CN114516655B - Method for producing copper hydroxide from circuit board waste - Google Patents
Method for producing copper hydroxide from circuit board waste Download PDFInfo
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- CN114516655B CN114516655B CN202210122951.0A CN202210122951A CN114516655B CN 114516655 B CN114516655 B CN 114516655B CN 202210122951 A CN202210122951 A CN 202210122951A CN 114516655 B CN114516655 B CN 114516655B
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- C01—INORGANIC CHEMISTRY
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- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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Abstract
The invention discloses a method for producing copper hydroxide by using circuit board waste, and belongs to the technical field of circuit board waste recovery. The method for producing copper hydroxide by using the circuit board waste comprises the following steps: s1, preparing acidified slurry; s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, regulating the pH to 3.2-3.5, heating to 70-90 ℃, maintaining the pH of the system unchanged, carrying out heat preservation reaction for 0.5-1 h, adding chemical copper waste liquid until the purple of the reaction system subsides, carrying out reaction for 15-30 min, carrying out solid-liquid separation to obtain a impurity-removing solid phase, and removing COD (chemical oxygen demand) from the liquid phase to obtain the impurity-removing liquid; s3, ammonia leaching to obtain ammonia leaching liquid; s4, preparing a copper-king precursor; s5, ammonia is converted to obtain a copper hydroxide product. The method fully utilizes the self characteristics of the circuit board sludge, the alkaline potassium permanganate waste liquid and the electroless copper plating waste liquid, treats waste with waste, realizes the maximum recycling of copper resources, and simultaneously prepares the copper hydroxide product with excellent quality.
Description
Technical Field
The invention relates to the technical field of circuit board waste recycling, in particular to a method for producing copper hydroxide by using circuit board waste.
Background
Copper-containing wastewater is generated in the production process of the circuit board, such as brushing the board, electroplating copper on patterns, etching, pickling, water washing and the like; in addition, the steps of tin plating, tin stripping and the like also produce a small amount of waste water containing heavy metals such as lead, tin and the like. The circuit board factories generally mix the waste water and the waste water, and precipitate the waste water by adding lime, alkali liquor and sulfide, and adding coagulants such as iron, aluminum and the like or compound flocculants for coagulation or flocculation, so that heavy metals in the waste water are removed, and waste water treatment sludge, namely the circuit board sludge is generated. The treatment method of the circuit board sludge generally comprises the following steps: (1) heat treatment process: the sludge heat treatment process is a process of carrying out high-temperature smelting after drying and proportioning the sludge. The sludge is dried and then mixed with other raw materials, and the mixture is fed into a furnace for smelting to obtain metallic copper, and smelting slag can be used for producing cement or used as an abrasive for ship rust removal after being processed, and the whole process basically realizes recycling and reutilization of the sludge. However, the main method of heat treatment is an incineration method, which has the defects of high energy consumption, certain requirements on incineration equipment and conditions, easy secondary pollution to the environment in the incineration process and the like, and a common small electroplating plant is difficult to bear huge treatment cost, so that the method is difficult to popularize in a large area. (2) Curing treatment method: the solidifying treatment method is to add a solidifying agent into the electroplating sludge, mix the electroplating sludge with the sludge for solidification, and seal harmful substances in the sludge in the solidified body so as not to be leached out, thereby achieving the aim of removing pollution. Curing agents can be classified into inorganic and organic types, wherein inorganic curing agents are represented by cement and phosphate systems; the organic curing agent may be classified into a high molecular liquid chelating agent and a low molecular liquid chelating agent. Chelating agents are mostly patent products, and the cost is high; when the cement curing agent is used alone, the heavy metal can be seriously influenced by long-term dissolution. (3) Chemical treatment method: the chemical treatment is a process for extracting valuable metal components from sludge by treating the sludge with an acid or an alkali. The acid leaching method is one of the most widely used methods for extracting soluble target components from electroplating sludge by using sulfuric acid, hydrochloric acid and other acids as leaching agents, but the method has high leaching efficiency on copper, zinc and nickel, poor selectivity on iron and chromium, and the extraction agent has to be used for separating leached metals, so that the price of the extraction agent is high, and the extraction efficiency is low. The alkaline leaching method generally adopts ammonia water solution or ammonia water plus ammonium salt as leaching agent to extract valuable metal components in the sludge, and has the advantages of convenient use, good selectivity and the like. However, ammonia water has an offensive odor, and has a high requirement for the sealability of the leaching device, and when the concentration of ammonia gas is more than 18%, the volatilization of ammonia water is high, so that the loss of ammonia water and the deterioration of the operation environment are caused. (4) Microbiological method: the principle of the microbiological method is to utilize the biological acidogenesis of the autotrophic acidophilic thiobacillus to dissolve out insoluble heavy metals from a solid phase into a liquid phase to become soluble metal ions, and then to recycle metal resources from the leaching solution by a proper method. However, how to cultivate the strain with strong adaptability and high waste treatment efficiency is still a great difficulty faced by the biological method at present.
