CN109517980B - Method for comprehensively recovering copper and nickel in electroplating sludge - Google Patents
Method for comprehensively recovering copper and nickel in electroplating sludge Download PDFInfo
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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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
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0017—Sulfating or sulfiding roasting
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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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
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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
Abstract
The invention relates to the field of hazardous solid waste environment-friendly treatment and resource regeneration, and particularly discloses a method for recovering copper and nickel by electroplating sludge treatment. The method provided by the invention comprises the steps of mixing electroplating sludge and a vulcanization roasting additive for pelletizing to obtain green pellets, drying the green pellets, carrying out vulcanization roasting at the temperature of 800-1200 ℃, and grinding roasted products until the granularity is-0.045 mm and accounts for 60-80% to obtain ore grinding pulp; and (3) carrying out flotation on the ground ore pulp, separating to obtain copper-nickel bulk concentrate, wherein flotation tailings are harmless tailings, the copper-nickel bulk concentrate is ground again until the granularity is-0.037 mm and accounts for 90-95%, and carrying out flotation to obtain a copper concentrate product and a nickel concentrate product respectively. The method provided by the invention treats the electroplating sludge through sulfuration roasting and flotation, can comprehensively recover valuable copper and nickel elements in the electroplating sludge, respectively obtain copper concentrate and nickel concentrate, remarkably reduce the heavy metal content of flotation tailings, and ensure that the leaching toxicity is lower than the national relevant standard.
Description
Technical Field
The invention relates to the technical field of hazardous waste treatment and resource regeneration, in particular to a method for recovering copper and nickel by electroplating sludge treatment.
Background
The electroplating sludge is sediment containing a plurality of heavy metals generated in the electroplating wastewater treatment process, the sediment has high water content, and heavy metal components have high thermal stability and are easy to migrate, so that secondary pollution is easily caused. In 1998, the electroplating sludge is listed as a typical example in national records of dangerous wastes; in 2004, "hazardous waste operation license management method (2013 revision)" strict regulations are made for collection, storage and disposal of electroplating sludge, so as to prevent secondary pollution of electroplating sludge.
In recent years, a great deal of research is carried out on the technology of electroplating sludge treatment, and the research on sludge treatment mainly focuses on the process technology aspects of solidification, stabilization and the like of heavy metal elements, and tries to realize the harmlessness of harmful heavy metal elements. However, from the viewpoint of metal resource recycling, the electroplating sludge is actually a material with relatively high-grade valuable metal elements, and the common valuable metal elements include copper, nickel, chromium, zinc and the like. However, since these valuable metal elements are often present in the form of highly dispersed oxides, it is difficult to enrich them by conventional means. The technological core of the current research on valuable metal element recovery mainly focuses on the leaching technical system of nonferrous metals, such as an ammonia leaching method, a sulfuric acid leaching method and the like, and the problems of high cost, complex flow, low operation efficiency and the like exist in the technological process. Therefore, research on the recycling technology of the electroplating sludge is needed to provide a treatment method with good practicability and good economical efficiency to meet the market demand.
Disclosure of Invention
The invention mainly solves the technical problem of providing a method for comprehensively recovering copper and nickel in electroplating sludge, the electroplating sludge is treated by sulfuration roasting and flotation, valuable elements of copper and nickel in the electroplating sludge can be comprehensively recovered, copper concentrate and nickel concentrate are respectively obtained, the heavy metal content of flotation tailings is obviously reduced, and the leaching toxicity is lower than the related national standard.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for comprehensively recovering copper and nickel in electroplating sludge comprises the following steps of but not limited to:
s1: mixing the electroplating sludge and a vulcanizing roasting additive, pelletizing to obtain green pellets, wherein the grain size range of the green pellets is 8-10 mm, the vulcanizing roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is any one or a combination of several of pyrite, sodium sulfide and sulfur, the flux is quartz and/or alumina, the fluxing agent is borax and/or sodium silicate, and the reducing agent is anthracite;
s2: drying the green pellets, then placing the dried green pellets at the temperature of 800-1200 ℃ for sulfurizing roasting for 60-120 min, and then naturally cooling to obtain roasted products;
s3: crushing the roasted product to the granularity of-2 mm, and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 60-80% under the ore grinding concentration of 60-65% to obtain ore grinding ore pulp;
s4: carrying out flotation on the ore grinding pulp, separating to obtain copper-nickel bulk concentrate, wherein flotation tailings are harmless tailings, and a flotation agent added into the ore grinding pulp during flotation is composed of a regulator I, a collecting agent and a foaming agent, wherein the regulator I is lime and/or copper sulfate, the collecting agent is butyl xanthate and/or butylamine black powder, and the foaming agent is No. two flotation oil;
s5: and grinding the obtained copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 90-95% to obtain copper-nickel bulk concentrate pulp, adding a regulator II into the copper-nickel bulk concentrate pulp to perform copper-nickel separation flotation to respectively obtain a copper concentrate product and a nickel concentrate product, wherein the regulator II is sodium sulfite and/or sodium sulfide.
