CN110759442A - Method for treating trivalent chromium passivation wastewater - Google Patents
Method for treating trivalent chromium passivation wastewater Download PDFInfo
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- CN110759442A CN110759442A CN201810848003.9A CN201810848003A CN110759442A CN 110759442 A CN110759442 A CN 110759442A CN 201810848003 A CN201810848003 A CN 201810848003A CN 110759442 A CN110759442 A CN 110759442A
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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
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- 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
- C02F1/54—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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
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Abstract
The invention discloses a method for treating trivalent chromium passivation wastewater, which comprises the steps of adding a ferrous chloride solution into a wastewater treatment tank, then adding lime emulsion to enable the pH value of the wastewater to be 10-11, precipitating a carboxyl-containing organic acid coordination agent by using ferrous ions and calcium ions together to enable metal ions such as trivalent chromium and the like to generate hydroxide precipitate, adding a flocculating agent to enable precipitate particles to be aggregated, filtering and separating precipitate, and adjusting the pH value of the wastewater to be 6-9. The treatment result meets the requirements of the GB 21900-. The invention creates a new method for removing the organic acid coordination agent containing carboxyl and the heavy metal ions in the wastewater by using ferrous ions and calcium ions, and the method has the advantages of simple and easy process, low treatment cost and better market application prospect.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a treatment method of trivalent chromium passivation wastewater.
Background
The trivalent chromium passivation is used for replacing the highly toxic hexavalent chromium passivation, so that the method is widely applied and obtains good environmental benefit and social benefit.
The trivalent chromium passivation solution contains trivalent chromium and cobalt metal ions and a carboxyl-containing organic acid coordination agent which generates complex ions with the trivalent chromium and cobalt metal ions, and some trivalent lattice passivation solutions also contain a small amount of rare earth salt. Trivalent chromium passivation is generally used for passivation treatment of zinc plating and zinc-nickel alloy plating, and passivation wastewater contains components of passivation solution, zinc ions, nickel ions, iron ions, rare earth element ions and the like.
The trivalent chromium passivation solution has the advantages that the components change rapidly in use and need to be replaced frequently, and more trivalent chromium passivation waste solution is generated, so that the treatment amount of the trivalent chromium passivation waste water is large. While the trivalent chromium passivation is short in time for large-scale production, and the wastewater treatment technology is not mature at present.
Citric acid has strong oxidation resistance, the citric acid destruction efficiency by the traditional oxidation method is low, a large amount of oxidant is generally needed, the treatment cost is high, and the citric acid is difficult to effectively remove in winter with lower temperature. Therefore, the trivalent chromium passivation wastewater containing citric acid is treated by the traditional oxidation-hydroxide precipitation method, and the content of the trivalent chromium in the treated wastewater can not meet the requirement of GB21900-2008 'discharge Standard of electroplating pollutants'.
Disclosure of Invention
Based on the above, there is a need for a method for treating trivalent chromium passivation wastewater, so that heavy metal ions such as complexing agent and trivalent chromium in the treated trivalent chromium passivation wastewater can be effectively treated.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for treating trivalent chromium passivation wastewater comprises the following steps:
(1) under the mechanical stirring, adding a ferrous chloride solution into the trivalent chromium passivation wastewater;
(2) under mechanical stirring, adding lime emulsion into the wastewater treated in the step (1), adjusting the pH to 10-11, precipitating a carboxyl-containing organic acid coordination agent in the wastewater under the synergistic action of ferrous ions and calcium ions, and generating hydroxide precipitates from metal ions such as trivalent chromium released from the coordination ions;
(3) under the mechanical stirring, adding a flocculating agent into the wastewater treated in the step (2) to enable precipitates to aggregate into large particles and then settle;
(4) filtering, and removing the precipitate treated in the step (3);
(5) and (5) adjusting the pH value of the wastewater treated in the step (4) to 6-9 to obtain the product.
Under the alkaline condition, ferrous ions and calcium ions can generate precipitates with organic acid containing carboxyl, and the organic acid coordination agent containing carboxyl in trivalent chromium passivation wastewater can be effectively removed by utilizing the synergistic effect of the ferrous ions and the calcium ions.
At the same time of precipitating the coordination agent, trivalent chromium ions, cobalt ions, zinc ions, nickel ions, iron ions, rare earth elements and other ions are released from the coordination agent and the coordination ions generated by the organic acid coordination agent containing carboxyl to generate hydroxide precipitates, so that the metal ions can be effectively removed.
