CN112853102A - Impurity removal method for recycling nonferrous metals from electroplating sludge by wet method - Google Patents
Impurity removal method for recycling nonferrous metals from electroplating sludge by wet method Download PDFInfo
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- CN112853102A CN112853102A CN202011629293.1A CN202011629293A CN112853102A CN 112853102 A CN112853102 A CN 112853102A CN 202011629293 A CN202011629293 A CN 202011629293A CN 112853102 A CN112853102 A CN 112853102A
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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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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 provides an impurity removing method for recycling nonferrous metals by electroplating sludge wet method, which comprises the following steps: 1) preparing materials: taking a feed liquid obtained after copper extraction or copper precipitation, and batching to obtain an impurity-removed feed liquid, wherein the molar concentration sum of chromium, iron and aluminum in the impurity-removed feed liquid maintains a certain proportion to the molar concentration of phosphorus; 2) primary impurity removal: adding an oxidant into the impurity-removed feed liquid, heating after reaction, adding alkali, adjusting the pH, and filtering after reaction; 3) secondary impurity removal: adding alkali into the filtrate obtained by filtering in the step 2), adjusting the pH value, reacting and filtering. The impurity removing method for recycling the nonferrous metals by the electroplating sludge wet method has the advantages of simple process, low cost and easy production and application, so that the belt loss of the nonferrous metals is reduced, the alkali utilization rate is improved and no waste slag is generated in the electroplating sludge wet method recycling.
Description
Technical Field
The invention relates to the field of electroplating sludge resource utilization, in particular to an impurity removal method for recovering nonferrous metals by electroplating sludge wet resource.
Background
The electroplating wastewater generally contains pollutants such as nickel, copper, zinc, chromium, cadmium, gold, silver, acid, alkali, cyanogen, COD and the like, and the electroplating plants are classified and then discharged to a sewage treatment plant from an electroplating park or a large-scale electroplating plant with sewage treatment facilities for treatment, wherein the Cr is generally treated firstly6+Reduction to Cr3+Then removing heavy metals through physical and chemical precipitation to obtain electroplating sludge, then carrying out biochemical treatment on COD, cyanogen and the like, and reusing or discharging the electroplating sludge as reclaimed water after the treatment reaches the standard. The electroplating sludge is generally divided into electroplating quality-divided sludge and electroplating mixed sludge according to different components. Wherein the sludge containing noble metals such as gold and silver has high utilization value but small amount. Cadmium electroplating is rarely used due to environmental protection problems. At present, the electroplating sludge is mainly mixed sludge and classified sludge such as chromium sludge, nickel sludge, copper sludge and the like. The electroplating sludge generally contains heavy metals such as nickel, copper, zinc, chromium and the like, and iron, aluminum, calcium and the like which are added in the physical and chemical processes are different in content, but it is noted that chromium and iron in the electroplating sludge exist in a trivalent form because chromium needs to be reduced for detoxification and ferric oxide needs to be flocculated. Because phosphorus-containing additives, degreasing agents and the like are mostly used in the electroplating process, pyrophosphate is used for copper plating, so that electroplating wastewater contains a certain amount of phosphorus. In the process of treating the electroplating wastewater, almost all phosphorus enters the electroplating sludge in the form of metal phosphate, and the phosphorus with a certain amount is beneficial to the physical and chemical processes, but the electroplating sludge can contain phosphorus with different degrees. Especially, the phosphorus content in the electroplating copper sludge and the electroplating mixed sludge is higher.