Further preferably, the obtained copper-nickel bulk concentrate pulp is subjected to flotation impurity removal, then a regulator II is added for copper-nickel separation flotation, and impurities obtained through flotation impurity removal are harmless tailings. The obtained copper-nickel bulk concentrate ore pulp is subjected to flotation and impurity removal, and then is subjected to copper-nickel separation and flotation, so that the grades of the obtained copper concentrate product and nickel concentrate product can be improved, and the separation efficiency of the copper-nickel separation and flotation is improved.
Preferably, in step S1, the usage amount of the sulfidizing agent is 2 to 3 times of the sum of the mole numbers of copper and nickel elements contained in the electroplating sludge.
Preferably, in the step S1, the amount of the flux is 10-30% of the dry weight of the electroplating sludge.
Preferably, in step S1, the amount of the flux is 1-3% of the dry weight of the electroplating sludge.
Preferably, in the step S1, the dosage of the reducing agent is 5-20% of the dry weight of the electroplating sludge.
Preferably, in step S4, the dosage of the modifier I is 200-2000 g per ton of electroplating sludge (dry weight), the dosage of the collector is 150-500 g per ton of electroplating sludge (dry weight), and the dosage of the foaming agent is 50-150 g per ton of electroplating sludge (dry weight).
Preferably, in step S5, the amount of the modifying agent II is 1500-3000 g per ton (dry weight) of electroplating sludge.
Preferably, in the step S4, the ore grinding pulp flotation process adopts multi-stage flotation, including 1-2 times of coarse flotation, 1-2 times of scavenging flotation, and 2-3 times of fine flotation. The number of the stages of rough flotation, scavenging flotation and fine flotation can be properly adjusted according to the actual separation condition.
Preferably, in the step S5, the copper-nickel separation flotation process adopts multi-stage flotation, including 1-2 times of coarse flotation, 1-2 times of scavenging flotation, and 3-4 times of fine flotation. The number of the stages of rough flotation, scavenging flotation and fine flotation can be properly adjusted according to the actual separation condition.
Wherein, the No. two flotation oil is also the No. 2 oil.
The method for comprehensively recovering copper and nickel in electroplating sludge provided by the invention comprises the steps of firstly mixing the electroplating sludge with a vulcanization roasting additive, pelletizing, enabling the particle size range of the obtained green pellets to be 8-10 mm, accelerating the drying speed in the particle size range, enabling the reaction contact area to be large during vulcanization roasting, enabling the reaction to be more thorough, improving the recovery rate of valuable elements, and then drying and carrying out high-temperature vulcanization roasting, wherein the vulcanization roasting additive comprises a vulcanizing agent, a flux, a fluxing agent and a reducing agent. The vulcanizing agent is any one or combination of several of pyrite, sodium sulfide and sulfur, the fusing agent is quartz and/or alumina, the fusing agent is borax and/or sodium silicate, and the reducing agent is anthracite. In the high-temperature vulcanizing roasting process, a vulcanizing agent is used as a sulfur source and mainly provides a sulfur element for vulcanizing operation to generate a sulfide mineral of valuable metals; the flux is mainly used for improving the fluidity of substances in the sintering process, so that the valuable metal embedded in the micro-fine particles can be effectively released and participate in the vulcanization reaction, and the purpose of separating the valuable metal from impurities is achieved; the fluxing agent is mainly used for reducing the melting temperature of a roasted product and improving the roasting efficiency; the reducing agent provides reducing atmosphere for roasting, and ensures that the sulfide products of the valuable metals are not oxidized. After roasting, the copper and nickel in the electroplating sludge are converted into sulfide form from the original oxide form, and flotation separation can be carried out by adopting a flotation method. Crushing the roasted product to the granularity of-2 mm, then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 60-80% under the ore grinding concentration of 60-65% to obtain ore grinding pulp, namely, the mass percentage of particles with the granularity of less than 0.045mm in the ore grinding pulp accounts for 60-80%, according to the imbedding structure analysis of the roasted product, under the ore grinding condition, basically completely dissociating copper, nickel sulfide and harmless tailings in the roasted product, then carrying out flotation, separating to obtain copper-nickel mixed concentrate, wherein the flotation tailings are harmless tailings. And (3) grinding the obtained copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 90-95% to obtain copper-nickel bulk concentrate ore pulp, basically completely dissociating copper sulfides and nickel