The trivalent chromium passivation wastewater is weakly acidic, ferrous chloride is added under the weakly acidic condition, then calcium hydroxide is added to adjust the pH of the wastewater from the weak acidity to 10-11, in the process of pH increase, ferrous ions can be guaranteed to generate precipitates in preference to an organic acid coordination agent containing carboxyl, the rest ferrous ions generate ferrous hydroxide precipitates, and when the pH is increased to 10-11, the ferrous ions are completely precipitated. If ferrous chloride is added under the condition that the pH value is 10-11, most ferrous ions firstly generate ferrous hydroxide and then slowly convert into precipitates generated by a complexing agent due to the kinetic reason, and the treatment effect is poor.
The trivalent chromium passivation solution does not generally contain organic additives, and when the complexing agent is precipitated and separated, other organic matters are not required to be treated for treating the trivalent chromium passivation wastewater.
Individual trivalent chromium passivation solution contains a small amount of organic additives, but the content of the organic additives in the wastewater is very low, so that the Chemical Oxygen Demand (COD) (chemical Oxygen demand) is not over standard, and the organic substances are not required to be oxidized.
In the treatment of electroplating wastewater, the method is divided into two stirring modes of mechanical stirring and air stirring, and the mechanical stirring is adopted in the invention for the reasons that: the mechanical stirring avoids the problem that ferrous ions can be oxidized by air to lose the functions of the ferrous ions caused by air stirring, and simultaneously avoids sand, sediment and the like from being buried and blocking the air blowing pipe in the wastewater treatment process.
In some embodiments, the ferrous chloride solution in the step (1) contains 150-250 g/L ferrous chloride tetrahydrate by mass.
In some embodiments, the volume ratio of the ferrous chloride solution added in the step (1) to the trivalent chromium passivation wastewater is (1-5): 100.
In some embodiments, the volume ratio of the ferrous chloride solution added in the step (1) to the trivalent chromium passivation wastewater is (1-2.5): 100.
In some embodiments, the mass concentration of calcium oxide in the lime emulsion in the step (2) is 50-100 g/L.
In some embodiments, the flocculant in the step (3) is a polyacrylamide aqueous solution with the mass concentration of 3-8 g/L and the type of PAM.
In some embodiments, the pH is adjusted in step (6) with dilute hydrochloric acid, which is 2% to 8% dilute hydrochloric acid.
Based on the technical scheme, the invention has the following beneficial effects:
1. according to the method for treating the trivalent chromium passivation wastewater, the synergistic effect of ferrous ions and calcium ions is utilized, and the ferrous chloride and the calcium hydroxide are used for precipitating the organic acid coordination agent containing carboxyl in the wastewater, so that the technical defect that the cost for damaging coordination agents such as citric acid and the like is high in the traditional method is overcome;
2. according to the method for treating the trivalent chromium passivation wastewater, after the complexing agent in the wastewater is precipitated, the trivalent chromium and other metal ions released from the complexing agent generate hydroxide precipitates, so that heavy metal pollutants are effectively removed; in the traditional method, part of trivalent chromium is oxidized into hexavalent chromium while a complexing agent is damaged by an oxidation method, the hexavalent chromium is still remained in the wastewater after the reduction by a reducing agent, the secondary pollution of the hexavalent chromium is caused, and the increase of COD is caused by the excessive addition of the reducing agent;
3. according to the method for treating the trivalent chromium passivation wastewater, the complexing agent is removed by using the ferrous chloride and the calcium hydroxide, so that the COD in the wastewater is greatly reduced, and the efficiency of reducing the COD by destroying the complexing agent by using a traditional oxidation method is very low;
4. the method for treating the trivalent chromium passivation wastewater can simultaneously remove heavy metal pollutants such as a coordination agent, trivalent chromium and the like in the wastewater, and has the advantages of simple process, low treatment cost and good market application prospect.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The trivalent chromium passivation wastewater comprises trivalent chromium passivation rinsing water and trivalent chromium passivation waste liquid, wherein the trivalent chromium passivation wastewater comprises a carboxyl-containing organic acid coordination agent, trivalent chromium ions, cobalt ions, zinc ion nickel ions and iron ions, the carboxyl-containing organic acid coordination agent comprises a citric acid coordination agent, a tartaric acid coordination agent, a malic acid coordination agent or an oxalic acid coordination agent, and the trivalent chromium passivation wastewater does not comprise an aminoacetic acid coordination agent; the trivalent chromium plating waste water does not contain fluoride.
