CN114934181A - Method for recycling valuable metals from waste charging pile power devices through wet method - Google Patents
Method for recycling valuable metals from waste charging pile power devices through wet method Download PDFInfo
- Publication number
- CN114934181A CN114934181A CN202210381199.1A CN202210381199A CN114934181A CN 114934181 A CN114934181 A CN 114934181A CN 202210381199 A CN202210381199 A CN 202210381199A CN 114934181 A CN114934181 A CN 114934181A
- Authority
- CN
- China
- Prior art keywords
- copper
- power devices
- charging pile
- powder
- valuable metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 150000002739 metals Chemical class 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000002386 leaching Methods 0.000 claims abstract description 54
- 238000001914 filtration Methods 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000010949 copper Substances 0.000 claims description 68
- 229910052802 copper Inorganic materials 0.000 claims description 49
- 239000012535 impurity Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 34
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 23
- 239000005750 Copper hydroxide Substances 0.000 claims description 23
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 229910052745 lead Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 229910052755 nonmetal Inorganic materials 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical group [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 9
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- -1 hydroxide ions Chemical class 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 47
- 230000008569 process Effects 0.000 description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering valuable metals from waste charging pile power devices by a wet method, which comprises the following steps: (1) disassembling and crushing; (2) leaching copper powder; (3) precipitation and enrichment; (4) filtering and washing; (5) and recycling ammonia gas and filtrate. The method has the characteristics of simple operation, environmental protection, low energy consumption, low extraction cost and high recovery rate, and simultaneously, the leaching reagent can be recycled, and the closed cycle of the waste water and the waste liquid can be realized.
Description
Technical Field
The invention belongs to the technical field of resource utilization of electronic wastes, and particularly relates to a method for recycling valuable metals from waste charging pile power devices by a wet method.
Background
With the technical progress and the lapse of time of charging piles, some existing charging devices reach the scrapped age, some charging piles constructed in early stage are not suitable for the charging technical requirements of the existing electric vehicles and need to be scrapped, the scrapped charging piles contain a large number of high-value reusable components, Insulated Gate Bipolar Transistor (IGBT) and metal-oxide field effect transistor (MOSFET) devices in a charging module are representative high-value devices, and contain a large number of metal resources, such as valuable metals like copper, tin, lead and the like, if the devices are directly discarded after being discarded, a large amount of environmental pollution can be generated, and simultaneously, the waste of the metal resources can be caused, and a large amount of waste gas containing difficult-to-treat dioxin can be generated by adopting pyrogenic process recycling, so that huge environmental pollution can be caused. Therefore, how to effectively treat the waste power devices and realize the recycling of valuable resources has important strategic significance.
Disclosure of Invention
The invention aims to provide a method for recovering valuable metals from waste charging pile power devices by a wet method, which has the characteristics of simplicity and convenience in operation, environmental protection, low energy consumption, low extraction cost and high recovery rate, and meanwhile, a leaching reagent can be recycled, so that closed cycle of waste water and waste liquid can be realized.
The above object of the present invention can be achieved by the following technical solutions: a method for recovering valuable metals from waste charging pile power devices by a wet method comprises the following steps:
(1) disassembling and crushing: disassembling power devices in the waste charging pile power supply module, and then crushing to obtain powder;
(2) leaching copper powder: adding the powder obtained in the step (1) into an alkaline leaching solution, leaching copper powder, separating insoluble impurity metals with high density and non-metal impurities with low density by adopting a cyclone separation device, then filtering, and separating the non-metal impurities in the copper-containing leaching solution to obtain the copper-containing leaching solution;
(3) precipitation and enrichment: adding a sodium hydroxide solution into the copper-containing leachate obtained in the step (2), and filtering after reaction to obtain a copper hydroxide precipitate and a filtrate;
(4) filtering and washing: filtering, washing and drying the copper hydroxide precipitate obtained in the step (3) to obtain industrial-grade copper hydroxide;
(5) and (3) recycling ammonia and filtrate: ammonia gas can be generated or volatilized in the reaction processes of the steps (2) to (3), and the ammonia water is absorbed by water to generate ammonia water which is reused for preparing the alkaline leaching solution in the step (2) for recycling; and (4) adding a precipitator into the filtrate generated in the step (3), and recycling the generated sodium hydroxide solution used in the step (3).
