CN111500864A - Method for recycling electroplating sludge based on chromium recovery - Google Patents
Method for recycling electroplating sludge based on chromium recovery Download PDFInfo
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- CN111500864A CN111500864A CN202010344081.2A CN202010344081A CN111500864A CN 111500864 A CN111500864 A CN 111500864A CN 202010344081 A CN202010344081 A CN 202010344081A CN 111500864 A CN111500864 A CN 111500864A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
- C01G37/033—Chromium trioxide; Chromic acid
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for recycling electroplating sludge based on chromium recovery, which adopts hydrogen peroxide as an oxidant to remove Fe in electroplating sludge leachate2+、Cr3+Is oxidized into Fe3+、Cr6+Then adding liquid alkali into the solution to generate precipitation to realize the complete separation of chromium ions in the solution, and then adding sodium metabisulfite into the solution to separate Cr6+Reduction to Cr3+Adding liquid alkali to precipitate chromium ions into chromium hydroxide, calcining at high temperature, and pulverizing to obtain chromium sesquioxide. The method can realize 99% efficient recovery of copper, nickel and zinc in the electroplating sludge, simultaneously realize more than 98% recovery efficiency of Cr in the electroplating sludge and prepare high-value products, the leaching residues are completely detoxified, so that hazardous waste of incoming materials is completely converted into common solid waste, the raw and auxiliary materials in the whole production process are low in price, the equipment operation is simple, the benefit is obvious, and no hazardous waste is discharged.
Description
Technical Field
The invention relates to a method for recovering metals in electroplating sludge, in particular to a method for recycling electroplating sludge based on chromium recovery.
Background
Electroplating is one of three major global pollution industries today. According to incomplete statistics, more than 1 million electroplating enterprises in China discharge electroplating wastewater of about 40 billions of cubic meters every year in the electroplating industry. Such a large amount of electroplating wastewater is chemically treated to produce electroplating sludge having a large amount of heavy metals. The main components of the electroplating sludge are chromium, iron, copper, nickel, aluminum, zinc, magnesium, calcium, silicon, sulfur, cyanogen and the like. Because the electroplating sludge contains a large amount of toxic and harmful heavy metals, the electroplating sludge is listed as dangerous waste by the nation. But simultaneously, the electroplating sludge is rich in a large amount of metal resources, the chromium content in the electroplating sludge is relatively high, and the recovery value is high.
In the prior art, heavy metals are recycled by recycling electroplating sludge, the heavy metals in the sludge are usually extracted and recycled by using a pyrogenic process and a wet process, the pyrogenic process technology comprises a high-temperature melting method, a roasting method and a burning method, the fuel is required to be used for treating the electroplating sludge by using the pyrogenic process, the energy consumption is more, and secondary pollution is easily caused in the burning process; the wet process technology is relatively low in cost and small in secondary pollution, but the existing wet process technology has poor selectivity on copper, nickel and chromium, so that the recovery rate is low.
Therefore, the prior art is subject to further improvement and development.
Disclosure of Invention
In order to solve the above problems, a method for treating electroplating sludge by recycling chromium has been proposed.
The invention provides the following technical scheme:
a method for recycling electroplating sludge based on chromium recovery comprises the following steps:
step 1, pulping the electroplating sludge, and performing primary leaching treatment to obtain a filtrate;
step 2, adding a copper extractant into the filtrate obtained in the step 1 for copper extraction to obtain a copper-rich liquid and a copper raffinate;
step 3, adding hydrogen peroxide into the copper raffinate to react, adding liquid alkali into the reacted solution until no precipitate is generated in the solution, and filtering;
and 4, performing filter pressing on the filtrate obtained after filtration in the step 3, adding sodium metabisulfite into the filtrate for reaction, and then adding liquid alkali to obtain chromium hydroxide precipitate from the solution.
Preferably, the electroplating sludge and water are subjected to pulping treatment according to a solid-to-liquid ratio of 1:4, and sulfuric acid is added into the pulping slurry to stabilize the pH of the slurry to be between 1.5 and 2.0.
