CN113787078A - Method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recycling valuable metals - Google Patents
Method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recycling valuable metals Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 51
- 239000002910 solid waste Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 150000002739 metals Chemical class 0.000 title claims abstract description 18
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title claims description 7
- 239000010949 copper Substances 0.000 claims abstract description 71
- 238000002386 leaching Methods 0.000 claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 claims abstract description 64
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005751 Copper oxide Substances 0.000 claims abstract description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 14
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000011084 recovery Methods 0.000 description 13
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- 229910052794 bromium Inorganic materials 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- 238000001914 filtration Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 239000007769 metal material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 copper and the like Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
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Abstract
The invention discloses a method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recovering valuable metals. Leaching the solid waste of the epoxy resin powder by adopting concentrated sulfuric acid and hydrogen peroxide solution to obtain copper-containing leaching solution and leaching residues; precipitating copper from the copper-containing leachate by adjusting the pH value to obtain a copper-containing precipitate; and washing, drying and calcining the copper-containing precipitate to obtain the copper oxide. The method utilizes concentrated sulfuric acid and hydrogen peroxide solution to perform synergistic oxidation leaching on the epoxy resin powder solid waste, can realize deep degradation of polybrominated diphenyl ethers in the epoxy resin powder solid waste, simultaneously converts metal copper into divalent copper ions easy to precipitate and recover, and obtains leaching residues capable of being used as building materials, so that harmless and resource utilization of the epoxy resin powder solid waste can be realized.
Description
Technical Field
The invention relates to a method for treating epoxy resin powder solid waste, in particular to a method for degrading polybrominated diphenyl ethers in the epoxy resin powder solid waste and recovering valuable metals such as copper and the like, belonging to the technical field of environmental protection and comprehensive recovery of solid waste resources.
Background
With the rapid development of the information industry, the production of circuit boards is rapidly increasing. In recent years, the annual average growth rate of the world printed circuit board industry is 8% -9%, and the growth rate in China is 14.4%. So far, about 40% of circuit boards are produced in China globally, and China has become the second largest world production country of circuit boards. The amount of waste printed circuit boards to be processed in continents of China is over 50 million tons every year. The world board market is growing rapidly, however the amount of waste is also increasing dramatically.
The circuit board is a mixture of epoxy resin, glass fiber and various metals, wherein the grade of the contained metals is dozens of times or even hundreds of times of that of natural mineral deposits. The value of metals has been a direct driver of waste circuit board recycling. At present, the most main industrialized recovery method of the waste circuit boards is mechanical recovery, namely, the waste circuit boards are separated and enriched through three process steps of disassembling, crushing and sorting according to the difference of physical and chemical properties among the components of the circuit boards. The sorted and enriched metal can be sent to a metal smelting company for further processing or electrolytic purification. And the epoxy resin powder (namely, the non-metallic material) which accounts for more than 70 percent of the mass of the circuit board is found through research, and the main component of the waste circuit board resin powder is epoxy resin, a small amount of glass fiber and a small amount of copper metal, and trace amounts of other metals and substances (see figure 1). Due to the complex components and relatively low recovery value, and the polybrominated diphenyl ether flame retardant is contained in the flame retardant. Polybrominated diphenyl ethers are widely used due to their good thermal stability, low price, high flame retardant efficiency, but they exhibit the characteristics of persistent organic pollutants after entering the environment: difficult degradation, easy migration and easy enrichment, and causes harm to the environment and human health. Therefore, in the process of recovering the metal in the circuit board, a large amount of epoxy resin powder is generated, and if the epoxy resin powder is not subjected to necessary treatment and is randomly stacked, not only a large amount of land is occupied, but also the environment is seriously polluted. Both incineration and landfill may cause secondary pollution and waste available resources.
At present, a physical recovery method of waste circuit board epoxy resin powder is a research hotspot, the recovery technology of the physical method does not need to change the state of a non-metal material, the treatment is simple, and the cost is low, but the application range of the product is also limited because the waste circuit board epoxy resin powder contains a certain amount of metal and the flame retardant is not removed. The reduction method reported in the literature at present is used for degrading polybrominated diphenyl ethers, and the debromination rate is the same. On one hand, the strong lipophilic hydrophobicity of the polybrominated diphenyl ether, and the multiple use of toxic organic solvents such as acetonitrile, acetone, toluene and the like do not meet the basic requirements of green chemistry and environmental protection; on the other hand, the reduction degradation can remove the high-brominated polybrominated diphenyl ethers relatively quickly, but the low-brominated intermediate products are difficult to be further reduced and accumulated in a large amount, and the debromination rate is not high. The low brominated diphenyl ethers have higher biotoxicity and greater harm to the environment and human body. Therefore, the research of the processing technology aiming at the epoxy resin powder in the waste circuit board is urgent, and the efficient degradation of the polybrominated diphenyl ethers is realized under the green reaction condition.