The method of the invention firstly crushes power devices such as IGBT, MOSFET and the like into powder with a certain mesh number, then adopts alkaline solution to leach copper contained in the powder, then filters and separates insoluble slag and copper leaching solution, and then adds a certain amount of alkaline solution to form copper hydroxide precipitate, thereby producing copper hydroxide products meeting the national standard.
In the method for recovering valuable metals from the waste charging pile power device by a wet method, the method comprises the following steps:
preferably, the power device in step (1) includes an insulated gate bipolar transistor IGBT, a metal-oxide field effect transistor MOSFET device, and the like.
Preferably, the grinding in the step (1) is carried out by a shearing type grinder to obtain powder of 40-60 meshes for later use.
Specifically, in the step (1), power devices in the waste power modules are disassembled, and then the disassembled waste power devices are crushed into powder of 40-60 meshes by a shear type crusher for later use.
Preferably, the dosage relation (solid-to-liquid ratio) of the powder and the alkaline leaching solution in the step (2) is 1 g: 5-10 mL.
Preferably, the pH value of the alkaline leaching solution in the step (2) is 8-9.
Preferably, the alkaline leaching solution in step (2) comprises: 0.05-0.1 mol/L of copper ammonium complex, 2-4 mol/L of ammonium salt, 0.5-1 mol/L of oxidation promoter and 1-3 mol/L of ammonia water.
Preferably, the copper ammonium complex in step (2) is derived from Cu (N)H 3 ) 4 CO 3 And Cu (NH) 3 ) 4 SO 4 One or two of them.
Preferably, in step (2), the ammonium salt is derived from (NH) 4 ) 2 CO 3 、(NH 4 ) 2 SO 4 、NH 4 HCO 3 And NH 4 HSO 4 One or more of (a).
Preferably, the oxidation promoter in step (2) is derived from (NH) 4 ) 2 S 2 O 8 And Na 2 S 2 O 8 One or more of them.
In the step (2) of the invention, the powder generated in the step (1) is added into an alkaline leaching solution to leach copper powder therein, the copper powder forms copper complex ions coordinated with ammonia in a multi-component aqueous solution system consisting of ammonia, ammonia salt, copper ammonium complex ions and an oxidation promoter, the complex ions are dissolved in the multi-component system to form stable copper ammonium complex ions with different coordination numbers, a small amount of impurity metals Fe, Ni, Sn, Pb, Al and Au contained in the powder are basically insoluble in the solution, and the metal and nonmetal epoxy resin packaging impurities are left in filter residues to be separated from copper by filtering, and the solution has certain selectivity on metal Fe, Ni, Sn, Pb, Al and Au leaching solutions, so that the impurity metal content in the copper is low, and good conditions are created for extracting high-purity copper compounds and metal copper subsequently.
Preferably, when the cyclone separation device is used for filtering in the step (2), insoluble impurity metals with high density and including Ni, Sn and Pb and non-metal impurities are separated, the impurity metals with high density are concentrated at the lower part of the cyclone device through centrifugal action, the non-metal impurities with low density flow out of the cyclone device along with water, and the impurity metal concentrates including Ni, Sn and Pb are recycled, wherein the non-metal impurities include epoxy resin glass fiber powder, silicon inorganic filler and the like.
In step (3) of the present invention, a certain amount of alkaline solution (preferably sodium hydroxide solution for recycling purposes, or other alkaline solution such as potassium hydroxide solution, etc. can be used) is added to the copper leaching solution obtained in step (2) to form a copper hydroxide precipitate, and copper and other impurities are separated to obtain copper hydroxide with high purity.
Preferably, the molar ratio of the copper ions in the copper-containing leachate in the step (3) to the hydroxide ions in the sodium hydroxide solution is 1: 2-2.3.
In the step (4), the copper hydroxide precipitate obtained in the step (3) is filtered, washed for a plurality of times as required, and then dried to obtain the industrial-grade copper hydroxide.
Preferably, the precipitant in step (5) is barium hydroxide.