Further, adding biological acid into the filter residue obtained by the primary leaching in the step 1, performing secondary leaching, and executing the step 2 on the obtained filtrate.
Preferably, the filter residue obtained by the primary leaching in the step 1 is added with biological acid according to the solid-to-liquid ratio of 1:8, and the pH value of the biological acid is 0.8.
And further, adding clear water into filter residues obtained by secondary leaching according to the solid-to-liquid ratio of 1:3 for slurrying and washing, carrying out filter pressing again, and reusing filter-pressed filter residue washing water in the step 1.
Preferably, the copper extractant consists of a copper-specific extractant L ix984 and a D110 solvent oil.
Further, evaporating and crystallizing the copper-rich liquid obtained in the step 2 to obtain copper sulfate pentahydrate.
Further, the chromium hydroxide precipitate obtained in the step 4 is calcined at high temperature to prepare chromium sesquioxide.
Further, sulfuric acid is added into the filter residue obtained after filtering in the step 3 for dissolving, a nickel extraction agent is added into the dissolved solution for extraction to obtain a nickel-rich liquid and a nickel raffinate, and the nickel-rich liquid is evaporated and crystallized to obtain nickel sulfate hexahydrate, wherein the nickel extraction agent is obtained by uniformly mixing a nickel extraction agent HB L110 and D110 solvent oil according to the volume ratio of 1:1 and then saponifying.
And further, adding a zinc extractant into the nickel raffinate to extract so as to obtain a zinc-rich solution and a zinc raffinate, and evaporating and crystallizing the zinc-rich solution so as to obtain zinc sulfate heptahydrate, wherein the zinc extractant is prepared by mixing a P204 extractant and a D110 solvent oil in a volume ratio of 1:5 evenly mixing the mixture and then saponifying the mixture to obtain the soap.
Advantageous effects
The method realizes the high-efficiency recovery of 99 percent of copper, nickel and zinc in the electroplating sludge, simultaneously realizes the recovery efficiency of more than 98 percent of Cr in the electroplating sludge, prepares a high-value product, completely detoxifies the leaching residue, completely converts hazardous waste of incoming materials into general solid waste, and has the advantages of low price of raw and auxiliary materials in the whole production process, simple equipment operation, obvious benefit and no hazardous waste discharge.
Drawings
FIG. 1 is a process flow diagram of a method for resource disposal of electroplating sludge based on chromium recovery in an embodiment of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description of the technical solutions of the present invention with reference to the accompanying drawings of the present invention is made clearly and completely, and other similar embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments in the present application shall fall within the protection scope of the present application. In addition, directional terms such as "upper", "lower", "left", "right", etc. in the following embodiments are directions with reference to the drawings only, and thus, the directional terms are used for illustrating the present invention and not for limiting the present invention.
A method for recycling electroplating sludge based on chromium recovery adopts hydrogen peroxide as an oxidant to remove Fe in electroplating sludge leachate2+、Cr3+Is oxidized into Fe3+、Cr6+Then adding liquid alkali into the solution to generate precipitation, realizing the complete separation of chromium ions in the solution, and then adding sodium metabisulfite into the solution to separate Cr6+Reduction to Cr3+Adding alkali to precipitate chromium hydroxide, calcining at high temperature, and pulverizing to obtain chromium oxide.
A method for recycling electroplating sludge based on chromium recovery is shown in figure 1 and comprises the following steps:
and S1, pulping the electroplating sludge and water according to a certain solid-to-liquid ratio, adding a certain amount of sulfuric acid into the pulp after the pulp is completely pulped, and stirring to react completely to ensure that the pH value of the pulp is acidic.
Preferably, the solid-to-liquid ratio of the electroplating sludge to the water in S1 is 1:4, the stirring time is 2 hours, and the pH value of the slurry is controlled to be 1.5-2.0.
Preferably, the electroplating sludge is prepared from electroplating sludge with the water content of 60% discharged from a certain plant in Zhejiang province, and the sludge contains 1.70% of nickel, 3.77% of copper, 4.44% of zinc, 4.98% of chromium and other valuable metals.