Disclosure of Invention
Aiming at the technical problems that a large amount of residual epoxy resin powder after valuable metals are extracted from a waste circuit board in the prior art contains toxic and harmful substances, namely polybrominated diphenyl ether flame retardant, and the conventional incineration and landfill method causes potential harm to the surrounding environment, the invention aims to provide a method for carrying out strong oxidation acid leaching on epoxy resin powder solid waste through the synergistic action of concentrated sulfuric acid and hydrogen peroxide solution and simultaneously realizing efficient oxidative degradation of polybrominated diphenyl ether and efficient oxidative leaching of metal copper, the method can efficiently recover valuable metals such as copper in the epoxy resin powder solid waste while realizing the harmless treatment of the epoxy resin powder solid waste, and the oxidative leaching residues are mainly glass fibers and the like and can be used as building materials or composite materials, thereby realizing the resource utilization of the epoxy resin powder solid waste; the method has the advantages of simplicity, rapidness, high efficiency, simple process, convenience in operation and the like, can realize harmless and resource comprehensive utilization of the waste circuit board resin powder, and has very important significance.
In order to realize the technical purpose, the invention provides a method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recovering valuable metals, which comprises the following steps:
1) leaching the epoxy resin powder solid waste by adopting concentrated sulfuric acid and hydrogen peroxide solution to obtain copper-containing leaching solution and leaching residues;
2) precipitating copper from the copper-containing leachate by adjusting the pH value to obtain a copper-containing precipitate;
3) and washing, drying and calcining the copper-containing precipitate to obtain the copper oxide.
The method utilizes the synergistic oxidation leaching of the concentrated sulfuric acid and the hydrogen peroxide solution to leach the solid waste of the epoxy resin powder, and the concentrated sulfuric acid and the hydrogen peroxide solution are mixed to generate the atomic oxygen (H) with high oxidation activity2SO4+H2O2＝H3O++HSO4- + O), the atomic oxygen has higher oxidation activity, not only can attack C-Br bond in polybrominated diphenyl ether to realize the removal of bromine element in the polybrominated diphenyl ether and enter the leachate in the form of soluble bromine salt to enable the polybrominated diphenyl ether to be deeply degraded, but also can oxidize metal copper into bivalent copper and be leached by sulfuric acid to enter the solution, the separation and recovery are easy to be carried out in a subsequent precipitation mode, and finally, slag phase after oxidation and leaching is mainly glass fiber and the like and can be reused as building materials.
As a preferable scheme, the volume ratio of concentrated sulfuric acid to hydrogen peroxide solution is 3-4: 1; the mass percentage concentration of the hydrogen peroxide solution is 25-35%. The mixed acid solution rich in atomic oxygen content can be obtained by controlling the proportion of concentrated sulfuric acid and hydrogen peroxide.
As a preferred embodiment, the leaching conditions are: the liquid-solid ratio L/S is 5-8 mL/g, the temperature is 20-25 ℃, and the time is 0.5-1 h. The strong oxidation leaching of the epoxy resin powder solid waste by using the mixed solution of concentrated sulfuric acid and hydrogen peroxide solution has mild conditions, can be carried out at normal temperature, and has short leaching time. Through the optimized leaching conditions, the polybrominated diphenyl ethers in the epoxy resin powder solid waste can be efficiently degraded, and the efficient oxidation leaching of the metal copper is realized.
As a preferable scheme, the pH value is adjusted to be 6.8-7.2 in the copper precipitation process. The pH is adjusted by using inorganic base commonly used in the prior art, such as sodium hydroxide, potassium hydroxide and the like.
As a preferred embodiment, the calcination conditions are: the temperature is 500-550 ℃ and the time is 0.5-1 h. The calcination is mainly to convert the hydroxide of copper and the like into copper oxide.
The epoxy resin powder solid waste is obtained by recovering metal from waste circuit boards through the process steps of disassembling, crushing, sorting and the like, wherein the main component is epoxy resin, and a small amount of glass fiber, a small amount of copper metal and trace amounts of other metals and substances (the main components are shown in figure 1).
The invention provides a method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recovering valuable metals, which comprises the following steps:
A) strong oxidation acid leaching: carrying out oxidation leaching on the epoxy resin powder solid waste in a mixed system of concentrated sulfuric acid and 30% hydrogen peroxide solution to obtain copper-containing leaching solution and leaching residues, wherein the leaching residues are mainly inorganic materials such as glass fibers and can be used as building materials and the like;
B) recovering the copper-containing compound: adjusting the pH value of the copper-containing leaching solution in the step A) to a proper value, so that copper ions are converted into copper precipitates, and obtaining the copper precipitates after solid-liquid separation.
