CN111500865A - Method for recycling heavy metals in electroplating sludge - Google Patents
Method for recycling heavy metals in electroplating sludge Download PDFInfo
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Abstract
The invention relates to the technical field of metal recovery in electroplating sludge, in particular to a method for recycling heavy metal in electroplating sludge, which comprises the steps of pretreatment, crushing treatment, thiobacillus thallus culture, material mixing and electrodeposition treatment to recover copper-nickel metal; through the domestication step, thiobacillus capable of resisting high-concentration heavy metal is obtained through screening and domestication, the thiobacillus and electroplating sludge are stirred and mixed together, bioleaching is carried out, a certain period of time is passed, electrodeposition is carried out on a copper-containing leaching solution after impurity removal, elemental copper is recovered, and metal nickel is recovered by electrodeposition after impurity removal of a nickel-containing leaching solution; low processing cost and safe operation environment.
Description
Technical Field
The invention relates to the technical field of metal recovery in electroplating sludge, in particular to a method for recycling heavy metals in electroplating sludge.
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. The electroplating sludge with a large amount of heavy metals is generated after the electroplating wastewater is chemically treated, the heavy metals with the largest content of the electroplating sludge are generally five types of Cu, Ni, Zn, Cr and Fe, and the electroplating sludge has high heavy metal content, so the electroplating sludge is listed as dangerous waste by the name of the state; but meanwhile, the electroplating sludge is rich in a large amount of metal resources, which is equivalent to low-grade ores, for example, the content of copper and nickel in the electroplating sludge is relatively high, and when the content of copper in the electroplating sludge is more than 5 wt%, the electroplating sludge is called copper-containing electroplating sludge and has recovery value;
at present, the first step of recovering heavy metals from electroplating sludge is a leaching process, and a method for chemically leaching heavy metals from electroplating sludge by using inorganic acid or organic complexing agents such as HNO3, HCl, EDTA and the like can leach heavy metals in a short time, but has the disadvantages of high acid consumption, high treatment cost, high pollution of acid mist generated in the operation process and poor operation environment of workers.
Disclosure of Invention
The invention aims to solve the defects of high treatment cost and poor operating environment of workers in the prior art, and provides a method for recycling heavy metals in electroplating sludge.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recycling heavy metals in electroplating sludge is designed, and comprises the following steps;
step 1: pretreating, namely mixing the electroplating sludge with a vulcanization roasting additive, pelletizing by pelletizing equipment to obtain green pellets, wherein the particle size range of the green pellets is 8-12 mm, drying the green pellets by drying equipment, then placing the dried green pellets at the temperature of 800-1200 ℃ for vulcanization roasting for 1-3 hours, and then naturally cooling to obtain a roasted product;
step 2: crushing, namely putting the roasted product into crushing equipment to be crushed until the granularity is 1-2 mm, then screening through a 150-220-mesh sieve, and collecting screened powder for later use;
and step 3: culturing Thiobacillus thallus, culturing Thiobacillus ferrooxidans in a 9K culture medium, and controlling the pH value of an enrichment culture system to be 1.1-2.3; carrying out centrifugal separation on the mixed material with the pH value of 1.1-2.3, wherein the precipitate at the lower layer of a centrifugal tube is the thiobacillus ferrooxidans thallus, and collecting the thallus;
and 4, step 4: mixing materials, namely adding the prepared electroplating sludge in the step 1 and powder fired by the vulcanizing roasting additive into a culture solution to obtain a reaction mixed material, then reacting the reaction mixed material at the temperature of 25-35 ℃ and the rotating speed of a shaking table of 120-200r/min, and testing the pH value of the mixed material every day; for copper-containing electroplating sludge treated by thiobacillus ferrooxidans, reducing the pH value of the mixed material to 1.4-1.8, stopping reaction, carrying out centrifugal separation on the reacted mixed material, and extracting and collecting the upper nickel-containing leachate or copper-containing nickel leachate;
and 5: electrodeposition treatment, the concrete implementation steps are as follows;
s1: removing impurities from the leachate obtained in the step 4, removing Fe2+ and Ca2+ to obtain an impurity-removed leachate;