sulfides in the copper-nickel bulk concentrate under the ore grinding condition, then performing flotation, and respectively obtaining a copper concentrate product and a nickel concentrate product under the action of sodium sulfite and/or sodium sulfide serving as adjusting agents. The adjusting agent is added in the flotation process to strengthen the adsorption of the collecting agent on the surface of the valuable metal sulfide or inhibit the adsorption of the collecting agent on the surface of impurity minerals, so that the selective adsorption efficiency of the collecting agent on the surface of the minerals is improved, the hydrophobic property of the valuable metal sulfide is improved by the collecting agent, so that valuable metals are enriched in flotation foam products, and the foaming agent is used for reducing the surface tension of flotation pulp, forming a stable foam layer and improving the flotation efficiency.
The method for comprehensively recovering copper and nickel in electroplating sludge provided by the invention mainly aims at the problem that the electroplating sludge is solidified sediment of electroplating plant waste liquid containing more than 1% of copper and nickel, the copper grade of the finally treated copper concentrate is more than 16%, and the copper recovery rate is more than 60%; the nickel grade of the nickel concentrate is more than 8 percent, and the nickel recovery rate is more than 60 percent; the content of copper and nickel in the tailings is lower than 0.5%, and the leaching toxicity is lower than the standard value for identifying the leaching toxicity in the identification Standard for hazardous waste (GB 5085.3-2007).
The method for comprehensively recovering copper and nickel in electroplating sludge provided by the invention treats the electroplating sludge by taking sulfidizing roasting and flotation as technical cores for the first time, can comprehensively recover copper and nickel valuable elements in the electroplating sludge, and respectively obtains copper concentrate and nickel concentrate; the process flow is reasonable, the adaptability to raw materials is wide, the solidified precipitates of the waste liquid of the electroplating plant containing more than 1% of copper and nickel can be treated, the heavy metal leaching technology is not involved, the implementation and the control are easier, the economic feasibility is high, and the method has good industrial prospect; compared with the original electroplating sludge, the heavy metal content of the tailings is obviously reduced, the leaching toxicity is lower than the national relevant standard, and the environmental protection benefit is outstanding.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
Example 1
The treatment object is electroplating sludge of a certain electroplating plant in Guangdong Jiangmen, wherein the mass percent of copper and nickel are respectively 2.48% and 1.59%, the electroplating sludge is treated by adopting the following processes, and the copper and the nickel are recovered:
(1) mixing the electroplating sludge and a sulfuration roasting additive, pelletizing to obtain green pellets, wherein the sulfuration roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is pyrite, the flux is quartz, the fluxing agent is borax, the reducing agent is anthracite, the dosage of the vulcanizing agent is 2 times of the sum of the mole numbers of copper and nickel elements contained in the electroplating sludge, the dosage of the flux is 25% of the dry weight of the electroplating sludge, the dosage of the fluxing agent is 1% of the dry weight of the electroplating sludge, and the dosage of the reducing agent is 20% of the dry weight of the electroplating sludge;
(2) drying the green pellets, vulcanizing and roasting at 1000 ℃ for 100min, and naturally cooling to obtain a roasted product;
(3) crushing the roasted product to the granularity of-2 mm (namely the granularity is less than 2mm), and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 80% under the grinding concentration of 60% to obtain ore grinding ore pulp;
(4) sequentially adding 1100g of regulator lime and copper sulfate, 1000g of collector butyl xanthate and butylamine black powder and No. two foaming agent flotation oil into ore grinding pulp, wherein the using amount of the regulator is that every ton of electroplating sludge (calculated according to dry weight, the same below), specifically, the using amount of the lime is that every ton of electroplating sludge is added, 100g of copper sulfate is that every ton of electroplating sludge is added, the using amount of the collector is that every ton of electroplating sludge is added, specifically, the using amount of the butyl xanthate is that every ton of electroplating sludge is added, 100g of the butylamine black powder is that every ton of electroplating sludge is added, the using amount of the foaming agent is that every ton of electroplating sludge is added, stirring is carried out for 30 minutes after the sequential addition is finished, and then carrying out flotation, wherein the flotation process adopts multistage flotation, specifically, the flotation processes of 1-time roughing, 2-time scavenging and 3-time fine flotation are adopted, and copper-nickel mixed concentrate is obtained by separation, flotation tailings are harmless tailings;