C) And (3) recovering copper oxide: and washing and drying the copper precipitate, and calcining to obtain the copper oxide.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the invention leads the epoxy resin powder solid waste to be subjected to strong oxidation leaching under the synergistic action of concentrated sulfuric acid and hydrogen peroxide solution at normal temperature and normal pressure, not only can realize the harmless treatment of the epoxy resin powder solid waste, but also can realize the oxidation leaching of metal copper, and is easy to realize precipitation recovery. After being mixed, concentrated sulfuric acid and hydrogen peroxide can generate high-activity atomic oxygen which is an extremely strong oxidant, can attack C-Br bonds in polybrominated diphenyl ethers and realize deep degradation, so that pollutants are thoroughly removed and mineralized, bromine elements in the polybrominated diphenyl ethers are removed and enter a leaching solution in the form of soluble bromine salt, and reducing resin, glass fiber and the like enter leaching residues; the copper in the resin powder is converted into Cu due to strong oxidation during leaching2And + the copper-containing substance is converted into copper precipitate by adding alkali to adjust the pH value, and the copper oxide is obtained after washing, drying and calcining, so that the problem of harmlessness of degradation of waste circuit board resin powder polybrominated diphenyl ethers is solved.
2. The method realizes the harmless deep bromine removal of the epoxy resin powder solid waste, also efficiently recovers the valuable metal copper of the resin powder, and the recovered slag can be used as building materials, composite materials and the like, thereby realizing the resource comprehensive utilization of the epoxy resin powder solid waste.
3. The technical method has the characteristics of simple process, convenient operation, rapidness, high efficiency, low cost and the like, and meets the requirement of industrial production.
Drawings
FIG. 1 shows the main components of the solid waste of epoxy resin powder.
FIG. 2 is a process flow chart of the degradation of polybrominated diphenyl ethers in epoxy resin powder solid waste and valuable metal recovery.
Detailed Description
For the convenience of clear understanding of the technical solutions of the present invention, the following detailed description is made with reference to the embodiments, but the scope of the present invention is not limited by the embodiments.
Example 1
The waste circuit board epoxy resin powder to be treated contains 2.645% of bromine and 1.63% of copper. Placing 600g of waste circuit board epoxy resin powder solid waste into a solution of 3L of concentrated sulfuric acid and 30% of hydrogen peroxide for strong oxidative leaching, wherein the leaching conditions are as follows: the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 3.5:1, the leaching temperature is 25 ℃, the leaching pressure is normal pressure, and the leaching time is 1h, so that polybrominated diphenyl ethers in the waste resin powder solid waste of the waste circuit board are degraded, and simultaneously, valuable metal copper is converted into copper ions, and a leaching solution containing the copper ions and leaching residues (mainly containing glass fibers and capable of being used as building materials) are obtained. Adding sodium hydroxide solution into the leachate for precipitation reaction, controlling the pH value to be 7, filtering to obtain copper precipitate, washing the obtained copper precipitate, drying the copper precipitate in a drying oven at 105 ℃ for 1h, and then calcining the copper precipitate in a tube furnace at 550 ℃ for 0.5h to obtain copper oxide, wherein the purity of the copper oxide is 92.35%, and the separation efficiency of copper ions is 98.53%. The results are shown in Table 1.
TABLE 1 results of bromine degradation and copper recovery in epoxy resin powder solid waste
| Sample (I) | Br content (%) | Br extraction (%) | Cu content (%) | Cu leaching rate (%) |
| Raw sample (%) | 2.645 | —— | 1.63 | —— |
| Leaching slag | 0.179 | 6.55 | 0.03 | 98.3 |
| Filtrate | 4943.505 | 93.45 | —— | —— |
Comparative example 1
The waste circuit board epoxy resin powder to be treated contains 2.645% of bromine and 1.63% of copper. Placing 600g of waste circuit board epoxy resin powder solid waste into a solution of 3L of concentrated sulfuric acid and 30% of hydrogen peroxide for strong oxidative leaching, wherein the leaching conditions are as follows: the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 2.5:1, the leaching temperature is 25 ℃, the leaching pressure is normal pressure, and the leaching time is 1h, so that polybrominated diphenyl ethers in the waste resin powder solid waste of the waste circuit board are degraded, and simultaneously, valuable metal copper is converted into copper ions, and a leaching solution containing the copper ions and leaching residues (mainly containing glass fibers and capable of being used as building materials) are obtained. Adding sodium hydroxide solution into the leachate for precipitation reaction, controlling the pH value to be 7, filtering to obtain copper precipitate, washing the obtained copper precipitate, drying the copper precipitate in a drying oven at 105 ℃ for 1h, and then calcining the copper precipitate in a tube furnace at 550 ℃ for 0.5h to obtain copper oxide, wherein the purity of the copper oxide is 92.35%, and the separation efficiency of copper ions is 96.47%. The results are shown in Table 2. As can be seen from table 2, the bromine removal effect was reduced when the leaching reaction conditions were changed.