s2: transferring the copper-containing leachate after impurity removal in the step S1 into an electrolytic bath for electrodeposition, and performing electrodeposition by using a titanium plate as an anode and a copper plate as a cathode to recover elemental copper so as to complete resource recovery of electroplating sludge;
s3: for the nickel-containing leachate after impurity removal in the step S1, a titanium plate is used as an anode, and a nickel plate is used as a cathode for electrodeposition recovery to obtain elemental nickel, so that the resource recovery of electroplating sludge is completed;
preferably, in step 2, the specific implementation steps for culturing Thiobacillus ferrooxidans are as follows:
A. culturing acidified sludge, namely taking sludge in an aeration tank of a sewage treatment plant, filtering to remove hair and large particles in the sludge, adjusting solid content, then taking the sludge from the sludge, putting the sludge into a conical flask into which a sterilized 9K culture medium is added, performing acclimation culture for 7 to 12 days at the temperature of 25 to 30 ℃ and the rotating speed of a shaking table of 120 to 200r/min, thus obtaining sludge after first-generation acclimation, sucking the sludge after first-generation acclimation, inoculating the sludge into a fresh sterilized 9K culture medium, culturing for 7 to 12 days according to the conditions, thus obtaining sludge after second-generation acclimation, repeating the steps until the pH of the sludge after acclimation is reduced to below 2.0, thus obtaining the acidified sludge, wherein in the acclimation process, the concentration of FeSO 4.7H2O in the used culture medium is increased by 1 g/L compared with that of the previous generation each time of sludge addition;
B. b, acclimatizing and culturing sludge resistant to heavy metal, namely adding the acidified sludge obtained in the step A into a 9K culture medium, and adjusting the initial pH value of the material to be 4.0, wherein the composition of the 9K culture medium is the same as that of a culture medium used for an acclimatization end point of the acidified sludge; gradually adding copper-containing electroplating sludge powder into the mixed material prepared freshly each time until the pH value is reduced to be below 3.0, then carrying out centrifugal separation on the reaction materials, and collecting lower-layer sediment which contains iron protoxide thiobacillus thalli resistant to electroplating sludge with corresponding concentration;
C. and D, carrying out enrichment culture on the precipitate of the thiobacillus ferrooxidans thallus containing the electroplating sludge with the highest concentration resistance centrifugally collected in the step B in a 9K culture medium for 9-10 days, and then separating, purifying and enriching to finish the preparation of the thiobacillus ferrooxidans thallus.
Preferably, in the step B, after the copper-containing electroplating sludge powder is added, if the pH value is reduced to be below 3.0 within 7 days to 10 days, the reaction material is centrifugally separated, and the lower-layer sediment is collected, wherein the lower-layer sediment contains the Thiobacillus ferrooxidans thallus which can resist electroplating sludge with corresponding concentration; when the pH value is increased to 7.0 or more within 7 to 10 days, the cells of Thiobacillus ferrooxidans which can withstand the previous concentration of the plating sludge are those which can withstand the highest concentration of the plating sludge.
Preferably, in step 5, for the copper-nickel-containing leachate after the impurity removal in S1, firstly, extracting nickel in the leachate with a nickel extractant to obtain a nickel extraction solution and a copper-containing solution, respectively, and for the nickel extraction solution, after back-extracting nickel in the nickel extraction solution with sulfuric acid, transferring the nickel extraction solution into an electrolytic bath, using a titanium plate as an anode, and using a nickel plate as a cathode for electrodeposition and recycling to obtain elemental nickel; and transferring the copper-containing solution into an electrolytic bath, and performing electrodeposition recovery by using a titanium plate as an anode and a copper plate as a cathode to obtain elemental copper so as to finish resource recovery of electroplating sludge.
Preferably, in step 5, the leachate is purified by heating the leachate to 90 ℃, and adding excessive sodium chlorate to completely oxidize Fe2+ to form Fe3 +; adding excessive sodium hydroxide into the leachate to combine Fe3+ with hydroxide particles to generate ferric hydroxide precipitate; and (3) filtering the ferric hydroxide precipitate, adding excessive sodium fluoride into the filtrate, generating calcium fluoride precipitate in the filtrate, and filtering again to remove calcium fluoride to obtain the filtrate, namely the copper-containing leachate after impurity removal.
