0 |
| Complete precipitation of pH | 4.0 | 5.0 | 8.5 |
TABLE 1Fe3+、Cr3+And Ni2+pH value of precipitate
The method adopts calcium-iron precipitation method, can precipitate metal ions such as Fe with high selectivity, and simultaneously can still store a large amount of high-value Ni in the solution. And further carrying out secondary precipitation on Ni by adjusting the pH value so as to realize the high-efficiency recovery of Ni. Compared with the original wastewater treatment process, the calcium-iron precipitation method focuses on adopting a method for adjusting the pH value. To perform fractional precipitation.
During the neutralization reaction, when the pH is <6, the chemical reactions that mainly occur are as follows:
2Fe(NO3)3+3Ca(OH)2→2Fe(OH)3↓+3Ca(O3)2
Ni(NO3)2+Ca(OH)2→Ni(OH)2↓+Ca(NO3)2
2Cr(NO3)3+3Ca(OH)2→2Cr(OH)3↓+3Ca(NO3)2
Ca(OH)2+2HF→CaF2↓+2H2O
Ca(OH)2+2HNO3→Ca(NO3)2+2H2O
side reaction (lime containing Mg (OH)2Impurities);
2Fe(NO3)3+3Mg(OH)2→2Fe(OH)3↓+3Mg(NO3)2
Ni(NO3)2+Mg(OH)2→Ni(OH)2↓+Mg(NO3)2
2Cr(NO3)3+3Mg(OH)2→Cr(OH)3↓+3Mg(NO3)2
2HF+Mg(OH)2→+MgF2↓+2H2O
Mg(OH)2+2HNO3→Mg(NO3)2+2H2O
when pH >6, the chemical reactions that mainly occur are as follows:
Ni(NO3)2+Ca(OH)2→Ni(OH)2↓+Ca(NO3)2
side reaction, in which the water contains Co, Mn and Mg metal ions
Mn(NO3)2+Ca(OH)2→Mn(OH)2↓+Ca(NO3)2
Co(NO3)2+Ca(OH)2→Co(OH)2↓+Ca(NO3)2
Mg(NO3)2+Ca(OH)2→Mg(OH)2↓+Ca(NO3)2
After the stainless steel acid pickling wastewater is neutralized and precipitated by lime to remove fluorine and heavy metals, the obtained wastewater contains calcium nitrate (Ca (NO) with higher concentration3)2) After MED or MVR concentration by 20 times, the TDS concentration in the solution is as high as 4 x 10mg/L, and the specific gravity is about 1.40. The concentrate contains Ca (NO) as main ingredient3)2Belongs to the solid waste which is difficult to dispose and easy to explode, and uses cheap H2SO4With Ca (NO)3)2Reaction for preparing HNO3For pickling stainless steel to realize NO3 -The resources are recycled, and meanwhile, calcium sulfate can be byproduct and can be processed into gypsum. The reaction equations are shown in (1) and (2):
H2SO4+Ca(NO3)2→2HNO3+CaSO4
CaSO4+2H2O→CaSO4+2H2O
in addition, the concentrated solution contains trace amount of heavy metal ions Ni2+，Mn2+，Co2Most of it remains in the nitric acid and a small amount may be adsorbed in the calcium sulfate. According to the concentration of the concentrated solution, the concentration of the prepared nitric acid can reach 40-45%.
Further, the acid mist is treated and fully contacted with the alkaline solution sprayed in the acid mist tower through the acid mist tower to form soluble salts, so that the soluble salts drip in a collecting tank for recycling, and the clean gas for removing the acid liquid is discharged
Drawings
FIG. 1 is a schematic process flow diagram according to an embodiment of the present invention.
