CN117646115A - Scrapped Pd/Al 2 O 3 Cooperative recovery method of catalyst and copper-containing waste - Google Patents
Scrapped Pd/Al 2 O 3 Cooperative recovery method of catalyst and copper-containing waste Download PDFInfo
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- CN117646115A CN117646115A CN202311624508.4A CN202311624508A CN117646115A CN 117646115 A CN117646115 A CN 117646115A CN 202311624508 A CN202311624508 A CN 202311624508A CN 117646115 A CN117646115 A CN 117646115A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000010949 copper Substances 0.000 title claims abstract description 112
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 112
- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 133
- 238000002386 leaching Methods 0.000 claims abstract description 56
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000004070 electrodeposition Methods 0.000 claims abstract description 33
- 238000004064 recycling Methods 0.000 claims abstract description 26
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 23
- 239000000571 coke Substances 0.000 claims abstract description 19
- 238000003723 Smelting Methods 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003546 flue gas Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000428 dust Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000010802 sludge Substances 0.000 claims description 15
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 229940062993 ferrous oxalate Drugs 0.000 claims description 9
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004071 soot Substances 0.000 claims description 8
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000023556 desulfurization Effects 0.000 description 13
- -1 copper and palladium Chemical class 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 238000007256 debromination reaction Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 238000003912 environmental pollution Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000002341 toxic gas Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- C22B7/001—Dry processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
- B03C3/017—Combinations of electrostatic separation with other processes, not otherwise provided for
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
- C22B11/028—Recovery of noble metals from waste materials from spent catalysts using solid sorbents, e.g. getters or catchment gauzes
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- 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
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2022—Bromine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of rare noble metal regeneration, and discloses a scrapped Pd/Al 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste comprises the following steps of: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture; step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy; step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution; step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium; step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper. The invention realizes the synergistic recovery of copper and palladium in copper-containing waste and waste catalyst, completes the harmless treatment of hazardous waste, avoids consuming a large amount of acid and organic matters, has the characteristics of high production efficiency, low cost, large income and no pollution, and is suitable for industrial application.
Description
Technical Field
The invention relates to the technical field of rare noble metal regeneration, in particular to a scrapped Pd/Al 2 O 3 A method for the co-recovery of a catalyst and copper-containing waste.
Background
With the continuous improvement of the industrial development level in China, the demands for various strategic metals are continuously increased. The secondary resources such as the waste catalyst, the waste circuit board, the copper-containing sludge and the like are rich in strategic metals, and the recycling of the waste catalyst, the waste circuit board, the copper-containing sludge and the like has remarkable economic and strategic values, and the Pd/Al is scrapped 2 O 3 The catalyst is derived from petrochemical industry and is commonly used for realizing selective hydrogenation reaction, such as hydrogen peroxide, aromatic aldehyde, nitroaromatic compound and the like. Copper-containing waste such as waste circuit boards and copper-containing sludge is rich in strategic metals such as copper and palladium, and toxic heavy metals such as lead, zinc, tin and nickel. Scrapped Pd/Al 2 O 3 The catalyst, the waste circuit board and the copper-containing sludge are all hazardous wastes, and the recycling of the catalyst, the waste circuit board and the copper-containing sludge saves resources and protects the environmentThe protection has important significance.