The method for recycling the heavy metals in the electroplating sludge has the beneficial effects that: the method comprises the following steps of adapting the used thiobacillus to the environment containing high-concentration heavy metals, obtaining thiobacillus capable of resisting the high-concentration heavy metals through screening and domestication through a domestication step, stirring and mixing the thiobacillus and electroplating sludge together, carrying out bioleaching, carrying out electrodeposition after impurity removal on a copper-containing leachate for a certain period of time, recovering to obtain elemental copper, and recovering to obtain metallic nickel through electrodeposition after impurity removal of a nickel-containing leachate; low processing cost and safe operation environment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1:
a method for recycling heavy metals in electroplating sludge comprises the following steps;
step 1: pretreating, namely mixing the electroplating sludge with a vulcanization roasting additive, pelletizing by pelletizing equipment to obtain green pellets, wherein the particle size range of the green pellets is 8-12 mm, drying the green pellets by drying equipment, then placing the dried green pellets at the temperature of 800-1200 ℃ for vulcanization roasting for 1-3 hours, and then naturally cooling to obtain a roasted product;
step 2: crushing, namely putting the roasted product into crushing equipment to be crushed until the granularity is 1-2 mm, then screening through a 150-220-mesh sieve, and collecting screened powder for later use;
and step 3: culturing Thiobacillus thallus, culturing Thiobacillus ferrooxidans in a 9K culture medium, and controlling the pH value of an enrichment culture system to be 1.1-2.3; carrying out centrifugal separation on the mixed material with the pH value of 1.1-2.3, wherein the precipitate at the lower layer of a centrifugal tube is the thiobacillus ferrooxidans thallus, and collecting the thallus;
and 4, step 4: mixing materials, namely adding the prepared electroplating sludge in the step 1 and powder fired by the vulcanizing roasting additive into a culture solution to obtain a reaction mixed material, then reacting the reaction mixed material at the temperature of 25-35 ℃ and the rotating speed of a shaking table of 120-200r/min, and testing the pH value of the mixed material every day; for copper-containing electroplating sludge treated by thiobacillus ferrooxidans, reducing the pH value of the mixed material to 1.4-1.8, stopping reaction, carrying out centrifugal separation on the reacted mixed material, and extracting and collecting the upper nickel-containing leachate or copper-containing nickel leachate;
and 5: electrodeposition treatment, the concrete implementation steps are as follows;
s1: removing impurities from the leachate obtained in the step 4, removing Fe2+ and Ca2+ to obtain an impurity-removed leachate;
s2: transferring the copper-containing leachate after impurity removal in the step S1 into an electrolytic bath for electrodeposition, and performing electrodeposition by using a titanium plate as an anode and a copper plate as a cathode to recover elemental copper so as to complete resource recovery of electroplating sludge;
s3: for the nickel-containing leachate after impurity removal in the step S1, a titanium plate is used as an anode, and a nickel plate is used as a cathode for electrodeposition recovery to obtain elemental nickel, so that the resource recovery of electroplating sludge is completed;
in step 2, the specific implementation steps for culturing Thiobacillus ferrooxidans are as follows:
A. culturing acidified sludge, namely taking sludge in an aeration tank of a sewage treatment plant, filtering to remove hair and large particles in the sludge, adjusting solid content, then taking the sludge from the sludge, putting the sludge into a conical flask into which a sterilized 9K culture medium is added, performing acclimation culture for 7 to 12 days at the temperature of 25 to 30 ℃ and the rotating speed of a shaking table of 120 to 200r/min, thus obtaining sludge after first-generation acclimation, sucking the sludge after first-generation acclimation, inoculating the sludge into a fresh sterilized 9K culture medium, culturing for 7 to 12 days according to the conditions, thus obtaining sludge after second-generation acclimation, repeating the steps until the pH of the sludge after acclimation is reduced to below 2.0, thus obtaining the acidified sludge, wherein in the acclimation process, the concentration of FeSO 4.7H2O in the used culture medium is increased by 1 g/L compared with that of the previous generation each time of sludge addition;
B. b, acclimatizing and culturing sludge resistant to heavy metal, namely adding the acidified sludge obtained in the step A into a 9K culture medium, and adjusting the initial pH value of the material to be 4.0, wherein the composition of the 9K culture medium is the same as that of a culture medium used for an acclimatization end point of the acidified sludge; gradually adding copper-containing electroplating sludge powder into the mixed material prepared freshly each time until the pH value is reduced to be below 3.0, then carrying out centrifugal separation on the reaction materials, and collecting lower-layer sediment which contains iron protoxide thiobacillus thalli resistant to electroplating sludge with corresponding concentration;
C. and D, carrying out enrichment culture on the precipitate of the thiobacillus ferrooxidans thallus containing the electroplating sludge with the highest concentration resistance centrifugally collected in the step B in a 9K culture medium for 9-10 days, and then separating, purifying and enriching to finish the preparation of the thiobacillus ferrooxidans thallus.