And (3) performing plate-and-frame filter pressing on the slurry in the S2-S1 to obtain a filtrate, storing the filtrate, adding biological acid into the filter residue according to a certain solid-to-liquid ratio, and stirring for two hours to completely react.
Preferably, the filtrate contains nickel with the concentration of 3.39 g/L, copper with the concentration of 6.86 g/L, zinc with the concentration of 9.29 g/L and chromium with the concentration of 6.94 g/L.
Preferably, the solid-to-liquid ratio of the filter residue to the biological acid in S2 is 1:8, and the pH value of the biological acid is 0.8.
Preferably, the biological acid is the biological acid with the pH value of 0.8 cultured by thiobacillus thiooxidans under the conditions of 35 ℃, 9k culture medium and sulfur as an energy substrate.
And (3) performing plate-and-frame filter pressing on the slurry in the S3: S2, mixing the filtrate with the filtrate of S2, feeding the mixture into an extraction system, adding clear water into filter residues according to a certain solid-to-liquid ratio, washing the slurry for a certain time, performing plate-and-frame filter pressing on the slurry, reusing the washing water into S2, and reusing the filter residues which are detoxified residues as building bricks.
Preferably, the solid-to-liquid ratio of the filter residue to the clear water in S3 is 1:3, and the time for washing the slurry is 1 hour.
S4, uniformly mixing a special copper extracting agent L ix984 and D110 solvent oil 1:5, adding mixed filtrate in S3, carrying out copper extraction, carrying out 3-stage countercurrent extraction, carrying out 1-stage washing, wherein 3-stage countercurrent reverse extraction totally comprises 7-stage extraction lines, wherein an organic phase after reverse extraction is unsaponifiable and directly enters a transfer tank for extraction, washing water is pure water, the washed water returns to a washing water storage tank for recycling, the reverse extracting agent is dilute sulfuric acid with the concentration of 200 g/L, the whole extraction operation is carried out in a multi-stage mixed clarifying tank, the temperature is controlled to be about 30 ℃, the phases of an extraction section, a washing section and a reverse extraction section (organic phase/aqueous phase) are respectively 1:1, 5-6: 1 and 6:1, after the extraction operation, a copper-rich liquid is obtained, wherein the concentration of copper is 39.74 g/L, the concentration of nickel is 0.003 g/L, the concentration of zinc is 0.0007 g/L, the concentration of chromium is 0.8 g/L, and the concentration of copper sulfate is obtained in an evaporation system, wherein the copper extraction raffinate is 0.03 g/L.
S5, adding a proper amount of hydrogen peroxide into the copper raffinate obtained in the S4 to obtain Fe in the solution2+、Cr3+Complete oxidation to Fe3+、Cr6+Then adding liquid caustic soda into the solution, wherein the mass concentration of the liquid caustic soda is 30 percent,until no more precipitation occurred in the solution.
S6, press-filtering the slurry in S5 by a plate-and-frame filter press, adding a proper amount of sodium metabisulfite into the filtrate to remove Cr6+Is completely reduced into Cr3+And then adding liquid caustic soda into the solution, wherein the mass concentration of the liquid caustic soda is 30%, precipitating chromium in the solution into chromium hydroxide, calcining the chromium hydroxide at high temperature to prepare chromium sesquioxide, and reusing the clear liquid as production water in S1.
S7, adding a proper amount of sulfuric acid into the filter residue obtained in the step S6, and completely neutralizing and dissolving the filter residue.