TABLE 2 results of bromine degradation and copper recovery in epoxy resin powder solid waste
Example 2
The method is adopted to treat the solid waste of the waste circuit board resin powder containing 2.328 percent of bromine and 1.49 percent of copper. Placing 600g of waste circuit board resin powder solid waste into 3L of concentrated sulfuric acid and 30% hydrogen peroxide solution for strong oxidative leaching, wherein the leaching conditions are as follows: the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 3.8:1, the leaching temperature is 20 ℃, the leaching pressure is normal pressure, and the leaching time is 1h, so that polybrominated diphenyl ethers in the waste resin powder solid waste of the waste circuit board are degraded, and simultaneously, valuable metal copper is converted into copper ions, and a leaching solution containing the copper ions and leaching residues (mainly containing glass fibers and capable of being used as building materials) are obtained. Adding sodium hydroxide solution into the leachate for precipitation reaction, controlling the pH value to be 7.2, filtering to obtain copper precipitate, washing the obtained copper precipitate, drying the copper precipitate for 1h in a drying oven at 105 ℃, and then calcining the copper precipitate for 0.6h in a tubular furnace at 530 ℃ to obtain copper oxide, wherein the purity of the copper oxide is 91.78%, and the separation efficiency of copper ions is 98.26%. The results are shown in Table 3.
TABLE 3 degradation of bromine and recovery of copper results from epoxy resin powder solid waste
| Sample (I) | Br content (%) | Br extraction (%) | Cu content (%) | Cu leaching rate (%) |
| Raw sample (%) | 2.328 | —— | 1.49 | —— |
| Leaching slag | 0.157 | 7.13 | 0.03 | 97.9 |
| Filtrate | 4324.027 | 92.87 | —— | —— |
Comparative example 2
The method is adopted to treat the solid waste of the waste circuit board resin powder containing 2.328 percent of bromine and 1.49 percent of copper. Placing 600g of waste circuit board resin powder solid waste into 3L of concentrated sulfuric acid and 30% hydrogen peroxide solution for strong oxidative leaching, wherein the leaching conditions are as follows: the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 2.5:1, the leaching temperature is 20 ℃, the leaching pressure is normal pressure, and the leaching time is 1h, so that polybrominated diphenyl ethers in the waste resin powder solid waste of the waste circuit board are degraded, and simultaneously, valuable metal copper is converted into copper ions, and a leaching solution containing the copper ions and leaching residues (mainly containing glass fibers and capable of being used as building materials) are obtained. Adding sodium hydroxide solution into the leachate for precipitation reaction, controlling the pH value to be 7.2, filtering to obtain copper precipitate, washing the obtained copper precipitate, drying the copper precipitate in a drying oven at 105 ℃ for 1h, and then calcining the copper precipitate in a tubular furnace at 530 ℃ for 0.6h to obtain copper oxide, wherein the purity of the copper oxide is 90.62%, and the separation efficiency of copper ions is 95.76%. The results are shown in Table 4.
TABLE 4 results of bromine degradation and copper recovery from epoxy resin powder solid waste
| Sample (I) | Br content (%) | Br extraction (%) | Cu content (%) | Cu leaching rate (%) |
| Raw sample (%) | 2.328 | —— | 1.49 | —— |
| Leaching slag | 0.270 | 11.27 | 0.08 | 94.8 |
| Filtrate | 4131.269 | 88.73 | —— | —— |
Claims (5)
1. A method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recovering valuable metals is characterized by comprising the following steps: the method comprises the following steps:
1) leaching the epoxy resin powder solid waste by adopting concentrated sulfuric acid and hydrogen peroxide solution to obtain copper-containing leaching solution and leaching residues;
2) precipitating copper from the copper-containing leachate by adjusting the pH value to obtain a copper-containing precipitate;
3) and washing, drying and calcining the copper-containing precipitate to obtain the copper oxide.
2. The method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recycling valuable metals according to claim 1, which is characterized in that: the volume ratio of concentrated sulfuric acid to hydrogen peroxide solution is 3-4: 1; the mass percentage concentration of the hydrogen peroxide solution is 25-35%.
3. The method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recycling valuable metals according to claim 1, which is characterized in that: the leaching conditions are as follows: the liquid-solid ratio L/S is 5-8 mL/g, the temperature is 20-25 ℃, and the time is 0.5-1 h.
4. The method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recycling valuable metals according to claim 1, which is characterized in that: and adjusting the pH value to 6.8-7.2 in the copper precipitation process.
5. The method for degrading polybrominated diphenyl ethers in epoxy resin powder solid waste and recycling valuable metals according to claim 1, which is characterized in that: the calcining conditions are as follows: the temperature is 500-550 ℃ and the time is 0.5-1 h.
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