At present, common methods for recovering palladium from waste catalysts are mainly classified into wet methods and fire methods. The wet process adopts acid, alkali and other leaching systems to transfer palladium from solid phase to liquid phase. The application number CN201810670273.5 discloses a method for recycling palladium from palladium-containing waste in a green way, which comprises the steps of carrying out ball milling and other pretreatment on the palladium-containing waste, carrying out oxidative leaching by acid and iron ions, and then carrying out resin adsorption, desorption and reduction to obtain palladium powder. The method has the advantages of low cost and simple operation, but has the problems of long recovery period, large acid-containing wastewater amount and the like. The pyrometallurgy process is to smelt the waste catalyst with the trapping agent, the fluxing agent and the reducing agent, and finally, palladium is gathered and settled into a metal phase to realize enrichment. The application number CN201911178983.7 discloses a method for collecting and crushing the iron-based alloy to recover the platinum group metals, which adopts iron powder as a collecting agent to smelt and recover the platinum group metals, and a large amount of aluminum and zinc are added as a crushing agent in order to make the alloy easy to crush and dissolve. The platinum group metals are subsequently recovered by two acidolysis. The method has high recovery rate of platinum group metals and short recovery period, but uses a large amount of iron powder, aluminum powder and zinc powder, and has high cost and large subsequent acid leaching amount. The application number CN201710856842.0 discloses a method for capturing platinum group metals by microwave heating and melting, which realizes the efficient recovery of the platinum group metals in the platinum group metal-containing waste catalyst at a lower smelting temperature, but cannot realize mass production at the present stage and is easy to generate a large amount of S-containing pollutant gas.
The current recovery method of copper-containing waste materials such as copper-containing sludge and waste circuit boards comprises a pyrolysis method and a smelting method, and the application number of the method is CN201911359327.7, which discloses a method for cooperatively disposing waste circuit board pyrolysis slag and smelting soot. The application number CN201810230086.5 discloses a method for recovering valuable metals from waste circuit boards, which solves the disposal problem of various wastes, but does not recover palladium in the waste circuit.
In summary, the current methods for palladium recovery and copper recovery have the problems of high cost, large pollution and low direct yield.
Disclosure of Invention
The invention aims to provide a scrapped Pd/Al 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste solves the problems of high cost, large pollution and low direct yield of the palladium-containing waste catalyst and the copper-containing waste recycling technology in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme: scrapped Pd/Al 2 O 3 A method for the co-recovery of a catalyst and copper-containing waste comprising the steps of:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
Preferably, as an improvement, the composition parts by weight of the mixture in the step 1 are: scrapped Pd/Al 2 O 3 50 parts of catalyst, 40-60 parts of copper-containing waste, 5-10 parts of coke and 40-100 parts of fluxing agent.
Preferably, as an improvement, the composition parts by weight of the mixture in the step 1 are: scrapped Pd/Al 2 O 3 50 parts of catalyst, 40 parts of copper-containing waste, 10 parts of coke and 80 parts of fluxing agent.
Preferably, as an improvement, the copper-containing waste is: 20-30 wt.% of copper-containing sludge, 40-60 wt.% of waste circuit board and 10-20 wt.% of scrap copper, wherein the fluxing agent is as follows: 60 to 80wt.% of calcium oxide, 10 to 30wt.% of ferrous oxalate and 10 to 20wt.% of borax. The copper content in the copper-containing waste materials is higher, and the copper-containing waste materials have higher recycling value.
Preferably, as an improvement, the mixture in the step 2 is heated and melted at 1000-1300 ℃ and then is kept for 20-40 min, and then the crude copper alloy is obtained by casting and slag-gold separation.
Preferably, as an improvement, the flue gas generated by smelting in the step 2 is firstly subjected to dust removal by a cooling tower and a cloth bag to collect soot, and then is subjected to dioxin removal and desulfurization by an alkaline absorption tower and an electric demister to be exhausted. The flue gas generated by the melting furnace is subjected to dust removal, debromination, dioxin removal and desulfurization, so that the treated flue gas meets the emission requirement, and the environmental pollution is reduced.
Preferably, as an improvement, in the step 3, acid and hydrogen peroxide are used as leaching agents, and in the step 3, leaching conditions are as follows: the solid-liquid ratio is 1:5-20 g/mL, H + Concentration of 2-8 mol/L, H 2 O 2 The volume fraction is 2-10%.
Preferably, as a modification, the leaching conditions in the step 3 are as follows: the solid-liquid ratio is 1:10g/mL, H + Concentration of 4mol/L, H 2 O 2 Volume fraction 6%.