In the production process of PCB circuit board hole metallization, an electroless copper plating technology is generally adopted, so that electroless copper plating waste liquid is generated, the waste liquid generally contains reducing agents such as EDTA, formaldehyde and the like, the pH is more than 12, and the direct discharge can cause serious pollution to the environment. The general treatment method of the electroless copper plating waste liquid comprises the following steps: copper recovery by precipitation, complexing agent recovery by precipitation, and subsequent biochemical or chemical treatment of wastewater. Precipitating and recovering copper: and the copper powder is subjected to precipitation reaction with sodium hydroxide solution to recover copper metal powder, or is subjected to precipitation reaction with lime to recover copper hydroxide. And (3) precipitating and recycling complexing agent: the pH was adjusted with an acid, and EDTA was recovered after standing. The subsequent biochemical or chemical treatment of the wastewater: for chemical copper waste liquid with lower COD concentration, adding a flocculating agent to remove COD after Fenton oxidation reaction; for the chemical copper waste liquid with higher COD concentration, fenton oxidation reaction and flocculating agent pretreatment are carried out, and then anaerobic-aerobic biological reaction treatment is carried out after dilution. Although copper and EDTA can be recovered step by the method, the residual formaldehyde and COD in the waste liquid are still higher, the subsequent wastewater treatment is more complex, and a large amount of chemical raw materials are consumed for repeatedly adjusting the pH value.
The alkaline potassium permanganate waste liquid is the production waste liquid in the production process of the PCB, and in the production process of the PCB for removing the drilling dirt, an alkaline solution prepared from potassium permanganate and potassium hydroxide is required to be added, and the alkaline potassium permanganate waste liquid is formed by mixing the cleaning water after the drilling dirt is removed. The pH of the waste liquid is more than 12, the content of potassium permanganate is about 5 percent, the manganese content exceeds the requirement of the national first-class discharge standard (manganese is less than or equal to 2mg/L, pH=6-9), and the waste liquid is purple-red no matter how much water is used for dilution, has poor chromaticity and cannot be directly discharged. The existing treatment method for the alkaline potassium permanganate waste liquid mainly comprises the steps of thermal decomposition and reduction by adding a reducing agent. The heating decomposition method is to remove manganese by adjusting pH, heating the potassium permanganate waste liquid to decompose and reduce to generate manganese dioxide solid, and has high energy consumption and waste of strong oxidizing property of potassium permanganate. The reducing method by adding reducing agent is to remove manganese by adjusting pH, adding reducing agent such as sulfurous acid, sodium sulfite, sodium bisulphite and the like to reduce potassium permanganate into manganese dioxide solid. The method has lower energy consumption, but chemical raw materials are additionally added, and the strong oxidizing property of the potassium permanganate is wasted.
In the prior art, the treatment schemes of the circuit board sludge, the potassium permanganate waste liquid and the electroless copper plating waste liquid cannot well utilize the value of the waste, and a large amount of chemical raw materials are required to be additionally added for treatment, so that the treatment cost is increased and the corresponding economic effect cannot be achieved.
Disclosure of Invention
The invention aims to overcome the defects that the existing circuit board sludge, potassium permanganate waste liquid, electroless copper plating waste liquid and other wastes cannot be efficiently recycled and the single treatment cost is high, and provides a method for producing copper hydroxide by using the circuit board waste, which realizes the comprehensive and cooperative utilization of the circuit board sludge, the potassium permanganate waste liquid and the electroless copper plating waste liquid, treats the waste with the waste, solves the waste treatment problem, and recycles and obtains the high-quality copper hydroxide product.
The above object of the present invention is achieved by the following technical scheme:
a method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: activating the sludge of the circuit board, adding the activated sludge into hydrochloric acid, and adjusting the pH to 2.5-3.0 to obtain acidified slurry;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, regulating the pH to 3.2-3.5, reacting for 0.5-1 h at 70-90 ℃, adding electroless copper plating waste liquid until the purple of a reaction system is resolved, reacting for 15-30 min, and carrying out solid-liquid separation to obtain a impurity-removing solid phase, and removing COD (chemical oxygen demand) from the liquid phase to obtain an impurity-removing liquid;
s3, ammonia leaching: fully mixing the impurity-removed solid phase with ammonia-containing solution, stirring, pulping, sieving, adding ammonia water to adjust the pH value to 8-8.8, reacting for 0.5-1 h at 45-55 ℃, carrying out solid-liquid separation, and removing COD (chemical oxygen demand) from the liquid phase to obtain ammonia leaching solution;
s4, preparing a copper master batch precursor: the impurity removing liquid in the S2 and the ammonia leaching liquid in the S3 are subjected to parallel flow reaction, the pH of the reaction is maintained to be 4.0-5.0, the reaction is carried out for 2-4 hours at 20-60 ℃, the solid-liquid separation is carried out, and the solid phase is the copper master precursor;
s5, converting ammonia into copper hydroxide: adding water into the copper master batch precursor in the step S4 to prepare slurry, adding ammonia water to adjust the pH value to 10-12, reacting for 1-2 h at 20-60 ℃, carrying out solid-liquid separation, removing residual alkali through solid phase, and drying to obtain a copper hydroxide product.
The following description is needed:
the specific operation of the sludge activation of the line board in S1 may be as follows:
adding water with equal mass into the sludge of the circuit board, fully stirring and pulping, stirring for 1-3 hours, sieving, removing impurities such as sediment and the like, and obtaining activated sludge slurry.
In order to further acidify thoroughly, the sludge of the circuit board is added into hydrochloric acid after being activated, the pH is adjusted to 2.5-3.0, and the mixture is stirred for 1-3 hours to obtain the acidized slurry. Wherein, the acidification pH value is 2.5-3.0, so that most copper in the circuit board sludge can be leached, and the leaching rate of copper is improved.