In the step B, after copper-containing electroplating sludge powder is added, if the pH value is reduced to be below 3.0 within 7-10 days, centrifugally separating the reaction material, and collecting lower-layer sediment which contains ferrous oxide thiobacillus thallus resisting electroplating sludge with corresponding concentration; when the pH value is increased to 7.0 or more within 7 to 10 days, the cells of Thiobacillus ferrooxidans which can withstand the previous concentration of the plating sludge are those which can withstand the highest concentration of the plating sludge.
The method comprises the steps of adapting the used thiobacillus to the environment containing high-concentration heavy metals, obtaining thiobacillus capable of resisting the high-concentration heavy metals through screening and domestication through a domestication step, stirring and mixing the thiobacillus and electroplating sludge together, carrying out bioleaching, carrying out electro-deposition after impurity removal on a copper-containing leachate for a certain period of time, recovering to obtain elemental copper, and recovering to obtain metallic nickel through electro-deposition after impurity removal of a nickel-containing leachate; low processing cost and safe operation environment.
Example 2:
as another preferred embodiment of the present invention, the difference from embodiment 1 is that, in step 5, for the copper-nickel-containing leachate after the impurity removal of S1, firstly, nickel in the leachate is extracted by using a nickel extractant, so as to obtain a nickel extraction solution and a copper-containing solution, respectively, and for the nickel extraction solution, after nickel in the nickel extraction solution is back-extracted by using sulfuric acid, the nickel extraction solution is transferred into an electrolytic bath, and a titanium plate is used as an anode, and a nickel plate is used as a cathode for electrodeposition recovery, so as to obtain elemental nickel; transferring the copper-containing solution into an electrolytic bath, and performing electrodeposition recovery on a titanium plate as an anode and a copper plate as a cathode to obtain elemental copper so as to complete resource recovery of electroplating sludge;
in the step 5, the process of removing impurities from the leachate is that the leachate is heated to 90 ℃, and excessive sodium chlorate is added to completely oxidize Fe2+ to generate Fe3 +; adding excessive sodium hydroxide into the leachate to combine Fe3+ with hydroxide particles to generate ferric hydroxide precipitate; and (3) filtering the ferric hydroxide precipitate, adding excessive sodium fluoride into the filtrate, generating calcium fluoride precipitate in the filtrate, and filtering again to remove calcium fluoride to obtain the filtrate, namely the copper-containing leachate after impurity removal.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A method for recycling heavy metals in electroplating sludge is characterized by comprising the following steps;
step 1: pretreating, namely mixing the electroplating sludge with a vulcanization roasting additive, pelletizing by pelletizing equipment to obtain green pellets, wherein the particle size range of the green pellets is 8-12 mm, drying the green pellets by drying equipment, then placing the dried green pellets at the temperature of 800-1200 ℃ for vulcanization roasting for 1-3 hours, and then naturally cooling to obtain a roasted product;
step 2: crushing, namely putting the roasted product into crushing equipment to be crushed until the granularity is 1-2 mm, then screening through a 150-220-mesh sieve, and collecting screened powder for later use;
and step 3: culturing Thiobacillus thallus, culturing Thiobacillus ferrooxidans in a 9K culture medium, and controlling the pH value of an enrichment culture system to be 1.1-2.3; carrying out centrifugal separation on the mixed material with the pH value of 1.1-2.3, wherein the precipitate at the lower layer of a centrifugal tube is the thiobacillus ferrooxidans thallus, and collecting the thallus;
and 4, step 4: mixing materials, namely adding the prepared electroplating sludge in the step 1 and powder fired by the vulcanizing roasting additive into a culture solution to obtain a reaction mixed material, then reacting the reaction mixed material at the temperature of 25-35 ℃ and the rotating speed of a shaking table of 120-200r/min, and testing the pH value of the mixed material every day; for copper-containing electroplating sludge treated by thiobacillus ferrooxidans, reducing the pH value of the mixed material to 1.4-1.8, stopping reaction, carrying out centrifugal separation on the reacted mixed material, and extracting and collecting the upper nickel-containing leachate or copper-containing nickel leachate;
and 5: electrodeposition treatment, the concrete implementation steps are as follows;
s1: removing impurities from the leachate obtained in the step 4, removing Fe2+ and Ca2+ to obtain an impurity-removed leachate;
s2: transferring the copper-containing leachate after impurity removal in the step S1 into an electrolytic bath for electrodeposition, and performing electrodeposition by using a titanium plate as an anode and a copper plate as a cathode to recover elemental copper so as to complete resource recovery of electroplating sludge;
s3: and (4) for the nickel-containing leachate after impurity removal in the step S1, using a titanium plate as an anode and a nickel plate as a cathode for electrodeposition recovery to obtain simple substance nickel, thereby completing resource recovery of electroplating sludge.