The equipment used in the following examples of the present invention is conventional equipment, and the main equipment and chemicals are as follows:
a trivalent chromium passivation wastewater adjusting tank, a feeding tank, a sedimentation tank, a flocculation tank, an inclined tube sedimentation tank, a neutralization tank and a plate and frame filter press;
ferrous chloride solution: ferrous chloride tetrahydrate aqueous solution with the mass concentration of 200 g/L;
lime emulsion: the mass concentration of the calcium oxide is 80 g/L;
flocculating agent: 5g/L type PAM polyacrylamide aqueous solution;
dilute hydrochloric acid: 5% diluted hydrochloric acid.
Example 1: treating trivalent chromium passivation wastewater containing 100mg/L of trivalent chromium ions
The embodiment provides a method for treating trivalent chromium passivation wastewater, which is used for treating trivalent chromium plating wastewater containing 100mg/L of trivalent chromium ions; the method comprises the following steps:
step one, adding ferrous chloride
And (3) conveying the trivalent chromium passivation wastewater from the wastewater adjusting tank to a feeding tank, adding 10L of ferrous chloride solution into each ton of wastewater, and stirring the tank liquid by using a stirrer.
Step two, precipitating the complexing agent and heavy metal ions
And (2) enabling the wastewater to flow into a precipitation tank from a feeding tank, stirring the tank liquid by using a stirrer, adding lime emulsion to enable the pH of the wastewater to be 10-11, enabling ferrous ions and calcium ions to generate precipitates with the organic acid coordination agent containing carboxyl, and enabling trivalent chromium ions, cobalt ions, zinc ions, nickel ions and rare earth element ions released from the complexes to generate hydroxide precipitates.
Step three, precipitation separation
And (3) enabling the wastewater to flow into a flocculation tank from the sedimentation tank, stirring the tank liquid by using a stirrer, adding a flocculating agent to enable the sediment to flocculate, and aggregating the sediment into large particles. The wastewater flows into the inclined tube sedimentation tank from the flocculation tank, and the sediment is settled at the bottom of the sedimentation tank. And pumping the precipitate into a plate and frame filter press by using a sludge pump, carrying out filter pressing, and enabling the filtrate to flow back to the trivalent chromium passivation wastewater regulating tank. The filter residue is treated (sintered) by qualified professional manufacturers.
Step four, neutralization treatment
And enabling the supernatant in the inclined tube sedimentation tank to flow into a neutralization tank, stirring the liquid in the tank, and adding diluted hydrochloric acid to adjust the pH value to 7-8.
Step five, discharging waste water
And discharging the treated trivalent chromium passivation wastewater from a water outlet of the equipment.
Example 2: treating trivalent chromium passivation wastewater containing 200mg/L of trivalent chromium ions
The embodiment provides a method for treating trivalent chromium passivation wastewater, which is used for treating trivalent chromium plating wastewater containing 200mg/L of trivalent chromium ions and 800mg/L of malic acid; the method comprises the following steps:
step one, adding ferrous chloride
And (3) conveying the trivalent chromium passivation wastewater regulating tank to a feeding tank, stirring the tank liquid by using a stirrer, and adding 20L of ferrous chloride solution into each ton of wastewater.
Step two, precipitating the complexing agent and heavy metal ions
And (3) enabling the wastewater to flow into a sedimentation tank from the feeding tank, stirring the tank liquid by using a stirrer, adding lime emulsion to enable the pH of the wastewater to be 10-11, enabling ferrous ions and calcium ions to generate precipitates with the organic acid coordination agent containing carboxyl, and enabling heavy metal ions such as trivalent chromium released from the complex to generate hydroxide precipitates.
Step three, precipitation separation
And (3) enabling the wastewater to flow into a flocculation tank from the sedimentation tank, stirring the tank liquid by using a stirrer, adding a flocculating agent to enable the sediment to flocculate, and aggregating the sediment into large particles. The wastewater flows into the inclined tube sedimentation tank from the flocculation tank, and the sediment is settled at the bottom of the sedimentation tank. And pumping the precipitate into a plate and frame filter press by using a sludge pump, carrying out filter pressing, and enabling the filtrate to flow back to the trivalent chromium passivation wastewater regulating tank. The filter residue is treated by qualified professional manufacturers.
Step four, neutralization treatment
And enabling the supernatant in the inclined tube sedimentation tank to flow into a neutralization tank, stirring the liquid in the tank, and adding diluted hydrochloric acid to adjust the pH value to 7-8.