Detailed Description
The first embodiment of the method for treating and recycling the pickling wastewater containing metallic iron, chromium and nickel of the invention is shown in figure 1: comprises the following steps of (a) carrying out,
step 1, oil removal adjustment, namely collecting pickling wastewater, separating the pickling wastewater through a PE (polyethylene) grid, and homogenizing in an oil removal tank;
step 2, performing neutralization reaction, namely introducing the homogenized acid washing wastewater into a neutralization reaction tank, adding calcium hydroxide into the neutralization reaction tank, standing for 4 hours, and controlling the pH value of the neutralization reaction tank to be 5.6-5.8;
step 3, performing advection precipitation, namely introducing the acid pickling wastewater subjected to the neutralization reaction into a flocculation tank, adding PAM (polyacrylamide) to perform sludge precipitation, staying for 24 hours to obtain Fe/Cr/Ni sludge, introducing supernate into a nickel precipitation tank, performing filter pressing on the Fe/Cr/Ni sludge to obtain first filtrate, and introducing the first filtrate into the nickel precipitation tank;
and 4, nickel precipitation, adding calcium hydroxide slurry with the concentration of 5% into a nickel precipitation tank to precipitate Ni ions into nickel hydroxide, controlling the pH value of the nickel precipitation tank to be 8.5-9.5, standing for 2 hours to obtain a third supernatant, introducing the precipitated nickel hydroxide into an inclined tube precipitation tank, performing pressure filtration to obtain a third filtrate, combining the third filtrate and the third supernatant into a treatment solution, introducing the treatment solution into a manganese precipitation tank, adding sodium sulfide into the manganese precipitation tank, performing aeration, controlling the aeration time to be 0.5-2.0 hours, obtaining manganous hydroxide or manganese sulfide precipitate, introducing a fourth supernatant into a transition tank, performing pressure filtration to the precipitate to obtain a fourth filtrate, introducing the fourth filtrate into the transition tank, and combining the fourth filtrate and the fourth supernatant to obtain the pretreated wastewater.
Step 5, concentrating the waste liquid, namely introducing the pretreated waste water in the transition tank into an MED falling film evaporator to perform MVR evaporation concentration to obtain a concentrated solution;
step 6, preparing nitric acid, introducing the concentrated solution into a first reaction tank, adding 98% concentrated sulfuric acid with half of the total reaction amount into the first reaction tank, reacting for 10-15 min, performing solid-liquid separation to obtain first separated solution and first slurry, adding the first separated solution into a second reaction tank, introducing the first slurry into a filter press for filter pressing to form a first filter cake and first pressure filtrate, adding the first pressure filtrate into the second reaction tank, adding 98% concentrated sulfuric acid with half of the total reaction amount into the second reaction tank, reacting for 10-15 min, performing solid-liquid separation to obtain second separated solution and second slurry, introducing the second slurry into the filter press for filter pressing to form a second filter cake and second pressure filtrate, placing the second pressure filtrate into a nitric acid storage tank, introducing high-pressure water into the filter press for flushing to obtain flushing wastewater, wherein the high-pressure water comes from an MED falling film evaporator, and introducing the flushing wastewater into a neutralization reaction tank, introducing compressed air into the second filter cake in a filter press, and introducing the blow-off liquid into a nitric acid storage tank for storage.
As a further arrangement of the invention, the blow-off gas of the compressed air after passing through the filter cake is discharged after being treated by the acid mist tower.
As a further configuration of the present invention, in the step 6, dry air is further introduced into the first filter cake and the second filter cake.
The second embodiment of the method for treating and recycling the pickling wastewater containing metallic iron, chromium and nickel of the invention comprises the following steps: the method comprises the following steps of 1, oil removal adjustment, namely, collecting pickling wastewater, separating the pickling wastewater through a PE (polyethylene) grid, and homogenizing in an oil removal tank;
step 2, performing neutralization reaction, namely introducing the homogenized acid washing wastewater into a neutralization reaction tank, adding calcium hydroxide into the neutralization reaction tank, standing for 4 hours, and controlling the pH value of the neutralization reaction tank to be 5.6-5.8;
step 3, performing advection precipitation, namely introducing the acid pickling wastewater subjected to the neutralization reaction into a flocculation tank, adding PAM (polyacrylamide) to perform sludge precipitation, staying for 24 hours to obtain Fe/Cr/Ni sludge, introducing supernate into a nickel precipitation tank, performing filter pressing on the Fe/Cr/Ni sludge to obtain first filtrate, and introducing the first filtrate into the nickel precipitation tank;
and 4, nickel precipitation, wherein vulcanizing agents added into a nickel precipitation tank are one or more of hydrogen sulfide, sodium hydrosulfide, sodium sulfide, barium sulfide and calcium sulfide, the pH range is 3.50-5.50 during vulcanization, the mixture stays for 1.5-2.5 hours to obtain a third supernatant, precipitated nickel hydroxide is introduced into an inclined tube precipitation tank and is subjected to filter pressing to obtain a third filtrate, the third filtrate and the third supernatant are combined to form a treatment solution, the treatment solution is introduced into a manganese precipitation tank, sodium sulfide is added into the manganese precipitation tank and is aerated, the aeration time is controlled to be 0.5-2.0 hours to obtain manganous hydroxide or manganese sulfide precipitation, the fourth supernatant is introduced into a transition tank, the precipitate is subjected to filter pressing to obtain a fourth filtrate, the fourth filtrate is introduced into the transition tank, and the fourth filtrate and the fourth supernatant are combined to obtain pretreated wastewater.
Step 5, concentrating the waste liquid, namely introducing the pretreated waste water in the transition tank into an MED falling film evaporator to perform MVR evaporation concentration to obtain a concentrated solution;
step 6, preparing nitric acid, introducing the concentrated solution into a first reaction tank, adding 98% concentrated sulfuric acid with half of the total reaction amount into the first reaction tank, reacting for 10-15 min, performing solid-liquid separation to obtain first separated solution and first slurry, adding the first separated solution into a second reaction tank, introducing the first slurry into a filter press for filter pressing to form a first filter cake and first pressure filtrate, adding the first pressure filtrate into the second reaction tank, adding 98% concentrated sulfuric acid with half of the total reaction amount into the second reaction tank, reacting for 10-15 min, performing solid-liquid separation to obtain second separated solution and second slurry, introducing the second slurry into the filter press for filter pressing to form a second filter cake and second pressure filtrate, placing the second pressure filtrate into a nitric acid storage tank, introducing high-pressure water into the filter press for flushing to obtain flushing wastewater, wherein the high-pressure water comes from an MED falling film evaporator, and introducing the flushing wastewater into a neutralization reaction tank, introducing compressed air into the second filter cake in a filter press, and introducing the blow-off liquid into a nitric acid storage tank for storage.
As a further arrangement of the invention, the blow-off gas of the compressed air after passing through the filter cake is discharged after being treated by the acid mist tower.
As a further configuration of the present invention, in the step 6, dry air is further introduced into the first filter cake and the second filter cake.
The above example is only one of the preferred embodiments of the present invention, and general changes and substitutions by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (10)
1. A method for treating and recycling pickling wastewater containing metal iron, chromium and nickel is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
step 1, oil removal adjustment, namely collecting pickling wastewater, separating the pickling wastewater through a PE (polyethylene) grid, and homogenizing in an oil removal tank;
step 2, performing primary neutralization reaction, namely introducing the homogenized acid washing wastewater into a primary neutralization reaction tank, neutralizing the acid washing wastewater with lime emulsion until the pH value is 3.0 +/-0.5, controlling the reaction time to be 0.5-2.0 hours, obtaining a calcium fluoride product and a neutralization filtrate, allowing the calcium fluoride product to enter a primary advection tank for precipitation, and allowing the neutralization filtrate to enter a secondary neutralization reaction tank;
step 3, performing secondary neutralization reaction, namely adding lime emulsion into a secondary neutralization reaction tank, standing for 3-5 hours, controlling the pH value of the secondary neutralization reaction tank to be 5.6-5.8, introducing acid washing wastewater subjected to the neutralization reaction into a flocculation tank, adding PAM (polyacrylamide) for sludge precipitation, staying for 22-26 hours to obtain Fe/Cr/Ni sludge, introducing a first supernatant into a nickel precipitation tank, performing filter pressing on the Fe/Cr/Ni sludge to obtain a first filtrate, and introducing the first filtrate into the nickel precipitation tank;
step 4, nickel precipitation, namely adding a vulcanizing agent or calcium hydroxide slurry into a nickel precipitation tank, filtering to obtain nickel precipitation and treatment liquid, treating the treatment liquid to obtain pretreated wastewater, and introducing the pretreated wastewater into a transition tank;
step 5, concentrating the waste liquid, namely introducing the pretreated waste water in the transition tank into an MED falling film evaporator to perform MVR evaporation concentration to obtain a concentrated solution;
and 6, preparing nitric acid, namely introducing the concentrated solution into a first reaction tank, adding 98% concentrated sulfuric acid with half of the total reaction metered amount into the first reaction tank, reacting for 10-15 min, carrying out solid-liquid separation to obtain first separated liquid and first slurry, adding the first separated liquid into a second reaction tank, adding 98% concentrated sulfuric acid with half of the reaction metered amount into the second reaction tank, reacting for 10-15 min, carrying out solid-liquid separation to obtain second separated liquid and second slurry, and placing the second separated liquid into a nitric acid storage tank for storage.
2. The method for treating the acid-containing wastewater and acid sludge generated in the acid washing of the stainless steel according to claim 1, which is characterized in that: and 4, adding 5% calcium hydroxide slurry in the step 4, precipitating Ni ions into nickel hydroxide, controlling the pH value of a nickel sedimentation tank to be 8.5-9.5, standing for 1.5-2.5 hours to obtain a third supernatant, introducing the precipitated nickel hydroxide into an inclined tube sedimentation tank, performing pressure filtration to obtain a third filtrate, and combining the third filtrate and the third supernatant to obtain a treatment solution.
3. The method for treating the acid-containing wastewater and acid sludge generated in the acid washing of the stainless steel according to claim 1, which is characterized in that: and 4, adding vulcanizing agents which are one or more of hydrogen sulfide, sodium hydrosulfide, sodium sulfide, barium sulfide and calcium sulfide into the mixture obtained in the step 4, keeping the mixture for 1.5-2.5 hours when the mixture is vulcanized, obtaining third supernatant, introducing the precipitated nickel hydroxide into an inclined tube sedimentation tank, performing pressure filtration to obtain third filtrate, and combining the third filtrate and the third supernatant to obtain the treatment solution.
4. The method for treating the acid-containing wastewater and acid sludge generated in the acid washing of the stainless steel according to claim 2 or 3, which is characterized by comprising the following steps: and 4, treating the treatment solution, namely introducing the treatment solution into a manganese sedimentation tank, adding sodium sulfide into the manganese sedimentation tank, aerating, controlling the aeration time to be 0.5-2.0 h, obtaining manganous hydroxide or manganese sulfide sediment, introducing a fourth supernatant into a transition tank, performing filter pressing on the sediment to obtain a fourth filtrate, introducing the fourth filtrate into the transition tank, and combining the fourth filtrate and the fourth supernatant to obtain the pretreated wastewater.
5. The method for treating and recycling pickling wastewater containing metal iron chromium nickel according to claim 4, characterized in that: step 6, introducing the first slurry into a filter press for filter pressing to form a first filter cake and a first pressure filtrate, and adding the first pressure filtrate into a second reaction tank; the method comprises the steps of introducing the second slurry into a filter press for filter pressing to form a second filter cake and a second pressure filtrate, and adding the second pressure filtrate into a nitric acid storage tank for storage.
6. The method for treating and recycling pickling wastewater containing metal iron chromium nickel according to claim 5, characterized in that: and step 6, introducing high-pressure water into the second filter cake in a filter press for washing to obtain washing wastewater, and introducing the washing wastewater into the neutralization reaction tank.
7. The method for treating and recycling pickling wastewater containing metal iron chromium nickel according to claim 6, characterized in that: the high pressure water comes from the MED falling film evaporator.
8. The method for treating and recycling pickling wastewater containing metal iron chromium nickel according to claim 5, characterized in that: and step 6, introducing compressed air into the second filter cake in a filter press, and introducing the blow-off liquid into a nitric acid storage tank for storage.
9. The method for treating and recycling pickling wastewater containing metal iron chromium nickel according to claim 8, characterized in that: and blowing out gas of the compressed air after the filter cake is treated in an acid mist tower, spraying an alkaline solution in the acid mist tower, and discharging the blown out gas out of the acid mist tower after the blown out gas is fully contacted with the alkaline solution.
10. The method for treating and recycling pickling wastewater containing metal iron chromium nickel according to claim 5, characterized in that: and 6, introducing dry air into the first filter cake and the second filter cake.
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| CN113772874A (en) * | 2021-10-16 | 2021-12-10 | 浙江永电环境科技有限公司 | Method for treating calcium nitrate generated in stainless steel pickling wastewater treatment process |
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| GB2134095B (en) * | 1983-01-25 | 1986-08-28 | Outokumpu Oy | Method for regenerating pickling acids |
| CN101648759A (en) * | 2009-09-01 | 2010-02-17 | 浙江大学 | Recycling processing method for wastewater produced by processing stainless steel |
| CN104310647B (en) * | 2014-10-21 | 2017-05-17 | 徐超群 | Recycling method for treating stainless steel pickling acid pickle and wastewater |
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| GB2134095B (en) * | 1983-01-25 | 1986-08-28 | Outokumpu Oy | Method for regenerating pickling acids |
| CN101648759A (en) * | 2009-09-01 | 2010-02-17 | 浙江大学 | Recycling processing method for wastewater produced by processing stainless steel |
| CN104310647B (en) * | 2014-10-21 | 2017-05-17 | 徐超群 | Recycling method for treating stainless steel pickling acid pickle and wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113772874A (en) * | 2021-10-16 | 2021-12-10 | 浙江永电环境科技有限公司 | Method for treating calcium nitrate generated in stainless steel pickling wastewater treatment process |
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