In the step of removing impurities in S2, the pH value of the system needs to be kept unchanged and is kept at 3.2-3.5, if the pH value is too low, divalent manganese in the potassium permanganate waste liquid is not completely converted, manganese cannot be fully recycled and used, and the manganese remains in a liquid phase, so that the impurity content of a subsequent product is high, the pH value is too high, copper in the circuit board sludge is difficult to leach, and more chemical raw materials are needed for subsequent ammonia leaching.
The alkaline potassium permanganate waste liquid has oxidability under the acidic heating condition, and the pH value of the acidified slurry is regulated to 3.2-3.5 by utilizing the alkaline potassium permanganate waste liquid, so that on one hand, the acidity of the acidified slurry is utilized, the pH value of the alkaline potassium permanganate waste liquid is regulated to be low, the use of acid is saved, and on the other hand, the alkalinity of the alkaline potassium permanganate waste liquid is utilized, the pH value of the acidified slurry is regulated to be high, and the use of alkali is saved.
Under the condition of acidic heating, potassium permanganate in the potassium permanganate waste liquid can effectively oxidize acidified slurry, COD of the potassium permanganate waste liquid and ferrous ions in the acidified slurry, and oxidation-reduction products in the pH range of 3.2-3.5 are a mixture of manganese dioxide and ferric hydroxide, so that the potassium permanganate waste liquid is a high-quality water purifying agent, has strong adsorptivity, can effectively remove manganese and ferric ions in pickling liquid, realizes effective separation of copper and iron, and obtains purer cupric chloride solution after further adsorbing COD by activated carbon, thereby providing guarantee for preparing high-quality recycling products.
Meanwhile, the mixture of the manganese dioxide and ferric hydroxide which are the reduction products is easy to dissolve in concentrated hydrochloric acid, and if the mixture contains noble metals, the mixture is convenient to recycle.
Because the consumption of the alkaline potassium permanganate waste liquid in the impurity removal process is excessive, the system is purple, and the potassium permanganate has strong oxidizing property under the acidic heating condition, and the electroless copper plating waste liquid contains formaldehyde, EDTA and other strong reducing substances, the excessive potassium permanganate can be reduced by the alkaline potassium permanganate waste liquid, meanwhile, COD in the electroless copper plating waste liquid is treated, and copper in the alkaline potassium permanganate waste liquid can be recycled in a concentrated manner. The reaction end point of the impurity removal reaction is simply judged, and the end of the reaction can be judged only by finding that the purple color just subsides.
The reaction temperature in the S2 impurity removal reaction is 70-90 ℃, if the reaction temperature is too low, the reaction is slow, the conversion of divalent manganese is incomplete, the purity of the subsequent products is affected, and if the reaction temperature is high, the energy consumption of waste recycling is high, so that the high economic benefit is not realized.
The ammonia-containing solution in S3 can be ammonia-containing wastewater such as liquid-phase copper-king mother liquor, basic copper chloride mother liquor and the like which are subjected to solid-liquid separation in S4.
And S3, stirring and pulping for 1-3 hours, so that the impurity-removing solid phase and the ammonia-containing solution are mixed more fully, and the slurry is obtained by sieving large-particle solids after the mixing and the sieving treatment.
And S3, the pH value of the reaction system is regulated by adopting ammonia water, so that the consistency of the front and rear reaction systems can be ensured, the introduction of impurity ions into the whole reaction system is avoided, and the impurity of an ammonium chloride product recovered later can be caused.
And S3, the solid phase of solid-liquid separation is a ferromanganese slag product, and the ferromanganese slag product can be recycled as a raw material of cement.
S4, the impurity removing liquid and the ammonia leaching liquid react in parallel, the flow ratio of the impurity removing liquid to the ammonia leaching liquid can be preferably 1-3:1, and the reaction is more sufficient.
The control of the reaction pH value in S4 has important influence on the yield of the copper oxychloride, the pH value is less than 4, the yield of the copper oxychloride is low, the copper oxychloride in the system is not converted into the copper oxychloride, and the copper oxychloride is difficult to filter. The pH value is more than 5, the yield of the copper master is low, and the copper master product is dissolved and becomes copper ammonia solution.
In S5, in order to prevent the copper hydroxide product from being discolored and prolong the shelf life, the residual alkali in the solid phase after solid-liquid separation needs to be removed, and the removal method can adopt water washing until the pH value of the washing water is 9-10.
The method for producing copper hydroxide by using the circuit board waste fully utilizes the self characteristics of the circuit board sludge, the alkaline potassium permanganate waste liquid and the electroless copper plating waste liquid, and can effectively remove most COD and impurity metals to obtain pure impurity-removing acid liquid; by utilizing the complex ammonia leaching method of ammonium chloride-ammonia water in the ammonia-containing solution, residual copper in the impurity-removed slag can be effectively leached out without introducing impurity anions basically, so that pure ammonia leaching liquid is obtained, and meanwhile, the maximum recycling of copper resources is realized. The copper oxide precursor prepared by the neutralization precipitation reaction of the impurity-removing acid liquid and ammonia leaching solution can be prepared into a copper hydroxide product with excellent quality after ammonia conversion.
Wherein, the liquid phase after synthesizing the copper master batch is copper master batch, part of the liquid phase can be recycled to the S3 step for ammonia leaching, and the rest of the liquid phase is absorbed by ion exchange resin to recover copper, and then an MVR evaporation concentration technology is utilized to recover an ammonium chloride product.
In a specific embodiment, the concentration of hydrochloric acid in S1 is preferably 10 to 15% by mass.