S8, mixing special nickel extracting agents HB L110 and D110 solvent oil uniformly according to a volume ratio of 1:1, adding a proper amount of sodium hydroxide solution with a mass concentration of 30% to carry out 1-stage saponification treatment, controlling the saponification rate to be 40%, adjusting the pH value of filtrate in S5 to 2.0, carrying out 5-stage extraction, 5-stage washing, 4-stage back extraction and 3-stage back washing to share 18-stage extraction lines, wherein washing water is pure water, the washed water is returned to a washing water storage tank for recycling, the back extracting agent is dilute sulfuric acid with a concentration of 75 g/L, the whole extraction process is carried out in a multi-stage mixing clarification tank, the temperature is controlled to be about 30 ℃, the second extraction step is 1.3/1.0 (organic phase/aqueous phase), the second extraction step is to obtain a nickel-rich liquid, wherein the nickel concentration is 35.25 g/L, the zinc concentration is 0.063 g/L, the chromium concentration is 0.066 g/L, the nickel-rich liquid is prepared into an evaporation concentration crystallization system to obtain nickel sulfate hexahydrate, and the nickel extraction raffinate with a concentration lower than 351.84 g/L.
S9, uniformly mixing a P204 extracting agent and D110 solvent oil in a ratio of 1:5, adding a proper amount of sodium hydroxide solution with the mass concentration of 30% to saponify the mixture, adding the solution in S8, performing 1-stage saponification, 4-stage countercurrent extraction, 2-stage washing, 3-stage countercurrent reverse extraction, and 2-stage backwashing, wherein the washing water is pure water, the washed water returns to a washing water storage tank for recycling, the back-extracting agent is dilute sulfuric acid with the concentration of 200 g/L, the whole extraction operation is performed in a multistage mixed clarifying tank, the temperature is controlled to be about 30 ℃, the phase ratio of extraction sections (organic phase/aqueous phase) is 1:1, after the extraction operation, firstly, a zinc-rich liquid is obtained, wherein the concentration of zinc is 45 g/L, the zinc-rich liquid enters an evaporation concentration crystallization system to prepare zinc sulfate heptahydrate, and secondly, the zinc raffinate is obtained and enters sewage treatment, wherein the concentration of zinc is 0.09 g/L.
The method can realize 99% efficient recovery of copper, nickel and zinc in the electroplating sludge, simultaneously realize more than 98% recovery efficiency of Cr in the electroplating sludge and prepare high-value products, the leaching residues are completely detoxified, so that hazardous waste of incoming materials is completely converted into common solid waste, the raw and auxiliary materials in the whole production process are low in price, the equipment operation is simple, the benefit is obvious, and no hazardous waste is discharged.
The present invention has been described in detail, and it should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Claims (10)
1. A method for recycling electroplating sludge based on chromium recovery is characterized by comprising the following steps:
step 1, pulping the electroplating sludge, and performing primary leaching treatment to obtain a filtrate;
step 2, adding a copper extractant into the filtrate obtained in the step S1 to perform copper extraction, so as to obtain a copper-rich liquid and a copper raffinate;
step 3, adding hydrogen peroxide into the copper raffinate to react, adding liquid alkali into the reacted solution until no precipitate is generated in the solution, and filtering;
and 4, performing filter pressing on the filtrate obtained after the filtration in the step S3, adding sodium metabisulfite into the filtrate for reaction, and then adding liquid alkali to obtain chromium hydroxide precipitate from the solution.
2. The method for recycling electroplating sludge based on chromium recovery as claimed in claim 1, wherein the electroplating sludge and water are slurried according to a solid-to-liquid ratio of 1:4, and sulfuric acid is added to the slurry after slurrying to stabilize the pH of the slurry between 1.5 and 2.0.
3. The method for chromium recovery-based resource disposal of electroplating sludge as claimed in claim 1, wherein the residue obtained from the primary leaching in step 1 is added with a biological acid and subjected to a secondary leaching, and the obtained filtrate is subjected to step S2.
4. The method for resource disposal of electroplating sludge based on chromium recovery as claimed in claim 3, wherein the filter residue obtained from the primary leaching in the step 1 is added with biological acid according to the solid-to-liquid ratio of 1:8, and the pH of the biological acid is 0.8.
5. The method for recycling electroplating sludge based on chromium recovery as claimed in claim 3, wherein the filter residue obtained by secondary leaching is washed with clear water slurry according to the solid-to-liquid ratio of 1:3, and then is subjected to pressure filtration again, and the filter residue washing water after pressure filtration is recycled to the step 1.