And (3) when the precipitator is barium hydroxide, adding barium hydroxide into the filtrate generated in the step (4), reacting the barium hydroxide with sodium sulfate in the filtrate to generate sodium hydroxide and barium sulfate precipitates, filtering and separating the barium sulfate precipitates, and returning the obtained sodium hydroxide filtrate to the copper hydroxide precipitate enrichment process for recycling.
Compared with the prior art, the invention has the following advantages:
(1) according to the method, the low-concentration ammoniacal solution is used for leaching the metal copper powder in the waste power device, the pH value of the solution is controlled within the range of 8-9, the metal copper can be selectively leached, a small amount of impurity metals such as Fe, Ni, Sn, Pb, Al and Au in the solution are basically insoluble, non-metallic impurities such as epoxy resin and silicon inorganic fillers of the epoxy resin are insoluble, and after filtration treatment, most of the impurities are left in leaching residues, so that the copper and most of the impurity substances are effectively separated, and a prerequisite condition is provided for subsequent extraction of high-purity copper hydroxide;
(2) the method can completely leach the copper powder under the normal-temperature alkaline condition, has less energy consumption, does not generate acid mist, has small corrosivity on production equipment, and saves the maintenance cost of the equipment;
(3) the invention adopts the normal temperature alkali precipitation process, can directly produce the copper hydroxide product which meets the national standard, and compared with the prior art which adopts high-purity copper powder to prepare copper sulfate and then adds sodium hydroxide to prepare copper hydroxide, the process has short flow and low energy consumption, the used raw materials are industrial waste materials, the production cost is low, and the economic benefit is better;
(4) the leached liquid after the alkaline precipitation and filtration contains sodium sulfate and ammonia water, and can directly return to the leaching process of copper powder, so that the regeneration and cyclic utilization of copper leaching liquid are realized, the sodium sulfate can be accumulated in the cyclic utilization process, after reaching a certain degree, barium hydroxide is added into the leached liquid to generate barium sulfate precipitate and sodium hydroxide, the filtered sodium hydroxide solution returns to the copper hydroxide precipitation process for cyclic utilization, the aqueous solution forms closed cycle in the whole process, ammonia gas overflowing from the copper powder leaching process and the alkaline precipitation process has good water solubility, and the ammonia gas returns to the copper powder leaching process for cyclic utilization after being absorbed by water;
(5) the method is energy-saving and environment-friendly, has high comprehensive utilization rate of resources, can recycle the waste liquid and the waste ammonia gas, and is a green low-carbon extraction method.
Drawings
Fig. 1 is a process flow of wet preparation of copper hydroxide from power devices such as waste IGBTs and MOSFETs in a specific embodiment.
Detailed Description
The present invention will be described in further detail with reference to the process flows and examples shown in the drawings, but the embodiments of the present invention are not limited thereto.
As shown in fig. 1, a wet method for preparing copper hydroxide from power devices such as waste IGBI and MOSFET includes the following steps:
(1) disassembling and crushing: power devices such as IGBTs and MOSFETs on a power module of a waste automobile charging pile are disassembled and are crushed into powder of 40-60 meshes by a shearing type crusher for later use, and the power devices are made of materials with certain toughness and can be crushed to the fineness required by the process only by shearing type crushing equipment, so that metal materials such as copper and the like are completely separated from external packaging resin materials, and conditions are created for the next copper leaching reaction;
(2) leaching copper powder: copper forms copper complex ions coordinated with ammonia with different coordination numbers in a multi-component aqueous solution system (0.05-0.1 mol/L of copper-ammonium complex, 2-4 mol/L of ammonium salt, 0.5-1 mol/L of oxidation promoter, 1-3 mol/L of ammonia water, pH value of 8-9) composed of ammonia, ammonia salt, copper-ammonium complex ions and oxidation promoter, the complex ions are dissolved in the multi-component system to form stable copper-ammonium complex ions with different coordination numbers, so that metal copper is dissolved in the system, and the leaching reaction mechanism is as follows:
Cu+Cu 2+ (NH 3 ) 4 ＝2Cu + (NH 3 ) 2
Cu + (NH 3 ) 2 monovalent Cu of (1) + The ions have no oxidation property and can not dissolve metallic copper, and the oxidation promoter oxidizes the metallic copper into bivalent Cu with oxidation property 2+ And (4) ions, and continuously dissolving copper.