Step seven, discharging waste water
And discharging the treated trivalent chromium passivation wastewater from a water outlet of the equipment.
Test example 1: synergistic effect of ferrous and calcium ions
Preparing trivalent chromium passivation wastewater containing 300mg/L of trivalent chromium ions and 400mg/L of citric acid by using an analytically pure reagent, adjusting the pH value of the trivalent chromium passivation wastewater to 2.5-3.5, heating to 80 ℃ to enable the trivalent chromium ions and the citric acid to generate complex ions, and cooling to room temperature to obtain a to-be-treated test solution.
3 parts of the sample solution to be treated are placed in a beaker, and 1L of the sample solution is taken. Adding 3g of anhydrous calcium chloride into No. 1 beaker, stirring to dissolve, adding calcium hydroxide under stirring to adjust the pH value to 11, and filtering with quantitative filter paper after 30 min. Adding 3g of ferrous chloride tetrahydrate into a No. 2 beaker, stirring to dissolve the ferrous chloride, adding calcium hydroxide under stirring to adjust the pH value to 11, and filtering by using quantitative filter paper after 30 min. Adding 3g of ferrous chloride tetrahydrate into a No. 3 beaker, stirring to dissolve the ferrous chloride, adding 50% of sodium hydroxide solution under stirring to adjust the pH value to 11, and filtering by quantitative filter paper after 30min to obtain a filtrate to be detected.
The chromium content of the filtrate to be tested was determined by atomic absorption spectrometry, and the results are shown in Table 1. Tests show that under the alkaline condition, citric acid and trivalent chromium cannot be effectively removed by singly using the calcium ion precipitation citric acid coordination agent, the efficiency of singly using ferrous ions to precipitate the citric acid and the trivalent chromium is not high enough, and the expected effect can be achieved by jointly precipitating the citric acid and the trivalent chromium by using the ferrous ions and the calcium ions. It can be seen that the organic acid containing carboxyl groups precipitated by ferrous ions and calcium ions has a synergistic effect.
TABLE 1 results of treating trivalent chromium plating wastewater with ferrous ion and calcium ion
Test example 2: process parameters for determining pH
The pH conditions for the trivalent chromium, cobalt, zinc, nickel, and ferrous ions to form the hydroxide are shown in Table 2. From the data in the table, it is clear that the proper pH range needs to be selected to precipitate the heavy metal ions in the trivalent chromium passivation wastewater as hydroxides. The method for treating the trivalent chromium passivation wastewater uses ferrous ions and calcium ions to precipitate the organic acid coordination agent containing carboxyl, and the ferrous ions can be completely precipitated when the pH value reaches 9.7, so the pH value of the method is not less than 10. The zinc hydroxide starts to dissolve when the pH reaches 10.5, so the upper process limit of the pH needs to be determined.
TABLE 2 pH conditions for precipitation of metal ions in trivalent chromium passivation wastewater
Preparing zinc sulfate solution containing 100mg/L of zinc ions, and adding 200mg/L of malic acid to serve as test solution to be treated.
Putting 3 parts of to-be-treated test solution into a beaker, adding 15mL of ferrous chloride solution into each 1L part of the to-be-treated test solution, adding lime emulsion under stirring to adjust the pH of each test solution to 10.0, 10.5, 11.0, 11.5 and 12.0 respectively, standing for 30min, and filtering with quantitative filter paper to obtain to-be-detected filtrate.
The mass concentration of zinc in each filtrate to be measured was measured by atomic absorption spectrometry, and the results are shown in Table 3.
TABLE 3 influence of pH on the treatment results
| pH | Zinc (mg/L) after treatment | Removal Rate (%) | GB21900- |
| 10.0 | 0.07 | 99.93 | Meet the requirements of Table 3 |
| 10.5 | 0.18 | 99.82 | Meet the requirements of Table 3 |
| 11.0 | 0.41 | 99.59 | Meet the requirements of Table 3 |
| 11.5 | 1.13 | 98.87 | Meet the requirements of Table 2 |
| 12.0 | 2.18 | 97.82 | Does not reach the standard |
The pH value is within the range of 10-11, the treatment result of the zinc ions can meet the requirements of GB21900-2008 standard table 3, and when the pH value reaches 12, the treatment result does not reach the standard. Therefore, the pH process parameter of the method for treating the trivalent chromium passivation wastewater is 10-11, and all hydroxides of metal pollutants in the treated wastewater have higher stability in the pH range.