Most of the existing electroplating sludge treatment methods are synergistic treatment of a rotary kiln, but the energy consumption is high, and valuable elements such as nickel, chromium, copper, zinc, phosphorus and the like in the electroplating sludge cannot be recovered, even two valuable elements are generatedSecondary pollution. And (3) part of electroplating sludge enters a wet recovery process: leaching → copper extraction or copper deposition → impurity removal → P204 zinc extraction or zinc deposition → P507 nickel extraction or nickel deposition. In the impurity removal process, the impurity removal feed liquid mainly contains Cr3+、Fe3+、Al3+、Ni2+、Zn2+. The impurity removing method mainly comprises a neutralization precipitation method, a goethite method or an ihleite method, a phosphate separation ferrochrome method and the like. The neutralization precipitation method uses alkali to adjust the pH value of the feed liquid to be nearly neutral, so that iron, aluminum and chromium are removed by hydroxide precipitation, meanwhile, part of non-ferrous metal precipitates such as zinc, nickel and the like are included, and then non-ferrous metals in the impurity-removed slag are separated by multi-stage dilute acid washing. The method forms colloid with strong adsorptivity such as ferric hydroxide, aluminum hydroxide and the like, so that the filter pressing is difficult, impurity-removed slag contains more nonferrous metals, the multi-stage dilute acid washing generally cannot achieve the ideal effect, acid and alkali can be circularly consumed, and the utilization rate of the alkali is low. Particularly, when the feed liquid with high phosphorus content is treated, a large amount of phosphate precipitates can be formed when ph is close to neutral by nonferrous metals such as zinc, nickel and the like, so that a large part of nonferrous metals enter impurity removal slag, and the significance of impurity removal is lost. The goethite method, the hematite method or the jarosite method mainly aim at removing impurities from high-iron feed liquid, iron is crystallized and precipitated in the form of goethite, hematite or jarosite by controlling reaction conditions and is removed, and chromium, aluminum and the like also enter iron slag along with the crystallization and precipitation. The band loss of the nonferrous metal in the method is lower than that of a neutralization precipitation method, but the condition is strictly controlled, the operation is difficult, a large amount of ferric hydroxide colloid can be formed by carelessness, the filtration is difficult, the band loss of the nonferrous metal is high, and the generated iron slag needs to be treated as hazardous waste. When the feed liquid containing no phosphorus or low phosphorus content is treated, the impurity removal effect is still good, but when the feed liquid containing high phosphorus content is treated, because of the existence of a large amount of phosphorus, iron crystals of goethite, hematite or jarosite cannot be formed in the feed liquid, so that the impurity removal process cannot be carried out. The phosphate selective ferrochrome separating process includes reducing iron into ferrous iron ion, adding soluble phosphate to eliminate chromium, oxidizing ferrous iron into ferric iron, and eliminating iron by neutralization precipitation, goethite process, hematite process or jarosite process. The method can separate chromium and iron, but the reducing agent, the oxidizing agent and the soluble componentThe consumption of auxiliary materials such as phosphate and the like is large, the cost is high, and after the chromium is precipitated by the phosphate, the problems of the belt loss of nonferrous metals and the generation of dangerous waste residues in the process of iron and aluminum precipitation still need to be solved. At present, the impurity removal process in the wet recovery process of the electroplating sludge inevitably generates dangerous wastes with low recycling value, such as iron removal slag, aluminum removal slag and the like, and the nonferrous metal strip loss is high, especially when the electroplating sludge with high phosphorus content is treated, the process is more serious.
Disclosure of Invention
Aiming at the problems of the prior art, the invention provides the impurity removing method for recycling the nonferrous metals by the electroplating sludge wet method, which has the advantages of simple operation, low cost, low damage of the nonferrous metal strips, high alkali utilization rate and no waste residue.
The embodiment of the invention provides an impurity removing method for recycling nonferrous metals from electroplating sludge by a wet method, which comprises the following steps: 1) preparing materials: taking a feed liquid obtained after copper extraction or copper precipitation, and batching to obtain an impurity-removed feed liquid, wherein the molar concentration sum of chromium, iron and aluminum in the impurity-removed feed liquid maintains a certain proportion to the molar concentration of phosphorus; 2) primary impurity removal: adding an oxidant into the impurity-removed feed liquid, heating after reaction, adding alkali, adjusting the pH, and filtering after reaction; 3) secondary impurity removal: adding alkali into the filtrate obtained by filtering in the step 2), adjusting the pH value, reacting and filtering. The impurity removing method for recycling the nonferrous metals by the electroplating sludge wet method has the advantages of simple process, low cost and easy production and application, so that the belt loss of the nonferrous metals is reduced, the alkali utilization rate is improved and no waste slag is generated in the electroplating sludge wet method recycling.