The method is characterized in that a small amount of impurity metals Fe, Ni, Sn, Pb, Al and Au contained in the powder are basically insoluble in the solution, most of impurity metals Fe, Ni, Sn, Pb, Al and Au and non-metal epoxy resin packaging impurities are left in filter residues through filtering and are separated from copper, the solution has a certain choice for the metals Fe, Ni, Sn, Pb, Al and Au, the non-metal impurity epoxy resin glass fiber powder does not generate ammonia-soluble reaction, and the non-metal impurity epoxy resin glass fiber powder can be subjected to centralized treatment or resource utilization after leaching treatment.
(3) Precipitation and filtration: adding a certain amount of sodium hydroxide into the copper leaching solution, wherein the molar ratio of the copper ions to the hydroxide ions is 1: 2 to form Cu (OH) 2 Precipitation, the reaction mechanism is as follows:
Cu 2+ (NH 3 ) 4 +2OH - ＝Cu(OH) 2 +4NH 3 ↑
mixing Cu (OH) 2 Filtering, washing and drying to obtain pure industrial-grade copper hydroxide.
(4) And (3) regenerating and utilizing alkali liquor in the filtrate: because of adding alkaline substances such as sodium hydroxide, the filtrate contains a certain amount of sodium sulfate, the sulfate radical in the sodium sulfate in the solution is converted into insoluble barium sulfate precipitate by adding barium hydroxide solution, and the sodium hydroxide in the insoluble barium sulfate precipitate is regenerated, wherein the reaction mechanism is as follows:
Na 2 SO 4 +Ba(OH) 2 ＝BaSO 4 ↓+NaOH
the regenerated sodium hydroxide solution is reused in the precipitation filtration process in the step (3), so that the regeneration and utilization of reaction byproducts are realized, the production cost is reduced, and the emission of pollutants is controlled from the source.
(5) And (3) ammonia gas recycling: and (3) volatilizing ammonia water in the copper powder leaching process, generating ammonia gas in the copper hydroxide precipitation filtering process in the step (3), absorbing the generated ammonia gas by using a spray tower, and regenerating an ammonia water solution by using water absorption, and then reusing the ammonia water solution in the copper powder leaching process in the step (2), wherein the reaction mechanism is as follows:
NH 3 +H 2 O＝NH 4 OH(NH 3 -H 2 O)
(6) separating impurity metals: harmful impurity metals such as Ni, Sn, Pb and the like contained in the copper-leaching reaction-removed copper slag can be subjected to data utilization only by separating the harmful impurity metals from the nonmetallic impurity epoxy resin glass fiber powder, the harmful impurity metals such as Ni, Sn, Pb and the like and the nonmetallic impurity epoxy resin glass fiber powder with high density can be concentrated at the lower part of the cyclone device by adopting the cyclone separation device through centrifugal action, the nonmetallic impurity epoxy resin glass fiber powder with low density flows out of the cyclone device along with water, and Sn, Pb and Ni metal concentrates are recycled.
Example 1
As shown in fig. 1, firstly, 100g of waste IGBT powder is weighed, the copper content of the known waste IGBT is about 30-40%, the solid-to-liquid ratio is determined to be 1: 10(100g of powder is added into 1000mL of leachate), the alkaline leachate is 1L, and the leachate consists of: cu (NH) 3 ) 4 CO 3 ：0.05mol/L、Cu(NH 3 ) 4 SO 4 ：0.05 mol/L、(NH 4 ) 2 SO 4 ：1mol/L、(NH 4 ) 2 CO 3 ：1mol/L、(NH 4 ) 2 S 2 O 8 ：0.5mol/L、NH 3 -H 2 O： 2mol/L。
Mechanically stirring the leaching solution, measuring the concentration of copper ions in the leaching solution to be 39.50g/L and the copper content of 100g of powder to be 39.50g/L multiplied by 1L to be 39.5g by an ICP-AES inductively coupled atomic emission spectrometer after the leaching reaction is finished, pumping the slurry into a cyclone separator by a pumpThe device is used for enriching and separating Sn, Pb, Ni and other impurity metals for subsequent resource utilization, the obtained impurity metal concentrate is washed, dried and weighed to be 4.245g, and 1mol Cu is obtained according to the mechanism of the precipitation and filtration step (3) 2+ 2mol of NaOH needs to be added, and the actual addition of NaOH is 10% excess for the reaction to be complete, and 39.5g of Cu is calculated 2+ 55g of NaOH is added, mechanical stirring is adopted, after the reaction is completed, 60.12g of copper hydroxide is obtained by filtering, washing and drying, the concentration of sodium sulfate in the filtrate is 88.5g/L, 180g of barium hydroxide is added to generate barium sulfate precipitate, and the concentration of sodium hydroxide in the filtrate is measured to be 56.5 g/L.