In the process of acidifying sludge by hydrochloric acid, the hydrochloric acid has too high acidity and can smoke (HCl gas), and the operation environment is bad; hydrochloric acid is too low in acid strength, and a large amount of wastewater is generated.
In a specific embodiment, the ammonia-containing solution in S3 is a solid-liquid separated liquid-phase copper alloy mother liquor of S4.
Preferably, the mass ratio of the impurity removing solid phase to the ammonia-containing solution in the S3 is 1:1.5-3. The solid-liquid ratio is too small, and the stirring is not uniform; the solid-liquid ratio is too large, so that a large amount of production wastewater is generated, and the subsequent wastewater treatment pressure is high.
The copper master solution comprises the following specific components:
copper content: 0.5-1.5 g/L; ammonia nitrogen content: 10-30 g/L.
In a specific embodiment, the liquid phase of the solid-liquid separation in the step S5 is copper ammonia solution, and the copper ammonia solution is recycled to the step S4 to prepare the copper master batch precursor.
In a specific embodiment, the mass concentration of the ammonia water in S3 and S5 is 15-20%.
In a specific embodiment, the impurity removing solution in S2 may be used to prepare a copper-king precursor in order to recycle the reaction product.
In a specific embodiment, in order to fully recycle the reaction product, it is preferable that the impurity removing liquid in S2 and the liquid phase separated by solid-liquid in S5 are both a mixture of the liquid phase separated by solid-liquid and the water washing liquid separated by solid phase.
In a specific embodiment, the production method can combine various potassium permanganate waste liquid, electroless copper plating waste liquid and circuit board sludge which are difficult to treat, treat waste with waste, recover high-quality copper hydroxide products, effectively separate iron and copper, recover manganese iron slag, and recycle the manganese iron slag as a production raw material of cement.
Wherein the potassium permanganate content of the potassium permanganate waste liquid is 4.5-5%, the COD content is 1000-2000 mg/L, and the pH is more than or equal to 12.
The copper content of the electroless copper plating waste liquid is 0.5-1 g/L, the COD content is 32-35 g/L, and the pH is more than or equal to 12.
The copper content of the circuit board sludge is 6-6.5%, and the iron content is 7-10%.
The invention also specifically protects the copper hydroxide produced by the method for producing copper hydroxide by using the circuit board waste.
Compared with the prior art, the invention has the beneficial effects that:
the method for producing copper hydroxide by using the circuit board waste fully utilizes the self characteristics of the circuit board waste, uses the alkaline potassium permanganate waste liquid to adjust the pH value of the acidified slurry, utilizes the strong oxidizing property of the alkaline potassium permanganate waste liquid under the condition that the pH value is 3.2-3.5, effectively oxidizes the acidified slurry and COD (chemical oxygen demand) of the acidified slurry and ferrous ions in the acidified slurry, realizes the effective separation of iron and copper, and obtains ferromanganese slag products and pure copper chloride solution.
The impurity removal process also utilizes the synergistic effect of the alkaline potassium permanganate waste liquid and the electroless copper plating waste liquid to reduce excessive potassium permanganate and remove COD in the system at the same time, thereby further promoting the centralized recycling of copper.
The invention fully utilizes the self characteristics of the circuit board sludge, the alkaline potassium permanganate waste liquid and the electroless copper plating waste liquid, and can effectively remove most COD and impurity metals to obtain pure impurity-removing acid liquid; by utilizing the complex ammonia leaching method of ammonium chloride-ammonia water, residual copper in the impurity-removed slag can be effectively leached out without introducing impurity anions basically, so that pure ammonia leaching liquid is obtained, the maximum recycling of copper resources is realized, and a copper hydroxide product with excellent quality is prepared. Meanwhile, the method realizes the treatment of three kinds of hazardous wastes by wastes, and compared with the independent treatment of various wastes in the industry, the method greatly reduces the investment of chemical raw materials such as oxidants, alkali liquor and the like, and can save about 500-1000 yuan per ton of cooperative treatment of the three kinds of wastes.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Among them, the waste raw materials of the main examples and comparative examples of the present invention are explained as follows:
circuit board sludge:
| moisture content/% | Copper/% | Iron/% | Chromium/% | Cadmium/% | Arsenic/% | Lead/% |
| 75％～85％ | 6～6.5 | 7～10 | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 |
Potassium permanganate waste liquid
| Potassium permanganate/% | COD/mg/L | pH |
| 4.5～5 | 1000～2000 | ＞12 |
Electroless copper plating waste liquid
| copper/g/L | COD/g/L | pH |
| 0.5～1 | 32～35 | ＞12 |
Example 1
A method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: adding water with equal mass into the circuit board sludge, fully stirring and pulping, stirring for 2 hours, sieving, removing impurities such as silt and the like to obtain activated sludge slurry, activating the circuit board sludge, adding the activated circuit board sludge into hydrochloric acid, and regulating the pH value to 3.0 to obtain acidified slurry, wherein the mass concentration of the hydrochloric acid is 15%;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.2, heating to 90 ℃, maintaining the pH of the system unchanged, preserving heat for reaction for 1h,
adding chemical copper waste liquid until the purple of a reaction system subsides, reacting for 30min, performing solid-liquid separation to obtain a impurity-removing solid phase, rinsing the impurity-removing solid phase, performing complex ammonia leaching, combining liquid phase continuous water, and further removing COD (chemical oxygen demand) by using active carbon to obtain an impurity-removing liquid for preparing a copper-king precursor;
s3, ammonia leaching: fully mixing the impurity-removing solid phase and the copper master solution, wherein the mass ratio of the impurity-removing solid phase to the copper master solution is 1:2, stirring for pulping for 2 hours, sieving, adding ammonia water into the slurry, adjusting and maintaining the pH value to 8, reacting at 50 ℃ for 1 hour, performing solid-liquid separation, wherein the solid phase is manganese iron slag and can be sold as a byproduct, combining liquid-phase continuous water, further removing COD (chemical oxygen demand) by using active carbon, and obtaining ammonia leaching liquid for preparing copper master precursor;
s4, preparing a copper master batch precursor:
carrying out concurrent flow reaction on the impurity removing liquid in the step S2 and the ammonia leaching liquid of the step S3, maintaining the reaction pH at 4.0, reacting at 40 ℃ for 3 hours, carrying out solid-liquid separation, wherein the solid phase is a copper-bearing precursor, a part of liquid phase is used for pulping the impurity removing solid phase of the step S3, and a part of liquid phase enters a wastewater station for subsequent treatment;
s5, converting ammonia into copper hydroxide:
adding water into the copper master batch precursor in the step S4 according to the solid-to-liquid ratio of 1:2 to prepare slurry, adding ammonia water with the mass concentration of 20%, adjusting and maintaining the reaction pH at 12, maintaining the reaction temperature at 40 ℃, reacting for 2 hours, carrying out solid-liquid separation, removing impurities from the solid phase until the pH of the water is 10, and drying at a low temperature of 40 ℃ to obtain a copper hydroxide product.