According to the invention, the influence of temperature on the ionization of hydrogen phosphate radicals and dihydrogen phosphate radicals is utilized, and a large amount of hydrogen phosphate radicals and dihydrogen phosphate radicals are ionized into phosphate radicals at higher temperature, so that chromium phosphate, iron phosphate and aluminum phosphate precipitate at a specific low pH value, nonferrous metals do not precipitate, the effect of removing most of phosphorus, chromium, iron and aluminum is achieved, and the precipitate is easy to filter. Then in the environment of feed liquid of phosphorus, chromium, iron and aluminum, the pH value is adjusted to be near neutral, and residual small amount of phosphorus, chromium, iron and aluminum are removed to obtain impurity-removed slag, wherein the slag mainly comprises chromium, iron, aluminum and nonferrous metalsThe hydroxide is precipitated, the amount of slag is small, washing is not needed, and after slurrying, the impurities are removed once again to replace part of alkali, so that an ideal impurity removing effect is obtained. In the invention, most of iron element in the electroplating sludge is Fe3+And a small amount of Fe2+The oxidizing agent oxidizes ferrous iron so as to ensure that all iron elements exist in a ferric form during impurity removal and precipitation. The oxidant can be one or more of hydrogen peroxide, compressed air, sodium chlorate and the like. Hydrogen peroxide is preferred.
According to the impurity removing method for recycling the nonferrous metals by the electroplating sludge wet method, provided by the embodiment of the invention, in the step 1), the sum of the molar concentrations of chromium, iron and aluminum in the impurity removing feed liquid is 0.8-1.5 times of the molar concentration of phosphorus; preferably, if the molar concentration sum of chromium, iron and aluminum is unbalanced with the molar concentration ratio of phosphorus, actively adding soluble phosphate and/or soluble ferric salt to maintain the ratio balance of chromium, iron, aluminum and phosphorus in the feed liquid system; more preferably, sodium phosphate and iron sulphate are added. In the present invention, the coprecipitation is carried out under the above pH condition by controlling the sum of the molar concentrations of chromium, iron and aluminum in the feed liquid and the molar concentration of phosphorus to maintain a specific ratio. On the one hand, phosphorus is not excessive (the ratio is not less than 0.8), otherwise, when the ph is adjusted to be nearly neutral by secondary impurity removal, a large amount of non-ferrous metal phosphate precipitates, the impurity removal slag amount is large, the non-ferrous metal content is high, although impurity removal slag can be returned to one-time impurity removal for use, the impurity removal efficiency is reduced, even impurity removal slag cannot be consumed, the output impurity removal slag is dangerous and waste, and the whole system is crashed. On the other hand, phosphorus cannot be too little (the ratio is not more than 1.5), otherwise, the precipitation rate of chromium, iron and aluminum in primary impurity removal is too low, so that more chromium, iron and aluminum enter secondary impurity removal, the burden of secondary impurity removal is increased, the impurity removal slag amount is large, and the impurity removal efficiency is low.
According to the impurity removal method for recycling nonferrous metals by using the electroplating sludge wet method, provided by the embodiment of the invention, the impurity removal feed liquid is a strong acid system, and preferably, the pH value of the impurity removal feed liquid is 1.0-3.0.
According to the impurity removing method for recycling nonferrous metals by using the electroplating sludge wet method, provided by the embodiment of the invention, in the step 2), the oxidant is hydrogen peroxide; preferably, the concentration of the hydrogen peroxide is 20-40%, and the dosage of the hydrogen peroxide is 1.0-1.5 times of the theoretical amount of ferrous iron in the oxidation feed liquid.
According to the impurity removing method for recycling nonferrous metals by using the electroplating sludge wet method, provided by the embodiment of the invention, in the step 2), the oxidant is added for reaction for 20-60 min, and the temperature is raised to 80-100 ℃ after the reaction.
According to the impurity removing method for recycling nonferrous metals by using the electroplating sludge wet method, provided by the embodiment of the invention, in the step 2), the alkali is added, the end point pH is maintained to be 1.5-3.5, and the reaction time is 20-60 min. Preferably, in step 2), the alkali is selected from one or more of sodium carbonate, sodium hydroxide, calcium oxide, calcium carbonate and calcium hydroxide. In the present invention, sodium alkali (sodium carbonate, sodium hydroxide) and calcium alkali (calcium oxide, calcium carbonate, calcium hydroxide) can be used, and sodium alkali is more preferable because calcium alkali has a disadvantage over sodium alkali.