Preferably, as a modification, the electrolyte adopted in the step 4 is the leaching solution generated in the step 3, stainless steel or platinum sheet is adopted as an electrode in the step 4, and the primary electrodeposition condition in the step 4 is as follows: the cell voltage is 0.4-1.0V, and the temperature is 25-90 ℃. The leaching solution generated in the previous step is used as electrolyte, so that the cost is saved; meanwhile, new substances are avoided being added, production procedures are reduced, production efficiency is improved, and subsequent treatment of the new substances is avoided; the bath voltage in this step is less than the electrodeposition voltage of copper, avoiding simultaneous electrodeposition of copper and palladium.
Preferably, as a modification, the secondary electrodeposition condition in the step 5 is: the tank voltage is 1.5-3.0V and the temperature is 25-90 ℃.
The principle of the scheme is as follows:
although copper-containing sludge and waste circuit boards contain metal components, the metal components are difficult to enrich and separate, and the inventor grafts waste Pd/Al 2 O 3 Al content in the catalyst up to 80% 2 O 3 The copper scraps are subjected to slag formation, so that the metal components in the copper scraps are enriched and separated; in addition, waste Pd/Al 2 O 3 Initial palladium concentration in the catalyst is extremely low, and conventional processIt is difficult to form large enough particles by collision aggregation to overcome the viscous force and settle, and the inventor forms solid solution with copper to form metal particles with critical size or more, and then the metal particles settle to the bottom by gravity to realize enrichment separation.
Finally, by utilizing the difference between palladium and copper on the standard electrode potential, an acidic condition is created, and by controlling the potential, palladium is deposited preferentially due to lower reduction potential, and after palladium is deposited cleanly, the voltage is increased to deposit copper.
The beneficial effect of this scheme:
1) The method cooperatively disposes the waste palladium catalyst and the copper-containing waste, and realizes harmless disposal of various hazardous wastes;
2) According to the invention, copper in the copper-containing waste is used as a trapping agent, so that the recovery cost of palladium in the waste catalyst is reduced, and the cooperative regeneration of various strategic metals is realized;
3) The method adopts quicklime, ferrous oxalate and borax as fluxing agents to construct CaO-Al 2 O 3 -SiO 2 -FeO-Na 2 O-B 2 O 3 Slag phase melting point and viscosity are obviously reduced, so that energy consumption is reduced and metal recovery rate is improved;
4) The method carries out the treatments of bag-type dust removal, debromination, dioxin removal and desulfurization of the flue gas, and the flue gas meets the emission requirement;
5) The method adopts an electrodeposition method to separate and recycle palladium and copper, shortens the recycling flow and the production period, avoids using organic reagents, and has the characteristics of high efficiency, environmental protection and safety.
Drawings
Fig. 1 is a schematic flow chart of an embodiment of the present invention.
Detailed Description
The following is a further detailed description of the embodiments:
example 1:
the embodiment comprises the following components in parts by weight: 50 parts of scrap Pd/Al 2 O 3 Catalyst, 40 parts copper-containing waste, 10 parts coke and 80 parts fluxing agent, to illustrate scrapped Pd/Al 2 O 3 The co-recovery process of the catalyst and the copper-containing waste material specifically comprises the following steps:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
wherein the mixture comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 40-60 parts of copper-containing waste, 5-10 parts of coke and 40-100 parts of fluxing agent. The composition of the mixture in this example is specifically in parts by weight of Pd/Al scrap 2 O 3 50 parts of catalyst, 40 parts of copper-containing waste, 10 parts of coke and 80 parts of fluxing agent.
Wherein the copper-containing waste is: 20-30 wt.% of copper-containing sludge, 40-60 wt.% of waste circuit board and 10-20 wt.% of scrap copper, and in the embodiment, 30wt.% of copper-containing sludge, 50wt.% of waste circuit board and 20wt.% of scrap copper. The fluxing agent is as follows: 60-80 wt.% of calcium oxide, 10-30 wt.% of ferrous oxalate and 10-20 wt.% of borax, in this embodiment 80wt.% of calcium oxide, 10wt.% of ferrous oxalate and 10wt.% of borax.
Step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
wherein the mixture is heated and melted at 1000-1300 ℃ (1200 ℃ in the embodiment) and then is kept for 20-40 min (30 min in the embodiment), and then the crude copper alloy is obtained by casting and slag-gold separation.
The flue gas generated by smelting in the step firstly passes through a cooling tower and a cloth bag for dust removal to collect soot, and then passes through an alkaline absorption tower and an electric demister for dioxin removal and desulfurization, and then is exhausted. Wherein the ash discharged from the cooling tower and the bag-type dust collector contains lead, tin and zinc components, and the extraction and the utilization are carried out subsequently. The flue gas generated by the melting furnace is subjected to dust removal, debromination, dioxin removal and desulfurization, so that the treated flue gas meets the emission requirement, and the environmental pollution is reduced.
Step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
in the step, acid and hydrogen peroxide are selected as leaching agents, so that carrier dissolution and toxic gases such as Cl are reduced 2 Is volatilized, and the reaction equation is as follows:Pd+2H + +4Cl - +H 2 O 2 ＝[PdCl 4 ] 2- +2H 2 o. The leaching conditions in this step are: the solid-liquid ratio is 1:5-20 g/mL, H + Concentration of 2-8 mol/L, H 2 O 2 The volume fraction is 2-10%. In the embodiment, the solid-liquid ratio is 1:10g/mL, H + Concentration of 4mol/L, H 2 O 2 Volume fraction 6%.
Step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
in the step, the leaching liquid produced in the step 3 is used as the electrolyte in the step, and the leaching liquid produced in the previous step is used as the electrolyte, so that the cost is saved. In this step, stainless steel or platinum sheet is used as an electrode, and the cell voltage is 0.4 to 1.0V (0.5V in this example) and the temperature is 25 to 90 ℃ (60 ℃ in this example). The bath voltage in this step is less than the electrodeposition voltage of copper, avoiding simultaneous electrodeposition of copper and palladium. The recovery of palladium in this example was found to be 98.3%.
Step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
The cell voltage in this step is 1.5-3.0V (2V in this example) and the temperature is 25-90 ℃ (60 ℃ in this example). The electrolyte and the electrode used for electrolysis in this step are the same as in step 4. The copper recovery in this example was found to be 99.6%.
Example 2:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
wherein the mixture comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 60 parts of copper-containing waste, 5 parts of coke and 50 parts of fluxing agent.
Wherein the copper-containing waste is: 20wt.% of copper-containing sludge, 60wt.% of waste circuit board and 20wt.% of scrap copper. The fluxing agent is as follows: 60wt.% of calcium oxide, 20wt.% of ferrous oxalate and 20wt.% of borax.
Step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
wherein the mixture is heated and melted at 1000-1300 ℃ (1100 ℃ in the embodiment) and then is kept for 20-40 min (20 min in the embodiment), and then the crude copper alloy is obtained by casting and slag-gold separation.
The flue gas generated by smelting in the step firstly passes through a cooling tower and a cloth bag for dust removal to collect soot, and then passes through an alkaline absorption tower and an electric demister for dioxin removal and desulfurization, and then is exhausted. Wherein the ash discharged from the cooling tower and the bag-type dust collector contains lead, tin and zinc components, and the extraction and the utilization are carried out subsequently. The flue gas generated by the melting furnace is subjected to dust removal, debromination, dioxin removal and desulfurization, so that the treated flue gas meets the emission requirement, and the environmental pollution is reduced.
Step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
in the step, acid and hydrogen peroxide are selected as leaching agents, so that carrier dissolution and toxic gases such as Cl are reduced 2 Is volatilized, and the reaction equation is as follows: pd+2H + +4Cl - +H 2 O 2 ＝[PdCl 4 ] 2- +2H 2 O. The leaching conditions in this example were: the solid-liquid ratio is 1:5g/mL, H + Concentration of 3mol/L, H 2 O 2 Volume fraction 4%.
Step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
in the step, the leaching liquid produced in the step 3 is used as the electrolyte in the step, and the leaching liquid produced in the previous step is used as the electrolyte, so that the cost is saved. In this step, stainless steel or platinum sheet is used as an electrode, and the cell voltage is 0.4 to 1.0V (0.4V in this example) and the temperature is 25 to 90 ℃ (40 ℃ in this example). The bath voltage in this step is less than the electrodeposition voltage of copper, avoiding simultaneous electrodeposition of copper and palladium. The palladium recovery in this example was found to be 95.9%.
Step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
The cell voltage in this step is 1.5 to 3.0V (1.5V in this example) and the temperature is 25 to 90℃in this example (30 ℃. The electrolyte and the electrode used for electrolysis in this step are the same as in step 4. The copper recovery in this example was detected to be 92.6%.
Example 3:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
wherein the mixture comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 50 parts of copper-containing waste, 7 parts of coke and 90 parts of fluxing agent.
The copper-containing waste in this example is: 25wt.% of copper-containing sludge, 60wt.% of waste circuit board and 15wt.% of scrap copper. The fluxing agent is as follows: 70wt.% of calcium oxide, 15wt.% of ferrous oxalate and 15wt.% of borax.
Step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
wherein the mixture is heated and melted at 1000-1300 ℃ (1300 ℃ in the embodiment) and then is kept for 20-40 min (40 min in the embodiment), and then the crude copper alloy is obtained by casting and slag-gold separation.
The flue gas generated by smelting in the step firstly passes through a cooling tower and a cloth bag for dust removal to collect soot, and then passes through an alkaline absorption tower and an electric demister for dioxin removal and desulfurization, and then is exhausted. Wherein the ash discharged from the cooling tower and the bag-type dust collector contains lead, tin and zinc components, and the extraction and the utilization are carried out subsequently. The flue gas generated by the melting furnace is subjected to dust removal, debromination, dioxin removal and desulfurization, so that the treated flue gas meets the emission requirement, and the environmental pollution is reduced.
Step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
in the step, acid and hydrogen peroxide are selected as leaching agents, so that carrier dissolution and toxic gases such as Cl are reduced 2 Is volatilized, and the reaction equation is as follows: pd+2H + +4Cl - +H 2 O 2 ＝[PdCl 4 ] 2- +2H 2 O. The leaching conditions in this example were: the solid-liquid ratio is 1:15g/mL, H + Concentration of 6mol/L, H 2 O 2 Volume fraction 8%.
Step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
in the step, the leaching liquid produced in the step 3 is used as the electrolyte in the step, and the leaching liquid produced in the previous step is used as the electrolyte, so that the cost is saved. In this step, stainless steel or platinum sheet is used as an electrode, and the cell voltage is 0.4 to 1.0V (0.8V in this example) and the temperature is 25 to 90 ℃ (70 ℃ in this example). The bath voltage in this step is less than the electrodeposition voltage of copper, avoiding simultaneous electrodeposition of copper and palladium. The recovery of palladium in this example was found to be 99.8%.
Step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
The cell voltage in this step is 1.5 to 3.0V (2.5V in this example) and the temperature is 25 to 90℃in this example (70 ℃. The electrolyte and the electrode used for electrolysis in this step are the same as in step 4. The copper recovery in this example was found to be 97.1%.
Example 4:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
wherein the mixture comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 45 parts of copper-containing waste, 9 parts of coke and 100 parts of fluxing agent.
The copper-containing waste in this example is: 27wt.% copper-containing sludge, 55wt.% waste circuit board, 18wt.% scrap copper. The fluxing agent is as follows: 60wt.% of calcium oxide, 25wt.% of ferrous oxalate and 15wt.% of borax.
Step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
wherein the mixture is heated and melted at 1000-1300 ℃ (1250 ℃ in the embodiment) and then is kept for 20-40 min (25 min in the embodiment), and then the crude copper alloy is obtained by casting and slag-gold separation.
The flue gas generated by smelting in the step firstly passes through a cooling tower and a cloth bag for dust removal to collect soot, and then passes through an alkaline absorption tower and an electric demister for dioxin removal and desulfurization, and then is exhausted. Wherein the ash discharged from the cooling tower and the bag-type dust collector contains lead, tin and zinc components, and the extraction and the utilization are carried out subsequently. The flue gas generated by the melting furnace is subjected to dust removal, debromination, dioxin removal and desulfurization, so that the treated flue gas meets the emission requirement, and the environmental pollution is reduced.
Step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
in the step, acid and hydrogen peroxide are selected as leaching agents, so that carrier dissolution and toxic gases such as Cl are reduced 2 Is volatilized, and the reaction equation is as follows: pd+2H + +4Cl - +H 2 O 2 ＝[PdCl 4 ] 2- +2H 2 O. The leaching conditions in this example were: the solid-liquid ratio is 1:20g/mL, H + Concentration of 8mol/L, H 2 O 2 Volume fraction 7%.
Step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
in the step, the leaching liquid produced in the step 3 is used as the electrolyte in the step, and the leaching liquid produced in the previous step is used as the electrolyte, so that the cost is saved. In this step, stainless steel or platinum sheet is used as an electrode, and the cell voltage is 0.4 to 1.0V (0.9V in this example) and the temperature is 25 to 90 ℃ (50 ℃ in this example). The bath voltage in this step is less than the electrodeposition voltage of copper, avoiding simultaneous electrodeposition of copper and palladium. The recovery of palladium in this example was found to be 99.9%.
Step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
The cell voltage in this step is 1.5 to 3.0V (2.7V in this example) and the temperature is 25 to 90℃in this example (55 ℃. The electrolyte and the electrode used for electrolysis in this step are the same as in step 4. The copper recovery in this example was found to be 98.9%.
Example 5:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
wherein the mixture comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 55 parts of copper-containing waste, 6 parts of coke and 70 parts of fluxing agent.
The copper-containing waste in this example is: 24wt.% copper-containing sludge, 58wt.% waste circuit board, 18wt.% scrap copper. The fluxing agent is as follows: 75wt.% of calcium oxide, 10wt.% of ferrous oxalate and 15wt.% of borax.
Step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
wherein the mixture is heated and melted at 1000-1300 ℃ (1200 ℃ in the embodiment) and then is kept for 20-40 min (35 min in the embodiment), and then the crude copper alloy is obtained by casting and slag-gold separation.
The flue gas generated by smelting in the step firstly passes through a cooling tower and a cloth bag for dust removal to collect soot, and then passes through an alkaline absorption tower and an electric demister for dioxin removal and desulfurization, and then is exhausted. Wherein the ash discharged from the cooling tower and the bag-type dust collector contains lead, tin and zinc components, and the extraction and the utilization are carried out subsequently. The flue gas generated by the melting furnace is subjected to dust removal, debromination, dioxin removal and desulfurization, so that the treated flue gas meets the emission requirement, and the environmental pollution is reduced.
Step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
in the step, acid and hydrogen peroxide are selected as leaching agents, so that carrier dissolution and toxic gases such as Cl are reduced 2 Is volatilized, and the reaction equation is as follows: pd+2H + +4Cl - +H 2 O 2 ＝[PdCl 4 ] 2- +2H 2 O. The leaching conditions in this example were: the solid-liquid ratio is 1:12g/mL, H + Concentration of 5mol/L, H 2 O 2 The volume fraction is 10%.
Step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
in the step, the leaching liquid produced in the step 3 is used as the electrolyte in the step, and the leaching liquid produced in the previous step is used as the electrolyte, so that the cost is saved. In this step, stainless steel or platinum sheet is used as an electrode, and the cell voltage is 0.4 to 1.0V (0.7V in this example) and the temperature is 25 to 90 ℃ (55 ℃ in this example). The bath voltage in this step is less than the electrodeposition voltage of copper, avoiding simultaneous electrodeposition of copper and palladium. The recovery of palladium in this example was found to be 99.7%.
Step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
The cell voltage in this step is 1.5 to 3.0V (2.2V in this example) and the temperature is 25 to 90℃in this example (45 ℃. The electrolyte and the electrode used for electrolysis in this step are the same as in step 4. The copper recovery in this example was found to be 98.4%.
The invention realizes the synergistic recovery of copper and palladium in copper-containing waste and waste catalyst, completes the harmless treatment of hazardous waste, avoids consuming a large amount of acid and organic matters, and has the characteristics of high production efficiency, low cost, large income and no pollution.
The foregoing is merely exemplary of the present invention, and specific structures, characteristics, and proportions of reactants, etc. that are well known in the art are not described in detail herein. It should be noted that it will be apparent to those skilled in the art that variations and modifications, such as simple parameter adjustment selections within or near the specified parameters, can be made without departing from the spirit of the invention, and such adjustment is intended to be a matter of the scope of the invention, which is not to be construed as affecting the effect of the invention and the utility of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. Scrapped Pd/Al 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps:
step 1: to scrap Pd/Al 2 O 3 Crushing and mixing the catalyst, copper-containing waste, coke and fluxing agent to obtain a mixture;
step 2: smelting the mixture, and then pouring and slag-gold separation to obtain a blister copper alloy;
step 3: acidolysis is carried out on the crude copper alloy to obtain leaching solution;
step 4: performing primary electrodeposition on the leaching solution to obtain cathode palladium, and recycling the palladium;
step 5: and (3) carrying out secondary electrodeposition on the leaching solution to obtain cathode copper, and recovering copper.
2. A rejected Pd/Al according to claim 1 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: the mixture in the step 1 comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 40-60 parts of copper-containing waste, 5-10 parts of coke and 40-100 parts of fluxing agent.
3. A rejected Pd/Al according to claim 2 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: the mixture in the step 1 comprises the following components in parts by weight: scrapped Pd/Al 2 O 3 50 parts of catalyst, 40 parts of copper-containing waste, 10 parts of coke and 80 parts of fluxing agent.
4. A rejected Pd/Al according to claim 2 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: the copper-containing waste is: 20-30 wt.% of copper-containing sludge, 40-60 wt.% of waste circuit board and 10-20 wt.% of scrap copper, wherein the fluxing agent is as follows: 60 to 80wt.% of calcium oxide, 10 to 30wt.% of ferrous oxalate and 10 to 20wt.% of borax.
5. A rejected Pd/Al according to claim 4 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: and (2) heating and melting the mixture in the step (2) at 1000-1300 ℃, preserving the heat for 20-40 min, and then pouring and separating slag from gold to obtain the blister copper alloy.
6. A rejected Pd/Al according to claim 1 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: and (2) collecting soot from the flue gas generated by smelting in the step (2) through a cooling tower and bag dust removal, and then removing dioxin and desulfurizing through an alkaline absorption tower and an electric demister and then evacuating.
7. A rejected Pd/Al according to claim 1 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: in the step 3, acid and hydrogen peroxide are used as leaching agents, and the leaching conditions in the step 3 are as follows: the solid-liquid ratio is 1:5-20 g/mL, H + Concentration of 2-8 mol/L, H 2 O 2 The volume fraction is 2-10%.
8. A rejected Pd/Al according to claim 7 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: the leaching conditions in the step 3 are as follows: the solid-liquid ratio is 1:10g/mL, H + Concentration of 4mol/L, H 2 O 2 Volume fraction 6%.
9. A rejected Pd/Al according to claim 1 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: in the step 4, the electrolyte is the leaching solution generated in the step 3, stainless steel or platinum sheets are used as electrodes, and the primary electrodeposition conditions are as follows: the cell voltage is 0.4-1.0V, and the temperature is 25-90 ℃.
10. A rejected Pd/Al according to claim 9 2 O 3 The method for cooperatively recycling the catalyst and the copper-containing waste is characterized by comprising the following steps of: the secondary electrodeposition conditions in the step 5 are as follows: the tank voltage is 1.5-3.0V and the temperature is 25-90 ℃.
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