6. The method for resource disposal of electroplating sludge based on chromium recovery as claimed in claim 3, wherein the copper extractant consists of copper-specific extractant L ix984 and D110 solvent oil.
7. The method for recycling electroplating sludge based on chromium recovery as claimed in claim 1, wherein the copper-rich solution obtained in step 2 is evaporated and crystallized to obtain copper sulfate pentahydrate.
8. The method for recycling electroplating sludge based on chromium recovery as claimed in claim 1, wherein the chromium hydroxide precipitate obtained in step 4 is calcined at high temperature to prepare chromium oxide.
9. The method for recycling electroplating sludge based on chromium recovery according to claim 1, wherein sulfuric acid is added to the filter residue obtained after filtration in step 3 for dissolution, a nickel extractant is added to the dissolved solution for extraction to obtain a nickel-rich solution and a nickel raffinate, and the nickel-rich solution is evaporated and crystallized to obtain nickel sulfate hexahydrate, wherein the nickel extractant is obtained by uniformly mixing a nickel extractant HB L110 and a D110 solvent oil according to a volume ratio of 1:1 and then performing saponification treatment.
10. The method for resource disposal of electroplating sludge based on chromium recovery as claimed in claim 9, wherein the zinc extraction agent is prepared by adding a zinc extraction agent into the nickel raffinate to extract zinc-rich liquid and zinc raffinate, and evaporating and crystallizing the zinc-rich liquid to obtain zinc sulfate heptahydrate, wherein the zinc extraction agent is prepared by mixing a P204 extraction agent and a D110 solvent oil according to a volume ratio of 1:5 evenly mixing the mixture and then saponifying the mixture to obtain the soap.
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Cited By (5)
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| CN112853101A (en) * | 2020-12-31 | 2021-05-28 | 北京首创环境科技有限公司 | Electroplating sludge recycling treatment method |
| CN114293015A (en) * | 2021-12-06 | 2022-04-08 | 生态环境部华南环境科学研究所 | Extraction method and equipment for extracting and recovering heavy metal from electroplating sludge |
| CN114702071A (en) * | 2022-04-15 | 2022-07-05 | 合肥工业大学 | Method for preparing chromium sesquioxide by utilizing high-chromium sludge generated by chromium electroplating rinsing wastewater treatment |
| CN114752767A (en) * | 2022-03-10 | 2022-07-15 | 中国恩菲工程技术有限公司 | Method for recovering copper, zinc and nickel from electroplating sludge |
| CN116891315A (en) * | 2023-07-12 | 2023-10-17 | 广东威特雅环境科技有限公司 | Method for chromium plating wastewater hazardous waste reduction and chromium mud recycling |
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| CN114293015A (en) * | 2021-12-06 | 2022-04-08 | 生态环境部华南环境科学研究所 | Extraction method and equipment for extracting and recovering heavy metal from electroplating sludge |
| CN114293015B (en) * | 2021-12-06 | 2023-05-09 | 生态环境部华南环境科学研究所 | Extraction method and equipment for extracting and recovering heavy metals from electroplating sludge |
| CN114752767A (en) * | 2022-03-10 | 2022-07-15 | 中国恩菲工程技术有限公司 | Method for recovering copper, zinc and nickel from electroplating sludge |
| CN114702071A (en) * | 2022-04-15 | 2022-07-05 | 合肥工业大学 | Method for preparing chromium sesquioxide by utilizing high-chromium sludge generated by chromium electroplating rinsing wastewater treatment |
| CN114702071B (en) * | 2022-04-15 | 2023-11-03 | 合肥工业大学 | Method for preparing chromium oxide by using high-chromium sludge generated by chromium electroplating rinsing wastewater treatment |
| CN116891315A (en) * | 2023-07-12 | 2023-10-17 | 广东威特雅环境科技有限公司 | Method for chromium plating wastewater hazardous waste reduction and chromium mud recycling |
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