According to the impurity removing method for recycling nonferrous metals by using the electroplating sludge wet method, provided by the embodiment of the invention, in the step 3), the alkali is added, the pH is maintained to be 4.0-6.0, and the reaction time is 20-60 min.
According to the impurity removing method for recycling nonferrous metals by using the electroplating sludge wet method, provided by the embodiment of the invention, in the step 3), the alkali is selected from one or more of sodium carbonate, sodium hydroxide, calcium oxide, calcium carbonate and calcium hydroxide; preferably, the sodium hydroxide is liquid sodium hydroxide with the concentration of 5-20%. In the invention, in the steps 2) and 3), the impurity removal can be well realized by adopting the above process conditions, and particularly, the impurity removal can be better realized by adopting the joint control of the temperature and the pH value, so that the yield of the nonferrous metal is higher, the alkali utilization rate is higher, and no waste residue is generated.
According to the impurity removing method for the wet resource recovery of nonferrous metals from electroplating sludge provided by the embodiment of the invention, the impurity removing method further comprises the following steps: returning filter residues in the step 3) to be used as alkali in the step 2); and/or washing the filter residue obtained in the step 3) with water to obtain impurity-removing residue, and preferably returning the impurity-removing residue to the step 1).
In the invention, the impurities are removed once, most of the impurities are precipitated under the condition of lower pH, the nonferrous metals are not precipitated, and the slag is washed by water to form an open circuit of the impurities, or stockpiled or continuously utilized; the secondary impurity removal only adjusts the pH value to be near neutral, removes a small amount of residual impurity elements, has small slag quantity, can be used as alkali to return to the primary impurity removal, is dangerous waste, can consume the slag when returning, and can improve the alkali utilization rate.
According to the invention, researches show that the impurity removing method for recycling nonferrous metals by using the electroplating sludge wet method comprises the steps of firstly ionizing dihydrogen phosphate and hydrogen phosphate into phosphate radicals at a high temperature of 80-100 ℃, so that most of chromium phosphate, iron phosphate and aluminum phosphate can be precipitated when the pH value is as low as 1.5-3.5, the precipitates are easy to filter, the precipitation rate of phosphorus, chromium, iron and aluminum is higher than 90%, and the precipitation rate of nonferrous metals such as nickel and zinc is lower than 1%. After the solid-liquid separation, phosphorus, chromium, iron and aluminum are effectively removed. And adjusting the pH to be nearly neutral at the temperature of 50-80 ℃, removing a small amount of residual phosphorus, chromium, iron, aluminum and the like to obtain impurity-removed slag, wherein the impurity-removed slag is small in amount and does not need to be washed, and the impurity-removed slag is directly returned to one-time impurity removal to replace part of alkali for maintaining the pH value. On the one hand, the production of impurity-removing slag which is treated as hazardous waste is avoided, and on the other hand, the loss of the non-ferrous metal strip is reduced and the utilization rate of alkali is improved. According to the invention, the method and the parameters are matched and adjusted to be applied to the field of electroplating sludge wet recycling, so that the aims of further reducing the loss of the non-ferrous metal strip, improving the alkali utilization rate and avoiding the generation of waste slag are achieved.
The invention has at least the following beneficial effects: the impurity removing method for recycling the nonferrous metals by the electroplating sludge wet method effectively reduces the belt loss of the nonferrous metals in the recycling of the nonferrous metals by the electroplating sludge wet method, and simultaneously, no impurity removing waste residue is generated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The instruments, raw materials and the like used are all conventional products which are purchased by normal merchants and are not indicated by manufacturers. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
In the following examples of the present invention, the feed liquid may be obtained from the extraction or deposition of copper from the electroplated sludge copper, and the treated feed liquid in the examples is specifically obtained from the extraction of copper from the feed liquid, and the ph of the strong acid system is 1.0-3.5.
Some embodiments of the invention provide an impurity removing method for recycling nonferrous metals by electroplating sludge wet method, comprising the following steps:
s1: preparation of impurity-removed feed liquid: the impurity removal feed liquid is taken from the feed liquid after copper extraction or copper precipitation, and the sum of the molar concentrations of chromium, iron and aluminum in the impurity removal feed liquid is 0.8-1.5 times of the molar concentration of phosphorus through reasonable proportioning, and the pH value of the impurity removal feed liquid is 1.0-3.5;
s2: primary impurity removal of feed liquid: and (2) adding the S1 impurity-removed material liquid into a reactor with a stirring and heating device, starting stirring, uniformly and slowly adding hydrogen peroxide with the concentration of 20-40%, wherein the hydrogen peroxide is 1.0-1.2 times of the theoretical amount of ferrous iron in the oxidized material liquid, and the reaction time is 20-60 min. Heating to 80-100 ℃, uniformly and slowly adding solid sodium carbonate, maintaining the end point pH value at 1.5-3.5, reacting for 20-60 min, filtering, reserving the filtrate for later use, and washing the filter residue to obtain the ferrochromium-aluminum phosphate residue;
s3: secondary impurity removal of feed liquid: and (3) putting the filtrate generated in the step (S2) into a reactor with a stirring and heating device, starting stirring, maintaining the temperature at 50-80 ℃, adding a 10-40% sodium hydroxide solution, adjusting the pH to 4.0-6.0, reacting for 20-60 min, filtering, returning filter residues to the step (S2) for primary impurity removal, and transferring the filtrate to a subsequent extraction process to separate nonferrous metals.
In summary, the invention firstly reasonably mixes the materials to ensure that the mixture ratio of chromium, iron, aluminum and phosphorus in the impurity removal feed liquid is reasonable, after ferrous iron is oxidized, the temperature is raised to nearly 100 ℃ under lower pH value, chromium phosphate, iron phosphate and aluminum phosphate precipitate is separated out, most of phosphorus, iron, chromium and aluminum are removed, a byproduct of chromium phosphate, iron and aluminum is obtained after washing, and the loss rate of the colored metal strip is very low. And then in a low-phosphorus, iron, chromium and aluminum feed liquid environment, adjusting the pH value to be nearly neutral to carry out secondary impurity removal, wherein the secondary impurity removal amount is small, and the primary impurity removal is returned to replace part of alkali. The invention effectively reduces the belt loss of nonferrous metals, improves the utilization rate of alkali and avoids the generation of dangerous waste residues.
Example 1
The embodiment provides an impurity removing method for recycling nonferrous metals by electroplating sludge wet method, which comprises the following steps:
s1: preparation of feed liquid: the feed liquid is taken from the feed liquid after copper extraction, and 3.5L of impurity-removed feed liquid is prepared by reasonable proportioning, and the feed liquid comprises the following components: fe 7.00g/l, Cr 7.01g/l, Al 1.91g/l, P10.32 g/l, Ni 5.85g/l, Zn 3.8g/l, sulfuric acid system, pH 1.5 (the sum of the molar concentrations of Cr, Fe and Al is 1.03 +/-0.01 times of the molar concentration of P);
s2: primary impurity removal: putting the S1 feed liquid into a reactor with a stirring and heating device, starting stirring, adding 30% hydrogen peroxide with the concentration 1.2 times of the theoretical amount of bivalent iron oxide, reacting for 30 minutes, heating to 95 ℃, slowly and uniformly adding solid sodium carbonate, maintaining the pH to be 3.0, reacting for 60 minutes, filtering, reserving filtrate, washing filter residues twice to obtain the chromium iron aluminum phosphate slag, and reserving;
s3: secondary impurity removal: and (3) putting the filtrate generated in the step (S2) into a reactor with a stirring and heating device, starting stirring, maintaining the temperature at 70 ℃, adding 30% sodium hydroxide solution, adjusting the pH value to be 4.8-5.0, reacting for 30 minutes, filtering, transferring the filtrate into an extraction process to separate nonferrous metals, and returning filter residues (impurity removal residues) to the step (S1) for removing impurities once.
In the impurity removal method for recycling non-ferrous metals by using electroplating sludge wet method provided in example 1, the yield of the aluminum-chromium phosphate slag is 701g, the yield of the impurity-removed slag is 43g, the removal rates of Fe, Cr, Al and P are respectively 99.02%, 94.30%, 91.01% and 96.35%, and the damage rates of Ni and Zn are respectively 0.26% and 0.22%).