And (3) adsorbing and recovering copper from a liquid phase obtained after synthesizing the copper master batch precursor by using ion exchange resin, and concentrating by using MVR evaporation to recover an ammonium chloride product.
Example 2
A method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: adding water with equal mass into the circuit board sludge, fully stirring and pulping, stirring for 2 hours, sieving, removing impurities such as silt and the like to obtain activated sludge slurry, activating the circuit board sludge, adding the activated circuit board sludge into hydrochloric acid, and regulating the pH value to 3.0 to obtain acidified slurry, wherein the mass concentration of the hydrochloric acid is 15%;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.5, heating to 90 ℃, maintaining the pH of the system unchanged, preserving heat for reaction for 1h,
adding chemical copper waste liquid until the purple of a reaction system subsides, reacting for 30min, performing solid-liquid separation to obtain a impurity-removing solid phase, rinsing the impurity-removing solid phase, performing complex ammonia leaching, combining liquid phase continuous water, and further removing COD (chemical oxygen demand) by using active carbon to obtain an impurity-removing liquid for preparing a copper-king precursor;
s3, ammonia leaching: fully mixing the impurity-removing solid phase and the copper master solution, wherein the mass ratio of the impurity-removing solid phase to the copper master solution is 1:2, stirring for pulping for 2 hours, sieving, adding ammonia water into the slurry, adjusting and maintaining the pH value to 8, reacting at 50 ℃ for 1 hour, performing solid-liquid separation, wherein the solid phase is manganese iron slag and can be sold as a byproduct, combining liquid-phase continuous water, further removing COD (chemical oxygen demand) by using active carbon, and obtaining ammonia leaching liquid for preparing copper master precursor;
s4, preparing a copper master batch precursor:
carrying out concurrent flow reaction on the impurity removing liquid in the step S2 and the ammonia leaching liquid of the step S3, maintaining the reaction pH at 4.0, reacting at 40 ℃ for 3 hours, carrying out solid-liquid separation, wherein the solid phase is a copper-bearing precursor, a part of liquid phase is used for pulping the impurity removing solid phase of the step S3, and a part of liquid phase enters a wastewater station for subsequent treatment;
s5, converting ammonia into copper hydroxide:
adding water into the copper master batch precursor in the step S4 according to the solid-to-liquid ratio of 1:2 to prepare slurry, adding ammonia water with the mass concentration of 20%, adjusting and maintaining the reaction pH at 12, maintaining the reaction temperature at 40 ℃, reacting for 2 hours, carrying out solid-liquid separation, removing impurities from the solid phase until the pH of the water is 10, and drying at a low temperature of 40 ℃ to obtain a copper hydroxide product.
And (3) adsorbing and recovering copper from a liquid phase obtained after synthesizing the copper master batch precursor by using ion exchange resin, and concentrating by using MVR evaporation to recover an ammonium chloride product.