And (3) copper leaching rate determination: weighing insoluble residue after filtering, washing and drying, wherein the weight of copper powder is the weight of powder minus the weight of residue, diluting the copper leaching solution to a constant volume, measuring the concentration of copper ions in the leaching solution, multiplying the volume of the solution by the concentration of copper ions to obtain the weight of copper contained in the solution, and then subtracting Cu (OH) added into the leaching solution 2 The copper content in 100g of the igbt powder was calculated to be 39.50g, the copper content in the added copper ammonium complex was 6.35g, the copper content in 100g of the igbt powder was 39.50-6.35 ═ 33.15g, the weight of the dried residue was 65.25g, the residue was digested with 1L 30% dilute nitric acid, the copper ion concentration in the digestion solution was measured by ICP to be 60ppm, the residual copper content in the residue was 1L × 60mg/L ═ 60mg ═ 0.06g, and the copper leaching rate was (33.15-0.06)/33.15 ═ 99.8%.
Example 2
As shown in fig. 1, firstly, 200g of waste MOSFET tubes are weighed and crushed into 40 mesh powder, and given that the copper content of the waste MOSFET tubes is about 25-30%, the solid-to-liquid ratio is determined to be 1: 5(200g of powder is added into 1000mL of leachate), the alkaline leachate is 1L, and the leachate consists of: cu (NH) 3 ) 4 SO 4 ：0.1mol/L，NH 4 HCO 3 ：1mol/L、NH 4 HSO 4 ：1.5mol/L、Na 2 S 2 O 8 ：0.5mol/L、NH 3 -H 2 O： 3mol/L。
Mechanically stirring the solution at 35 deg.C, and inductively coupling with ICP-AES to emit lightMeasuring the concentration of copper ions in the leaching solution by a spectrometer to be 58.2g/L, measuring the concentration of 200g of powder containing copper 58.20g/L multiplied by 1L to be 58.2g, pumping the slurry into a cyclone separation device by a pump, enriching and separating impurity metals such as Sn, Pb, Ni and the like in the slurry for subsequent resource utilization, cleaning, drying and weighing the obtained impurity metal concentrate to be 5.1g, and obtaining 1mol Cu according to the mechanism of the precipitation and filtration step (3) 2+ 2mol of NaOH is required to be added, and the actual addition amount of the NaOH is 10 percent in excess for complete reaction, and 58.2g of Cu is calculated 2+ 80.3g of NaOH is added, mechanical stirring is adopted, after complete reaction, 88.5g of copper hydroxide is obtained by filtering, washing and drying, the concentration of sodium sulfate in the filtrate is 130g/L, 288g of barium hydroxide is added to generate barium sulfate precipitate, and the concentration of sodium hydroxide in the filtrate is measured to be 80 g/L.
And (3) measuring the copper leaching rate: weighing insoluble residue after filtering, washing and drying, wherein the weight of copper powder is the weight of powder minus the weight of residue, diluting the copper leaching solution to a constant volume, measuring the concentration of copper ions in the leaching solution, multiplying the volume of the solution by the concentration of copper ions to obtain the weight of copper contained in the solution, and then subtracting Cu (OH) added into the leaching solution 2 The copper content of 200g of MOSFET powder is obtained by calculating the copper content of 58.20g in the leaching solution, the copper content of the added copper-ammonium complex is 6.35g, the copper content of 200g of MOSFET powder is 58.20-6.35-51.85 g, the weight of the dried filter residue is 65.25g, the filter residue is digested by 1L of 30% diluted nitric acid, the copper ion concentration of the digestion solution is 92ppm by ICP measurement, the residual copper content of the filter residue is 1L multiplied by 92 mg/L-72 mg-0.072 g, and the copper leaching rate is (51.85-0.092)/51.85-99.8%.