It is to be noted that the term "comprises," "comprising," or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An impurity removal method for recovering nonferrous metals by using electroplating sludge wet method is characterized by comprising the following steps:
1) preparing materials: taking a feed liquid obtained after copper extraction or copper precipitation, and batching to obtain an impurity-removed feed liquid, wherein the molar concentration sum of chromium, iron and aluminum in the impurity-removed feed liquid maintains a certain proportion to the molar concentration of phosphorus;
2) primary impurity removal: adding an oxidant into the impurity-removed feed liquid, heating after reaction, adding alkali, adjusting the pH, and filtering after reaction;
3) secondary impurity removal: adding alkali into the filtrate obtained by filtering in the step 2), adjusting the pH value, reacting and filtering.
2. An impurity removal method for recycling nonferrous metals by using a wet electroplating sludge process according to claim 1, wherein in the step 1), the sum of the molar concentrations of chromium, iron and aluminum in the impurity removal feed liquid is 0.8-1.5 times of the molar concentration of phosphorus; preferably, if the molar concentration sum of chromium, iron and aluminum is unbalanced with the molar concentration ratio of phosphorus, actively adding soluble phosphate and/or soluble ferric salt to maintain the ratio balance of chromium, iron, aluminum and phosphorus in the feed liquid system; more preferably, sodium phosphate and iron sulphate are added.
3. An impurity removal method for wet resource recovery of nonferrous metals from electroplating sludge according to claim 2, characterized in that in the step 1), the impurity removal feed liquid is a strong acid system; preferably, the pH value of the impurity-removing feed liquid is 1.0-3.0.
4. An impurity removing method for electroplating sludge wet resource recovery of nonferrous metals according to claim 1, wherein in the step 2), the oxidant is hydrogen peroxide; preferably, the concentration of the hydrogen peroxide is 20-40%, and the dosage of the hydrogen peroxide is 1.0-1.5 times of the theoretical amount of ferrous iron in the oxidation feed liquid.
5. An impurity removing method for recycling nonferrous metals by using electroplating sludge wet method according to claim 4, wherein in the step 2), the oxidant is added for reaction for 20-60 min, and the temperature is raised to 80-100 ℃ after the reaction.
6. An impurity removal method for electroplating sludge wet reclamation of nonferrous metals according to any one of claims 1 to 5, wherein the alkali is added in the step 2), the end point pH is maintained to be 1.5-3.5, and the reaction time is 20-60 min.
7. An impurity removing method for recycling nonferrous metals by using a wet method through electroplating sludge according to claim 1, characterized in that in the step 3), the alkali is added, the pH is maintained to be 4.0-6.0, and the reaction time is 20-60 min; preferably, in step 2), the alkali is selected from one or more of sodium carbonate, sodium hydroxide, calcium oxide, calcium carbonate and calcium hydroxide. In the present invention, sodium alkali (sodium carbonate, sodium hydroxide) and calcium alkali (calcium oxide, calcium carbonate, calcium hydroxide) can be used, and sodium alkali is more preferable because calcium alkali has a disadvantage over sodium alkali.
8. An impurity removing method for recycling nonferrous metals by using a wet method through electroplating sludge according to claim 7, wherein in the step 3), the alkali is added, the pH value is maintained to be 4.0-6.0, and the reaction time is 20-60 min.
9. An impurity removing method for recovering nonferrous metals by electroplating sludge wet reclamation according to claim 7 or 8, wherein in the step 3), the alkali is selected from one or more of sodium carbonate, sodium hydroxide, calcium oxide, calcium carbonate and calcium hydroxide; preferably, the sodium hydroxide is liquid sodium hydroxide with the concentration of 5-20%.
10. An impurity removing method for electroplating sludge wet resource recovery of nonferrous metals according to claim 1, further comprising: the slag obtained in the step 3) is returned to the step 2) to be used as alkali; and/or washing the filter residue obtained in the step 3) with water to obtain impurity-removing residue, and preferably returning the impurity-removing residue to the step 1).
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| CN117466502A (en) * | 2023-12-28 | 2024-01-30 | 深圳星河环境股份有限公司 | Recovery method of phosphorus-containing waste liquid |
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