Example 3
A method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: adding water with equal mass into the circuit board sludge, fully stirring and pulping, stirring for 2 hours, sieving, removing impurities such as silt and the like to obtain activated sludge slurry, activating the circuit board sludge, adding the activated circuit board sludge into hydrochloric acid, and regulating the pH value to 3.0 to obtain acidified slurry, wherein the mass concentration of the hydrochloric acid is 15%;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.5, heating to 70 ℃, maintaining the pH of the system unchanged, preserving heat for reaction for 1h,
adding chemical copper waste liquid until the purple of a reaction system subsides, reacting for 30min, performing solid-liquid separation to obtain a impurity-removing solid phase, rinsing the impurity-removing solid phase, performing complex ammonia leaching, combining liquid phase continuous water, and further removing COD (chemical oxygen demand) by using active carbon to obtain an impurity-removing liquid for preparing a copper-king precursor;
s3, ammonia leaching: fully mixing the impurity-removing solid phase and the copper master solution, wherein the mass ratio of the impurity-removing solid phase to the copper master solution is 1:2, stirring for pulping for 2 hours, sieving, adding ammonia water into the slurry, adjusting and maintaining the pH value to 8, reacting at 50 ℃ for 1 hour, performing solid-liquid separation, wherein the solid phase is manganese iron slag and can be sold as a byproduct, combining liquid-phase continuous water, further removing COD (chemical oxygen demand) by using active carbon, and obtaining ammonia leaching liquid for preparing copper master precursor;
s4, preparing a copper master batch precursor:
carrying out concurrent flow reaction on the impurity removing liquid in the step S2 and the ammonia leaching liquid of the step S3, maintaining the reaction pH at 4.0, reacting at 40 ℃ for 3 hours, carrying out solid-liquid separation, wherein the solid phase is a copper-bearing precursor, a part of liquid phase is used for pulping the impurity removing solid phase of the step S3, and a part of liquid phase enters a wastewater station for subsequent treatment;
s5, converting ammonia into copper hydroxide:
adding water into the copper master batch precursor in the step S4 according to the solid-to-liquid ratio of 1:2 to prepare slurry, adding ammonia water with the mass concentration of 20%, adjusting and maintaining the reaction pH at 12, maintaining the reaction temperature at 40 ℃, reacting for 2 hours, carrying out solid-liquid separation, removing impurities from the solid phase until the pH of the water is 10, and drying at a low temperature of 40 ℃ to obtain a copper hydroxide product.
And (3) adsorbing and recovering copper from a liquid phase obtained after synthesizing the copper master batch precursor by using ion exchange resin, and concentrating by using MVR evaporation to recover an ammonium chloride product.
Comparative example 1
A method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: adding water with equal mass into the circuit board sludge, fully stirring and pulping, stirring for 2 hours, sieving, removing impurities such as silt and the like to obtain activated sludge slurry, activating the circuit board sludge, adding the activated circuit board sludge into hydrochloric acid, and regulating the pH value to 3.0 to obtain acidified slurry, wherein the mass concentration of the hydrochloric acid is 15%;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.8, heating to 90 ℃, maintaining the pH of the system unchanged, preserving heat for reaction for 1h,
adding chemical copper waste liquid until the purple of a reaction system subsides, reacting for 30min, performing solid-liquid separation to obtain a impurity-removing solid phase, rinsing the impurity-removing solid phase, performing complex ammonia leaching, combining liquid phase continuous water, and further removing COD (chemical oxygen demand) by using active carbon to obtain an impurity-removing liquid for preparing a copper-king precursor;
s3, ammonia leaching: fully mixing the impurity-removing solid phase and the copper master solution, wherein the mass ratio of the impurity-removing solid phase to the copper master solution is 1:2, stirring for pulping for 2 hours, sieving, adding ammonia water into the slurry, adjusting and maintaining the pH value to 8, reacting at 50 ℃ for 1 hour, performing solid-liquid separation, wherein the solid phase is manganese iron slag and can be sold as a byproduct, combining liquid-phase continuous water, further removing COD (chemical oxygen demand) by using active carbon, and obtaining ammonia leaching liquid for preparing copper master precursor;
s4, preparing a copper master batch precursor:
carrying out concurrent flow reaction on the impurity removing liquid in the step S2 and the ammonia leaching liquid of the step S3, maintaining the reaction pH at 4.0, reacting at 40 ℃ for 3 hours, carrying out solid-liquid separation, wherein the solid phase is a copper-bearing precursor, a part of liquid phase is used for pulping the impurity removing solid phase of the step S3, and a part of liquid phase enters a wastewater station for subsequent treatment;
s5, converting ammonia into copper hydroxide:
adding water into the copper master batch precursor in the step S4 according to the solid-to-liquid ratio of 1:2 to prepare slurry, adding ammonia water with the mass concentration of 20%, adjusting and maintaining the reaction pH at 12, maintaining the reaction temperature at 40 ℃, reacting for 2 hours, carrying out solid-liquid separation, removing impurities from the solid phase until the pH of the water is 10, and drying at a low temperature of 40 ℃ to obtain a copper hydroxide product.
And (3) adsorbing and recovering copper from a liquid phase obtained after synthesizing the copper master batch precursor by using ion exchange resin, and concentrating by using MVR evaporation to recover an ammonium chloride product.
Comparative example 2
A method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: adding water with equal mass into the circuit board sludge, fully stirring and pulping, stirring for 2 hours, sieving, removing impurities such as silt and the like to obtain activated sludge slurry, activating the circuit board sludge, adding the activated circuit board sludge into hydrochloric acid, and regulating the pH value to 3.0 to obtain acidified slurry, wherein the mass concentration of the hydrochloric acid is 15%;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.0, heating to 90 ℃, maintaining the pH of the system unchanged, preserving heat for reaction for 1h,
adding chemical copper waste liquid until the purple of a reaction system subsides, reacting for 30min, performing solid-liquid separation to obtain a impurity-removing solid phase, rinsing the impurity-removing solid phase, performing complex ammonia leaching, combining liquid phase continuous water, and further removing COD (chemical oxygen demand) by using active carbon to obtain an impurity-removing liquid for preparing a copper-king precursor;
s3, ammonia leaching: fully mixing the impurity-removing solid phase and the copper master solution, wherein the mass ratio of the impurity-removing solid phase to the copper master solution is 1:2, stirring for pulping for 2 hours, sieving, adding ammonia water into the slurry, adjusting and maintaining the pH value to 8, reacting at 50 ℃ for 1 hour, performing solid-liquid separation, wherein the solid phase is manganese iron slag and can be sold as a byproduct, combining liquid-phase continuous water, further removing COD (chemical oxygen demand) by using active carbon, and obtaining ammonia leaching liquid for preparing copper master precursor;
s4, preparing a copper master batch precursor:
carrying out concurrent flow reaction on the impurity removing liquid in the step S2 and the ammonia leaching liquid of the step S3, maintaining the reaction pH at 4.0, reacting at 40 ℃ for 3 hours, carrying out solid-liquid separation, wherein the solid phase is a copper-bearing precursor, a part of liquid phase is used for pulping the impurity removing solid phase of the step S3, and a part of liquid phase enters a wastewater station for subsequent treatment;
s5, converting ammonia into copper hydroxide:
adding water into the copper master batch precursor in the step S4 according to the solid-to-liquid ratio of 1:2 to prepare slurry, adding ammonia water with the mass concentration of 20%, adjusting and maintaining the reaction pH at 12, maintaining the reaction temperature at 40 ℃, reacting for 2 hours, carrying out solid-liquid separation, removing impurities from the solid phase until the pH of the water is 10, and drying at a low temperature of 40 ℃ to obtain a copper hydroxide product.