The present invention is illustrated by the following examples, which are not intended to limit the scope of the invention. Other insubstantial modifications and adaptations of the present invention can be made without departing from the scope of the present invention.
Claims (8)
1. A method for recycling valuable metals from waste charging pile power devices by a wet method is characterized by comprising the following steps:
(1) disassembling and crushing: disassembling power devices in the waste charging pile power supply module, and then crushing to obtain powder;
(2) leaching copper powder: adding the powder obtained in the step (1) into an alkaline leaching solution, leaching copper powder in the powder, separating insoluble impurity metal with high density and non-metal impurities with low density by adopting a cyclone separation device, then filtering, and separating the non-metal impurities in the copper-containing leaching solution to obtain the copper-containing leaching solution;
(3) precipitation and enrichment: adding a sodium hydroxide solution into the copper-containing leachate obtained in the step (2), and filtering after reaction to obtain a copper hydroxide precipitate and a filtrate;
(4) filtering and washing: filtering, washing and drying the copper hydroxide precipitate obtained in the step (3) to obtain industrial-grade copper hydroxide;
(5) and (3) recycling ammonia and filtrate: ammonia gas can be generated or volatilized in the reaction processes of the steps (2) to (3), and the ammonia water is absorbed by water to generate ammonia water which is reused for preparing the alkaline leaching solution in the step (2) for recycling; and (4) adding a precipitator into the filtrate generated in the step (3), and using the generated sodium hydroxide solution for recycling in the step (3).
2. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 1, wherein the method comprises the following steps: and (2) crushing in the step (1) into powder of 40-60 meshes by using a shear type crusher for later use.
3. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 1, wherein the method comprises the following steps: the dosage relationship between the powder and the alkaline leaching solution in the step (2) is 1 g: 5-10 mL.
4. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 1, wherein the method comprises the following steps: the alkaline leaching solution in the step (2) comprises: 0.05-0.1 mol/L of copper ammonium complex, 2-4 mol/L of ammonium salt, 0.5-1 mol/L of oxidation promoter and 1-3 mol/L of ammonia water.
5. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 4, wherein the method comprises the following steps: the copper ammonium complex in the step (2) is derived from Cu (NH) 3 ) 4 CO 3 And Cu (NH) 3 ) 4 SO 4 One or two of them; said ammonium salt is derived from (NH) 4 ) 2 CO 3 、(NH 4 ) 2 SO 4 、NH 4 HCO 3 And NH 4 HSO 4 One or more of (a); the oxidation promoter is derived from (NH) 4 ) 2 5 2 O 8 And Na 2 S 2 O 8 One or two of them.
6. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 1, wherein the method comprises the following steps: when the cyclone separation device is adopted for filtering in the step (2), insoluble impurity metals with high density and including Ni, Sn and Pb and non-metal impurities are separated, the impurity metals with high density are enriched at the lower part of the cyclone device through centrifugal action, the non-metal impurities with low density flow out of the cyclone device along with water, and the impurity metal enriched bodies including Ni, Sn and Pb are recycled, wherein the non-metal impurities include epoxy resin and silicon inorganic fillers thereof.
7. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 1, wherein the method comprises the following steps: and (3) the molar ratio of the copper ions in the copper-containing leaching solution to the hydroxide ions in the sodium hydroxide solution is 1: 2-2.3.