Test example 3: treatment result of trivalent chromium passivation wastewater
Taking 1L of passivation rinsing water on a zinc-nickel alloy coating trivalent chromium natural color passivation production line, wherein the passivation rinsing water contains trivalent chromium ions, cobalt ions, zinc ions, nickel ions and iron ions, and contains complexing agents of malic acid and oxalic acid. Adding 15mL of ferrous chloride solution, adding lime emulsion under stirring until the pH value is 10.5, adding 1mL of flocculating agent, stirring uniformly, standing for 30min, and filtering to obtain a filtrate to be detected.
The test filtrate was measured by atomic absorption spectrometry, and the results are shown in Table 4. The wastewater treatment result meets the requirements of table 3 in GB21900-2008 'discharge Standard of electroplating pollutants'.
TABLE 4 treatment results for trivalent chromium natural color passivation wastewater
| Processing items | Treatment results (mg/L) | GB21900- |
| Cr3+ | 0.06 | Meet the requirements of Table 3 |
| Co2+ | 0.12 | Without requirement |
| Zn2+ | 0.23 | Meet the requirements of Table 3 |
| Ni2+ | 0.07 | Meet the requirements of Table 3 |
| Fe2+ | 0.56 | Meet the requirements of Table 3 |
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The method for treating the trivalent chromium passivation wastewater is characterized by comprising the following steps of:
(1) under the mechanical stirring, adding a ferrous chloride solution into the trivalent chromium passivation wastewater;
(2) under mechanical stirring, adding lime emulsion into the wastewater treated in the step (1), adjusting the pH to 10-11, precipitating a carboxyl-containing organic acid coordination agent in the wastewater under the synergistic action of ferrous ions and calcium ions, and generating hydroxide precipitates from metal ions such as trivalent chromium released from the coordination ions;
(3) under the mechanical stirring, adding a flocculating agent into the wastewater treated in the step (2) to enable precipitates to aggregate into large particles and then settle;
(4) filtering, and removing the precipitate treated in the step (3);
(5) and (5) adjusting the pH value of the wastewater treated in the step (4) to 6-9 to obtain the product.
2. The method for treating trivalent chromium passivation wastewater according to claim 1, wherein the ferrous chloride solution in the step (1) contains ferrous chloride tetrahydrate with a mass concentration of 150-250 g/L.
3. The method for treating trivalent chromium passivation wastewater according to claim 2, wherein the volume ratio of the ferrous chloride solution added in the step (1) to the trivalent chromium passivation wastewater is (1-5): 100.
4. The method for treating trivalent chromium passivation wastewater according to claim 3, wherein the volume ratio of the ferrous chloride solution added in the step (1) to the trivalent chromium passivation wastewater is (1-2.5): 100.
5. The method for treating trivalent chromium passivation wastewater according to claim 1, wherein the mass concentration of calcium oxide in the lime emulsion in the step (2) is 50-100 g/L.
6. The method for treating trivalent chromium passivation wastewater according to claim 1, wherein the flocculant in the step (3) is a polyacrylamide aqueous solution with a mass concentration of 3-8 g/L and a type of PAM.
7. The method for treating trivalent chromium passivation wastewater of claim 1, wherein the pH is adjusted by using dilute hydrochloric acid in the step (5).
8. The method for treating trivalent chromium passivation wastewater as set forth in claim 7, wherein the dilute hydrochloric acid is 2-8% of dilute hydrochloric acid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705639A (en) * | 1985-05-10 | 1987-11-10 | The United States Of America As Represented By The Secretary Of The Air Force | Ferrous and sulfide treatment of electroplating wastewater |
| CN106915811A (en) * | 2015-12-28 | 2017-07-04 | 南京源泉环保科技股份有限公司 | A kind of trivalent chromium passivation washings contact break agent and preparation method and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4705639A (en) * | 1985-05-10 | 1987-11-10 | The United States Of America As Represented By The Secretary Of The Air Force | Ferrous and sulfide treatment of electroplating wastewater |
| CN106915811A (en) * | 2015-12-28 | 2017-07-04 | 南京源泉环保科技股份有限公司 | A kind of trivalent chromium passivation washings contact break agent and preparation method and application |
Non-Patent Citations (1)
| Title |
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| 中国环境保护产业协会: "《中国环境保护产业技术装备水平评价》", 30 September 2000, 中国环境科学出版社 * |
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