And (3) adsorbing and recovering copper from a liquid phase obtained after synthesizing the copper master batch precursor by using ion exchange resin, and concentrating by using MVR evaporation to recover an ammonium chloride product.
Comparative example 3
A method for producing copper hydroxide from circuit board waste comprises the following steps:
s1, preparing acidified slurry: adding water with equal mass into the circuit board sludge, fully stirring and pulping, stirring for 2 hours, sieving, removing impurities such as silt and the like to obtain activated sludge slurry, activating the circuit board sludge, adding the activated circuit board sludge into hydrochloric acid, and regulating the pH value to 3.0 to obtain acidified slurry, wherein the mass concentration of the hydrochloric acid is 15%;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.2, heating to 60 ℃, maintaining the pH of the system unchanged, preserving heat for reaction for 1h,
adding chemical copper waste liquid until the purple of a reaction system subsides, reacting for 30min, performing solid-liquid separation to obtain a impurity-removing solid phase, rinsing the impurity-removing solid phase, performing complex ammonia leaching, combining liquid phase continuous water, and further removing COD (chemical oxygen demand) by using active carbon to obtain an impurity-removing liquid for preparing a copper-king precursor;
s3, ammonia leaching: fully mixing the impurity-removing solid phase and the copper master solution, wherein the mass ratio of the impurity-removing solid phase to the copper master solution is 1:2, stirring for pulping for 2 hours, sieving, adding ammonia water into the slurry, adjusting and maintaining the pH value to 8, reacting at 50 ℃ for 1 hour, performing solid-liquid separation, wherein the solid phase is manganese iron slag and can be sold as a byproduct, combining liquid-phase continuous water, further removing COD (chemical oxygen demand) by using active carbon, and obtaining ammonia leaching liquid for preparing copper master precursor;
s4, preparing a copper master batch precursor:
carrying out concurrent flow reaction on the impurity removing liquid in the step S2 and the ammonia leaching liquid of the step S3, maintaining the reaction pH at 4.0, reacting at 40 ℃ for 3 hours, carrying out solid-liquid separation, wherein the solid phase is a copper-bearing precursor, a part of liquid phase is used for pulping the impurity removing solid phase of the step S3, and a part of liquid phase enters a wastewater station for subsequent treatment;
s5, converting ammonia into copper hydroxide:
adding water into the copper master batch precursor in the step S4 according to the solid-to-liquid ratio of 1:2 to prepare slurry, adding ammonia water with the mass concentration of 20%, adjusting and maintaining the reaction pH at 12, maintaining the reaction temperature at 40 ℃, reacting for 2 hours, carrying out solid-liquid separation, removing impurities from the solid phase until the pH of the water is 10, and drying at a low temperature of 40 ℃ to obtain a copper hydroxide product.
And (3) adsorbing and recovering copper from a liquid phase obtained after synthesizing the copper master batch precursor by using ion exchange resin, and concentrating by using MVR evaporation to recover an ammonium chloride product.
Result detection
The embodiment and the comparative example are tested for the manganese content and the iron content of the impurity-removed liquid after impurity removal, and the specific testing method refers to the national standard inductively coupled plasma emission spectrometry (ICP-OES) for testing impurity elements of inorganic chemical products (GB/T30902-2014).
The specific detection results are shown in Table 1 below.
Table 1. The main properties of the impurity removing liquid are as follows:
in the embodiment of the invention, the COD of the system in the S2 impurity removal step is more than 3000mg/L, the COD in the system is removed by the synergistic effect of the alkaline potassium permanganate waste liquid and the electroless copper plating waste liquid, the COD is reduced to below 300mg/L, and the COD is further removed to below 90mg/L by activated carbon adsorption.
As can be seen from the data in the table 1, in the method for producing copper hydroxide by using the circuit board waste, the impurity removal step can realize the effective separation and recovery of iron and copper, and the ferromanganese slag product and the pure copper chloride solution are obtained.
In comparative example 1, the COD was reduced to 90mg/L or less, and the content of manganese and iron in the impurity-removed liquid was low, but the leaching rate of copper was significantly reduced by 43%, and it was apparent that efficient recovery of copper from circuit board waste could not be achieved. The impurity removing solutions in comparative example 2 and comparative example 3 have significantly higher manganese content and iron content than the present invention, and obviously, high-efficiency separation and recovery of iron and copper cannot be achieved.