(5) the method comprises the steps of finely grinding copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 95%, adding adjusting agents of sodium sulfite and sodium sulfide, wherein the amount of the adjusting agents is 1500g per ton of electroplating sludge, specifically 500g per ton of electroplating sludge and 1000g per ton of electroplating sludge, stirring for 30 minutes after adding, and then performing flotation, wherein the flotation process adopts multi-section flotation, and specifically adopts the processes of 1-time flotation roughing, 1-time flotation scavenging and 3-time flotation concentrating to separate and obtain a copper concentrate product and a nickel concentrate product.
The yield of the copper concentrate product relative to the original dried electroplating sludge was 9.16%, the copper and nickel grades were 20.49% and 3.16%, respectively, and the copper and nickel recovery rates were 75.68% and 18.20%, respectively; the yield of the nickel concentrate product relative to the original dried electroplating sludge was 12.14%, the grades of copper and nickel were 2.23% and 9.46%, respectively, and the recovery rates of copper and nickel were 10.92% and 72.23%, respectively; the yield of the tailings relative to the original dried electroplating sludge was 110.47%, and the contents of copper and nickel were 0.30% and 0.14%, respectively.
Example 2
The treatment object is electroplating sludge of a certain electroplating plant in Guangdong Fushan, wherein the mass percent of copper and nickel are respectively 5.16% and 3.37%, the electroplating sludge is treated by adopting the following processes, and the copper and the nickel are recovered:
(1) mixing electroplating sludge and a sulfuration roasting additive, pelletizing to obtain green pellets, wherein the sulfuration roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is a mixture of pyrite and sulfur (the mass ratio of the pyrite to the sulfur is 3: 1), the flux is a mixture of quartz and alumina (the mass ratio of the quartz to the alumina is 2: 1), the fluxing agent is a mixture of borax and sodium silicate (the mass ratio of the borax to the sodium silicate is 1: 1), the reducing agent is anthracite, the dosage of the vulcanizing agent is 3 times of the sum of the mole numbers of copper and nickel elements contained in the electroplating sludge, the dosage of the flux is 30% of the dry weight of the electroplating sludge, the dosage of the fluxing agent is 2% of the dry weight of the electroplating sludge, and the dosage of the reducing agent is;
(2) drying the green pellets, vulcanizing and roasting at 800 ℃ for 120min, and naturally cooling to obtain a roasted product;
(3) crushing the roasted product to the granularity of-2 mm (namely the granularity is less than 2mm), and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 60% under the ore grinding concentration of 65% to obtain ore grinding ore pulp;
(4) adding regulators lime and copper sulfate, a collector butyl xanthate and foaming agent II flotation oil into the ore grinding pulp in sequence, wherein the using amount of the regulators is 1700g per ton of electroplating sludge (calculated by dry weight, the same applies below), specifically, the using amount of the lime is 1500g per ton of electroplating sludge, the using amount of the copper sulfate is 200g per ton of electroplating sludge, the using amount of the collector is 400g per ton of electroplating sludge, the using amount of the foaming agent is 150g per ton of electroplating sludge, stirring is performed for 40 minutes after the sequential addition is completed, then, carrying out flotation, wherein the flotation process adopts multiple sections, specifically adopts the processes of 1-time coarse flotation, 1-time scavenging and 2-time fine flotation, separating to obtain copper-nickel mixed concentrate, and flotation tailings are harmless tailings;
(5) finely grinding the copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 90%, then carrying out flotation impurity removal on the obtained copper-nickel bulk concentrate pulp, wherein the impurities obtained by the flotation impurity removal are harmless tailings, adding sodium sulfite and sodium sulfide serving as adjusting agents into the pulp subjected to the flotation impurity removal, wherein the using amount of the adjusting agents is 3000g per ton of electroplating sludge, specifically, 1000g per ton of electroplating sludge is used as the using amount of the sodium sulfite, 2000g per ton of electroplating sludge is used as the using amount of the sodium sulfide, stirring for 20 minutes after the addition is finished, then carrying out flotation, wherein the flotation process adopts multi-section flotation, specifically adopts the processes of 1-time flotation roughing, 2-time flotation scavenging and 3-time flotation concentrating, and separating to obtain a copper concentrate product and a nickel concentrate product.
The yield of the copper concentrate product relative to the original dried electroplating sludge is 16.04%, the grades of copper and nickel are respectively 26.47% and 3.25%, and the recovery rates of copper and nickel are respectively 82.28% and 15.47%; the yield of the nickel concentrate product relative to the original dried electroplating sludge was 18.21%, the grades of copper and nickel were 2.44% and 14.22%, respectively, and the recovery rates of copper and nickel were 8.61% and 76.84%, respectively; the yield of the tailings relative to the original dried electroplating sludge was 107.14%, and the contents of copper and nickel were 0.44% and 0.24%, respectively.
Example 3
The treatment object is electroplating sludge of a certain electroplating plant in Ningbo of Zhejiang, wherein the mass percent of copper and nickel are respectively 2.87% and 3.05%, the electroplating sludge is treated by adopting the following processes, and the copper and the nickel are recovered:
(1) mixing electroplating sludge and a sulfuration roasting additive, pelletizing to obtain green pellets, wherein the sulfuration roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is a mixture of pyrite and sodium sulfide (the mass ratio of the pyrite to the sodium sulfide is 1: 1), the flux is a mixture of quartz and alumina (the mass ratio of the quartz to the alumina is 1: 1), the fluxing agent is a mixture of borax and sodium silicate (the mass ratio of the borax to the sodium silicate is 1: 2), the reducing agent is anthracite, the dosage of the vulcanizing agent is 3 times of the sum of the mole numbers of copper and nickel elements contained in the electroplating sludge, the dosage of the flux is 10% of the dry weight of the electroplating sludge, the dosage of the fluxing agent is 3% of the dry weight of the electroplating sludge, and the dosage of the reducing agent is;
(2) drying the green pellets, vulcanizing and roasting at 1200 ℃ for 60min, and naturally cooling to obtain a roasted product;
(3) crushing the roasted product to the granularity of-2 mm (namely the granularity is less than 2mm), and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 70% under the grinding concentration of 62% to obtain ore grinding ore pulp;
(4) sequentially adding regulator lime, collecting agents butyl xanthate and butylamine black powder and flotation oil II as a foaming agent into ore grinding pulp, wherein the using amount of the regulator is 2000g per ton of electroplating sludge (calculated according to dry weight, the same below), the using amount of the collecting agent is 500g per ton of electroplating sludge, specifically, the using amount of the butyl xanthate is 400g per ton of electroplating sludge, the using amount of the butylamine black powder is 100g per ton of electroplating sludge, the using amount of the foaming agent is 150g per ton of electroplating sludge, stirring for 20 minutes after the sequential addition is finished, then performing flotation, wherein the flotation process adopts multi-stage flotation, specifically adopts the processes of 1-time coarse flotation, 2-time scavenging and 2-time fine flotation, separating to obtain copper-nickel mixed concentrate, and flotation tailings are harmless tailings;
(5) the method comprises the steps of finely grinding copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 92%, then carrying out flotation impurity removal on the obtained copper-nickel bulk concentrate pulp, wherein impurities obtained by the flotation impurity removal are harmless tailings, adding sodium sulfite and sodium sulfide serving as adjusting agents into the pulp subjected to the flotation impurity removal, wherein the using amount of the adjusting agents is 2300g of the adding amount of each ton of electroplating sludge, specifically, the using amount of the sodium sulfite is 800g of the adding amount of each ton of electroplating sludge, the using amount of the sodium sulfide is 1500g of the adding amount of each ton of electroplating sludge, stirring for 20 minutes after the adding is finished, then carrying out flotation, wherein the flotation process adopts multi-section flotation, specifically adopts the processes of 1-time flotation roughing, 1-time flotation scavenging and 4-time flotation concentrating, and separating to obtain a copper concentrate product and a.
The yield of the copper concentrate product relative to the original dried electroplating sludge is 10.13%, the grades of copper and nickel are 23.48% and 3.34% respectively, and the recovery rates of copper and nickel are 82.88% and 11.09% respectively; the yield of the nickel concentrate product relative to the original dried electroplating sludge was 16.51%, the grades of copper and nickel were 1.52% and 14.72%, respectively, and the recovery rates of copper and nickel were 8.74% and 79.68%, respectively; the yield of the tailings relative to the original dried electroplating sludge was 109.41%, and the contents of copper and nickel were 0.22% and 0.26%, respectively.
Example 4
The treatment object is electroplating sludge of a certain electroplating plant in Anhui Pozhou, wherein the mass percent of copper and nickel are respectively 1.14% and 1.06%, the electroplating sludge is treated by adopting the following processes, and the copper and the nickel are recovered:
(1) mixing the electroplating sludge and a sulfuration roasting additive, pelletizing to obtain green pellets, wherein the sulfuration roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is a mixture of pyrite and sodium sulfide (the mass ratio of the pyrite to the sodium sulfide is 1: 1), the flux is aluminum oxide, the fluxing agent is sodium silicate, the reducing agent is anthracite, the dosage of the vulcanizing agent is 2 times of the sum of the mole numbers of copper and nickel contained in the electroplating sludge, the dosage of the flux is 20% of the dry weight of the electroplating sludge, the dosage of the fluxing agent is 3% of the dry weight of the electroplating sludge, and the dosage of the reducing agent is 5% of the dry weight of;
(2) drying the green pellets, vulcanizing and roasting at 900 ℃ for 120min, and naturally cooling to obtain roasted products;
(3) crushing the roasted product to the granularity of-2 mm (namely the granularity is less than 2mm), and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 75% under the grinding concentration of 60% to obtain ore grinding ore pulp;
(4) adding a regulator lime, a copper sulfate, a collector butyl xanthate and a foaming agent II flotation oil into the ore grinding pulp in sequence, wherein the using amount of the regulator is 550g per ton of electroplating sludge (calculated by dry weight, the same below), specifically, the using amount of the lime is 500g per ton of electroplating sludge, the using amount of the copper sulfate is 50g per ton of electroplating sludge, the using amount of the collector is 150g per ton of electroplating sludge, and the using amount of the foaming agent is 50g per ton of electroplating sludge, stirring for 40 minutes after the sequential addition is finished, then carrying out flotation, wherein the flotation process adopts multiple sections, specifically adopts the processes of 1-time coarse flotation, 1-time scavenging and 2-time fine flotation, separating to obtain copper-nickel mixed concentrate, and separating flotation tailings to obtain harmless tailings;
(5) the method comprises the steps of finely grinding copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 95%, then carrying out flotation impurity removal on the obtained copper-nickel bulk concentrate pulp, wherein impurities obtained by the flotation impurity removal are harmless tailings, adding adjusting agents of sodium sulfite and sodium sulfide into the pulp subjected to the flotation impurity removal, wherein the amount of the adjusting agents is 1500g per ton of electroplating sludge, specifically, 500g per ton of electroplating sludge is added with the amount of the sodium sulfite, 1000g per ton of electroplating sludge is added with the amount of the sodium sulfide, stirring for 20 minutes after the addition is finished, then carrying out flotation, wherein the flotation process adopts multi-section flotation, specifically adopts the processes of 1 flotation roughing, 1 flotation scavenging and 3 flotation concentrating, and separating to obtain a copper concentrate product and a nickel concentrate product.
The yield of the copper concentrate product relative to the original dried electroplating sludge is 4.85 percent, the grades of copper and nickel are 16.57 percent and 1.94 percent respectively, and the recovery rates of copper and nickel are 70.50 percent and 8.88 percent respectively; the yield of the nickel concentrate product relative to the original dried electroplating sludge was 9.12%, the grades of copper and nickel were 1.72% and 8.17%, respectively, and the recovery rates of copper and nickel were 13.76% and 70.29%, respectively; the yield of the tailings relative to the original dried electroplating sludge was 105.63%, and the contents of copper and nickel were 0.17% and 0.21%, respectively.
Example 5
The treatment object is the electroplating sludge of a certain electroplating plant in Guangdong Heizhou, wherein the mass percent of copper and nickel are respectively 2.14% and 2.37%, the electroplating sludge is treated by adopting the following processes, and the copper and the nickel are recovered:
(1) mixing the electroplating sludge and a vulcanizing roasting additive, pelletizing to obtain green pellets, wherein the vulcanizing roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is a mixture of pyrite, sulfur and sodium sulfide (the mass ratio of the pyrite, the sodium sulfide and the sulfur is 2: 1), the flux is quartz, the fluxing agent is sodium silicate, the reducing agent is anthracite, the dosage of the vulcanizing agent is 2 times of the sum of the mole numbers of copper and nickel contained in the electroplating sludge, the dosage of the flux is 15% of the dry weight of the electroplating sludge, the dosage of the fluxing agent is 1% of the dry weight of the electroplating sludge, and the dosage of the reducing agent is 8% of the dry weight of the;
(2) drying the green pellets, vulcanizing and roasting at 1200 ℃ for 60min, and naturally cooling to obtain a roasted product;
(3) crushing the roasted product to the granularity of-2 mm (namely the granularity is less than 2mm), and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 65% under the grinding concentration of 62.5% to obtain ore grinding ore pulp;
(4) sequentially adding 220g of regulator lime, 220g of copper sulfate, 120g of collector butylamine black powder and 100g of foaming agent into each ton of electroplating sludge (calculated by dry weight, the same below), specifically adding 120g of lime into each ton of electroplating sludge, adding 100g of copper sulfate into each ton of electroplating sludge, adding 300g of collector into each ton of electroplating sludge, adding 100g of foaming agent into each ton of electroplating sludge, stirring for 40 minutes after the sequential addition is finished, then performing flotation, wherein the flotation process adopts multiple sections, specifically adopts the processes of 1-time coarse flotation, 1-time scavenging and 3-time fine flotation, separating to obtain copper-nickel mixed concentrate, and the flotation tailings are harmless tailings;
(5) finely grinding the copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 90%, then carrying out flotation impurity removal on the obtained copper-nickel bulk concentrate pulp, wherein the impurities obtained by the flotation impurity removal are harmless tailings, adding sodium sulfite and sodium sulfide serving as adjusting agents into the pulp subjected to the flotation impurity removal, wherein the using amount of the adjusting agents is 2300g of the adjusting agents added to each ton of electroplating sludge, specifically, the using amount of the sodium sulfite is 800g of the adjusting agents added to each ton of electroplating sludge, the using amount of the sodium sulfide is 1500g of the adjusting agents added to each ton of electroplating sludge, stirring for 20 minutes after the addition is finished, then carrying out flotation, wherein the flotation process adopts multi-section flotation, and specifically adopts the processes of 1 flotation roughing, 1 flotation scavenging and 3 flotation concentrating, and separating to obtain a copper concentrate product and a nickel concentrate product.
The yield of the copper concentrate product relative to the original dried electroplating sludge was 7.19%, the copper and nickel grades were 22.89% and 3.34%, respectively, and the copper and nickel recovery rates were 76.91% and 10.13%, respectively; the yield of the nickel concentrate product relative to the original dried electroplating sludge was 14.10%, the grades of copper and nickel were 2.34% and 12.11%, respectively, and the recovery rates of copper and nickel were 15.42% and 72.05%, respectively; the yield of the tailings relative to the original dried electroplating sludge was 98.46%, and the contents of copper and nickel were 0.17% and 0.43%, respectively.
The harmless tailings obtained in the above examples 1 to 5 were tested according to the tailings toxicity leaching test standard executed in hazardous waste identification standard (GB5085.3-2007), and the results are shown in the following table, and it can be seen that the leaching toxicity of the tailings obtained in the above examples is lower than the standard requirement.
Toxicity leaching results of tailings of each example (unit: mg/L)
The embodiment shows that the method provided by the invention can carry out harmless treatment on the electroplating sludge and recover the copper and nickel valuable elements in the electroplating sludge, the copper grade of the finally treated copper concentrate is more than 16 percent, and the copper recovery rate is more than 60 percent; the nickel grade of the nickel concentrate is more than 8 percent, and the nickel recovery rate is more than 60 percent; the content of copper and nickel in the tailings is lower than 0.5%, and the leaching toxicity is lower than the standard value for identifying the leaching toxicity in the identification Standard for hazardous waste (GB 5085.3-2007).
Claims (9)
1. A method for comprehensively recovering copper and nickel in electroplating sludge is characterized by comprising the following steps:
s1: mixing the electroplating sludge and a vulcanizing roasting additive, pelletizing to obtain green pellets, wherein the grain size range of the green pellets is 8-10 mm, the vulcanizing roasting additive consists of a vulcanizing agent, a flux, a fluxing agent and a reducing agent, the vulcanizing agent is any one or a combination of several of pyrite, sodium sulfide and sulfur, the consumption of the vulcanizing agent is 2-3 times of the sum of the mole numbers of copper and nickel elements contained in the electroplating sludge, the flux is quartz and/or alumina, the fluxing agent is borax and/or sodium silicate, and the reducing agent is anthracite;
s2: drying the green pellets, then placing the dried green pellets at the temperature of 800-1200 ℃ for sulfurizing roasting for 60-120 min, and then naturally cooling to obtain roasted products;
s3: crushing the roasted product to the granularity of-2 mm, and then grinding the crushed roasted product to the granularity of-0.045 mm accounting for 60-80% under the ore grinding concentration of 60-65% to obtain ore grinding ore pulp;
s4: carrying out flotation on the ore grinding pulp, separating to obtain copper-nickel bulk concentrate, wherein flotation tailings are harmless tailings, and a flotation agent added into the ore grinding pulp during flotation is composed of a regulator I, a collecting agent and a foaming agent, wherein the regulator I is lime and/or copper sulfate, the collecting agent is butyl xanthate and/or butylamine black powder, and the foaming agent is No. two flotation oil;
s5: and grinding the obtained copper-nickel bulk concentrate until the granularity is-0.037 mm and accounts for 90-95% to obtain copper-nickel bulk concentrate pulp, adding a regulator II into the copper-nickel bulk concentrate pulp to perform copper-nickel separation flotation to respectively obtain a copper concentrate product and a nickel concentrate product, wherein the regulator II is sodium sulfite and/or sodium sulfide.
2. The method for comprehensively recovering copper and nickel in electroplating sludge according to claim 1, characterized in that the obtained copper-nickel bulk concentrate pulp is subjected to flotation for impurity removal, and then a regulator II is added for copper-nickel separation flotation, and impurities obtained by flotation for impurity removal are harmless tailings.
3. The method for comprehensively recovering copper and nickel in electroplating sludge according to claim 1, wherein in step S1, the dosage of the flux is 10-30% of the dry weight of the electroplating sludge.
4. The method for comprehensively recovering copper and nickel from electroplating sludge according to claim 3, wherein in step S1, the amount of the fluxing agent is 1-3% of the dry weight of the electroplating sludge.
5. The method for comprehensively recovering copper and nickel in electroplating sludge according to claim 4, wherein in step S1, the amount of the reducing agent is 5-20% of the dry weight of the electroplating sludge.
6. The method for comprehensively recovering copper and nickel from electroplating sludge according to claim 5, wherein in step S4, the amount of the modifier I is 200-2000 g per ton of electroplating sludge, the amount of the collector is 150-500 g per ton of electroplating sludge, and the amount of the foaming agent is 50-150 g per ton of electroplating sludge.
7. The method for comprehensively recovering copper and nickel in electroplating sludge according to claim 6, wherein in step S5, the amount of the modifier II is 1500-3000 g per ton of electroplating sludge.
8. The method for comprehensively recovering copper and nickel in electroplating sludge according to claim 7, wherein in step S4, the ore grinding pulp flotation process adopts multi-stage flotation, which comprises 1-2 times of flotation roughing, 1-2 times of flotation scavenging and 2-3 times of flotation concentrating.
9. The method for comprehensively recovering copper and nickel in electroplating sludge according to claim 8, wherein in step S5, the copper and nickel separation flotation process adopts multi-stage flotation, which comprises 1-2 times of flotation roughing, 1-2 times of flotation scavenging and 3-4 times of flotation concentrating.
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