2. The method for resource recovery of heavy metals in electroplating sludge according to claim 1, wherein the step 2 of culturing Thiobacillus ferrooxidans comprises the following specific implementation steps:
A. culturing acidified sludge, namely taking sludge in an aeration tank of a sewage treatment plant, filtering to remove hair and large particles in the sludge, adjusting solid content, then taking the sludge from the sludge, putting the sludge into a conical flask into which a sterilized 9K culture medium is added, performing acclimation culture for 7 to 12 days at the temperature of 25 to 30 ℃ and the rotating speed of a shaking table of 120 to 200r/min, thus obtaining sludge after first-generation acclimation, sucking the sludge after first-generation acclimation, inoculating the sludge into a fresh sterilized 9K culture medium, culturing for 7 to 12 days according to the conditions, thus obtaining sludge after second-generation acclimation, repeating the steps until the pH of the sludge after acclimation is reduced to below 2.0, thus obtaining the acidified sludge, wherein in the acclimation process, the concentration of FeSO 4.7H2O in the used culture medium is increased by 1 g/L compared with that of the previous generation each time of sludge addition;
B. b, acclimatizing and culturing sludge resistant to heavy metal, namely adding the acidified sludge obtained in the step A into a 9K culture medium, and adjusting the initial pH value of the material to be 4.0, wherein the composition of the 9K culture medium is the same as that of a culture medium used for an acclimatization end point of the acidified sludge; gradually adding copper-containing electroplating sludge powder into the mixed material prepared freshly each time until the pH value is reduced to be below 3.0, then carrying out centrifugal separation on the reaction materials, and collecting lower-layer sediment which contains iron protoxide thiobacillus thalli resistant to electroplating sludge with corresponding concentration;
C. and D, carrying out enrichment culture on the precipitate of the thiobacillus ferrooxidans thallus containing the electroplating sludge with the highest concentration resistance centrifugally collected in the step B in a 9K culture medium for 9-10 days, and then separating, purifying and enriching to finish the preparation of the thiobacillus ferrooxidans thallus.
3. The method for recycling heavy metals in electroplating sludge according to claim 2, wherein in the step B, after the copper-containing electroplating sludge powder is added, if the pH value is reduced to below 3.0 within 7 days to 10 days, the reaction material is centrifugally separated, and the lower-layer precipitate is collected, wherein the lower-layer precipitate contains the Thiobacillus ferrooxidans thallus which can resist the electroplating sludge with corresponding concentration; when the pH value is increased to 7.0 or more within 7 to 10 days, the cells of Thiobacillus ferrooxidans which can withstand the previous concentration of the plating sludge are those which can withstand the highest concentration of the plating sludge.
4. The method according to claim 1, wherein in step 5, for the leachate containing copper and nickel after the impurity removal in S1, firstly, nickel in the leachate is extracted by a nickel extractant to obtain a nickel extraction solution and a copper-containing solution, respectively, and for the nickel extraction solution, after nickel in the nickel extraction solution is back-extracted by sulfuric acid, the nickel extraction solution is transferred into an electrolytic bath, a titanium plate is used as an anode, and a nickel plate is used as a cathode for electrodeposition recovery to obtain elemental nickel; and transferring the copper-containing solution into an electrolytic bath, and performing electrodeposition recovery by using a titanium plate as an anode and a copper plate as a cathode to obtain elemental copper so as to finish resource recovery of electroplating sludge.
5. The method as claimed in claim 1, wherein in the step 5, the leachate is purified by heating the leachate to 90 ℃, and excess sodium chlorate is added to completely oxidize Fe2+ into Fe3 +; adding excessive sodium hydroxide into the leachate to combine Fe3+ with hydroxide particles to generate ferric hydroxide precipitate; and (3) filtering the ferric hydroxide precipitate, adding excessive sodium fluoride into the filtrate, generating calcium fluoride precipitate in the filtrate, and filtering again to remove calcium fluoride to obtain the filtrate, namely the copper-containing leachate after impurity removal.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112941320A (en) * | 2021-01-22 | 2021-06-11 | 西南林业大学 | Method for recovering heavy metals in electroplating sludge through bioleaching and hydrothermal synthesis |
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