The properties of the copper hydroxide products of the examples and comparative examples of the present invention were examined in relation to each other, and the specific examination results are shown in Table 2 below.
TABLE 2 principal Properties of copper hydroxide products
| Sequence number | Copper/% | Copper hydroxide/% |
| Example 1 | 63.34 | 97.23 |
| Example 2 | 63.65 | 97.70 |
| Example 3 | 63.26 | 97.10 |
| Comparative example 1 | 62.51 | 95.95 |
| Comparative example 2 | 57.36 | 88.05 |
| Comparative example 3 | 61.73 | 94.76 |
From the detection results in table 2, it can be seen that the copper hydroxide content of the copper hydroxide product can reach more than 97%, the copper content is more than 63%, the high-efficiency recycling of the circuit board waste is realized, and the high-quality copper hydroxide product is prepared.
The content of lead, arsenic and cadmium in the copper hydroxide product prepared by the method is below 5mg/kg, and the water content of the product is below 1.5%.
The invention fully utilizes the self characteristics of the circuit board sludge, the alkaline potassium permanganate waste liquid and the electroless copper plating waste liquid, and can effectively remove most COD and impurity metals to obtain pure impurity-removing acid liquid; by utilizing the complex ammonia leaching method of ammonium chloride-ammonia water, residual copper in the impurity-removed slag can be effectively leached out without introducing impurity anions basically, so that pure ammonia leaching liquid is obtained, the maximum recycling of copper resources is realized, and a copper hydroxide product with excellent quality is prepared. Meanwhile, the method realizes the treatment of three kinds of hazardous wastes by wastes, and compared with the independent treatment of various wastes in the industry, the method greatly reduces the investment of chemical raw materials such as oxidants, alkali liquor and the like, and can save about 500-1000 yuan per ton of cooperative treatment of the three kinds of wastes.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The method for producing copper hydroxide by using the circuit board waste is characterized by comprising the following steps:
s1, preparing acidified slurry: activating the sludge of the circuit board, adding the activated sludge into hydrochloric acid, and adjusting the pH to 2.5-3.0 to obtain acidified slurry;
s2, removing impurities: adding alkaline potassium permanganate waste liquid into the acidified slurry, adjusting the pH to 3.2-3.5, reacting for 0.5-1 h at 70-90 ℃, adding electroless copper plating waste liquid until the purple of a reaction system is resolved, reacting for 15-30 min, and carrying out solid-liquid separation to obtain a impurity-removing solid phase, and removing COD (chemical oxygen demand) from the liquid phase to obtain an impurity-removing liquid;
s3, ammonia leaching: fully mixing the impurity-removed solid phase with an ammonia-containing solution, stirring, pulping, sieving, adding ammonia water to adjust the pH value to 8-8.8, reacting for 0.5-1 h at 45-55 ℃, carrying out solid-liquid separation, and removing COD (chemical oxygen demand) from the liquid phase to obtain an ammonia leaching solution;
s4, preparing a copper master batch precursor: the impurity removing liquid in the step S2 and the ammonia leaching liquid in the step S3 are subjected to parallel flow reaction, the pH of the reaction is maintained to be 4.0-5.0, the reaction is carried out for 2-4 hours at 20-60 ℃, solid-liquid separation is carried out, and the solid phase is a copper-bearing precursor;
s5, converting ammonia into copper hydroxide: adding water into the copper master batch precursor in the step S4 to prepare slurry, adding ammonia water to adjust the pH value to 10-12, reacting for 1-2 hours at 20-60 ℃, carrying out solid-liquid separation, removing residual alkali through solid phase, and drying to obtain a copper hydroxide product.
2. The method for producing copper hydroxide by using circuit board waste according to claim 1, wherein the concentration of hydrochloric acid in S1 is 10-15% by mass.
3. The method for producing copper hydroxide according to claim 1, wherein the ammonia-containing solution in S3 is a liquid-phase copper alloy mother liquor separated from solid-liquid in S4.
4. The method for producing copper hydroxide by using circuit board waste according to claim 3, wherein the weight ratio of the impurity removal solid phase in S3 to the copper master batch is 1:1.5-3.
5. The method for producing copper hydroxide by using circuit board waste as claimed in claim 1, wherein the liquid phase obtained by solid-liquid separation in the step S5 is copper ammonia solution, and the copper ammonia solution is recycled to the step S4 to be used as ammonia immersion liquid for preparing copper master precursor.
6. The method for producing copper hydroxide from circuit board waste according to claim 1, wherein the mass concentration of ammonia water in S3 and S5 is 15-20%.
7. The method for producing copper hydroxide by using circuit board waste according to any one of claims 1 to 6, wherein the potassium permanganate waste liquid has a potassium permanganate mass content of 4.5 to 5%, a COD content of 1000 to 2000mg/L and a pH of not less than 12.
8. The method for producing copper hydroxide from circuit board waste according to any one of claims 1 to 6, wherein the copper content of the electroless copper plating waste liquid is 0.5 to 1g/L, the COD content is 32 to 35g/L, and the pH is not less than 12.
9. The method for producing copper hydroxide from circuit board waste according to any one of claims 1 to 6, wherein the copper content of the circuit board sludge is 6 to 6.5% and the iron content is 7 to 10%.
10. A copper hydroxide produced by the method for producing copper hydroxide from the circuit board waste according to any one of claims 1 to 6.
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