8. The method for wet recovery of valuable metals from waste charging pile power devices as claimed in claim 1, wherein the method comprises the following steps: and (5) the precipitator is barium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210381199.1A CN114934181A (en) | 2022-04-12 | 2022-04-12 | Method for recycling valuable metals from waste charging pile power devices through wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210381199.1A CN114934181A (en) | 2022-04-12 | 2022-04-12 | Method for recycling valuable metals from waste charging pile power devices through wet method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114934181A true CN114934181A (en) | 2022-08-23 |
Family
ID=82863147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210381199.1A Pending CN114934181A (en) | 2022-04-12 | 2022-04-12 | Method for recycling valuable metals from waste charging pile power devices through wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114934181A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05195103A (en) * | 1991-11-13 | 1993-08-03 | Sumitomo Metal Ind Ltd | Method for separating and recovering copper in ferroscrap |
| CN101315996A (en) * | 2008-06-20 | 2008-12-03 | 北京矿冶研究总院 | Method for selectively removing copper from waste lithium ion battery |
| CN101575715A (en) * | 2009-06-22 | 2009-11-11 | 中南大学 | Method for extracting valuable metals from electronic waste |
| CN102230083A (en) * | 2011-07-11 | 2011-11-02 | 湖南宇腾有色金属股份有限公司 | Method for separating copper from lead copper matte |
| CN104745824A (en) * | 2015-03-17 | 2015-07-01 | 昆明理工大学 | Method for recovering copper from waste circuit board |
-
2022
- 2022-04-12 CN CN202210381199.1A patent/CN114934181A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05195103A (en) * | 1991-11-13 | 1993-08-03 | Sumitomo Metal Ind Ltd | Method for separating and recovering copper in ferroscrap |
| CN101315996A (en) * | 2008-06-20 | 2008-12-03 | 北京矿冶研究总院 | Method for selectively removing copper from waste lithium ion battery |
| CN101575715A (en) * | 2009-06-22 | 2009-11-11 | 中南大学 | Method for extracting valuable metals from electronic waste |
| CN102230083A (en) * | 2011-07-11 | 2011-11-02 | 湖南宇腾有色金属股份有限公司 | Method for separating copper from lead copper matte |
| CN104745824A (en) * | 2015-03-17 | 2015-07-01 | 昆明理工大学 | Method for recovering copper from waste circuit board |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112410556B (en) | Method for recovering waste lithium iron phosphate powder | |
| US9150942B2 (en) | Process of leaching precious metals | |
| CN105969993A (en) | Comprehensive recycling method for high-arsenic soot | |
| CN108893617B (en) | Method for efficiently separating and recovering zinc and cobalt from purified cobalt slag | |
| CN103773961A (en) | Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue | |
| CN102011008A (en) | Method for preparing high-purity copper oxide superfine powder from waste printed circuit boards | |
| CN103614556A (en) | Method for treating waste mobile phone circuit board and recovering precious metals | |
| CN102140581A (en) | Process method for producing copper sulfate by using copper scale at normal temperature and normal pressure | |
| CN104018184A (en) | Brand new method of producing electrolytic manganese metal | |
| CN110028111A (en) | The preparation method of ternary anode material precursor and lithium carbonate | |
| CN108467942A (en) | A method of Selectively leaching zinc, lead, gallium and germanium from zinc replacement slag | |
| CN105886769A (en) | Method for enriching precious metal by dissolving multi-metal alloy material through nitric acid | |
| CN107619068A (en) | A kind of iron sulfonium prepares the method that hydrogen sulfide is used for waste acid processing | |
| CN103898328A (en) | Method for extracting cobalt from manganese-cobalt-nickel waste residues | |
| CN110550611A (en) | Method for efficiently leaching tellurium from copper separating slag of copper anode slime enhanced by external field effect | |
| CN103898327A (en) | Method for extracting nickel from manganese cobalt nickel waste slag | |
| CN103805789B (en) | A kind of method of comprehensively recovering valuable metal of copper nickel slag | |
| CN103233123B (en) | Integrated recovery method of waste and old rare earth capacitance battery | |
| CN103602807B (en) | Treating method of removed molybdenum slag produced from tungsten smelting processes | |
| CN101314820A (en) | Method for producing zinc finemeal with zinc oxide mine or zinc slag | |
| CN105861836B (en) | A method of collecting noble metal from more metal alloy materials | |
| CN103834814A (en) | Method for preparing iron oxide red by using copper nickel slag | |
| CN103950961A (en) | Method for preparing aluminum hydroxide from industrial waste residue generated in aluminum alloy surface treatment | |
| CN105586494A (en) | Method for recycling gold from iodide gold leaching pregnant solution on basis of recycling of waste solution | |
| CN114934181A (en) | Method for recycling valuable metals from waste charging pile power devices through wet method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |