CN114107669A - Metal refining and recycling method based on waste electronic chip crushing material - Google Patents
Metal refining and recycling method based on waste electronic chip crushing material Download PDFInfo
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- CN114107669A CN114107669A CN202111336992.1A CN202111336992A CN114107669A CN 114107669 A CN114107669 A CN 114107669A CN 202111336992 A CN202111336992 A CN 202111336992A CN 114107669 A CN114107669 A CN 114107669A
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 238000007670 refining Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 239000011812 mixed powder Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 34
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 239000010931 gold Substances 0.000 claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 15
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 11
- 239000007769 metal material Substances 0.000 claims abstract description 11
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- 239000000428 dust Substances 0.000 claims description 40
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 36
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 24
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 18
- 235000019253 formic acid Nutrition 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002912 waste gas Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 238000006479 redox reaction Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 6
- 239000010970 precious metal Substances 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000010793 electronic waste Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0073—Leaching or slurrying with acids or salts thereof containing nitrogen
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a metal refining and recycling method based on waste electronic chip crushed materials, which belongs to the technical field of comprehensive utilization of waste resources and comprises the following steps: s1, sorting the electronic chips from the electronic products; s2, primary crushing; s3, carrying out secondary crushing; s4, screening and dividing into four mixed powders with different meshes; s5, separating metal powder and non-metal powder by an air separator; s6, recovering large-diameter particles; s7, obtaining a sintered metal material; s8, separating the leachate containing copper and aluminum and acid leaching filter residue; s9, obtaining aluminum hydroxide and copper hydroxide; s10, obtaining aqua regia solution containing gold, palladium and platinum; s11, precipitating gold in the aqua regia filtrate; s12, refining to obtain spongy platinum; s13, obtaining crude palladium powder. The metal refining and recycling method based on the waste electronic chip crushing material shortens the process flow, reduces the processing time, accelerates the refining of precious metals and improves the recycling efficiency of the precious metals.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of waste resources, and particularly relates to a metal refining and recycling method based on a waste electronic chip crushed material.
Background
As a breeding product of rapid development of information industry, electronic waste represented by computers, mobile phones and televisions draws more and more attention on the influence of environment and social development, and from the viewpoint of changing waste into valuable, the resource value contained in the electronic waste is far higher than that of the traditional waste, and waste electronic chips in the electronic waste can be recycled.
In the prior art, the existing waste electronic chip recovery processing technology in China is still immature, the development investment is seriously insufficient, the processing and processing technology of the waste electronic chip is lagged behind, the technology and equipment level is extremely low, and the recovery rate is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a metal refining and recycling method based on waste electronic chip crushed materials, which aims to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a metal refining and recycling method based on waste electronic chip crushing materials comprises the following steps:
s1, cleaning and drying the waste electronic products, crushing the shells of the products, and sorting out the electronic chip parts in the products;
s2, crushing the sorted electronic chips by a coarse crusher into electronic chip crushed materials with the diameter of 0.5-2 cm;
s3, crushing the crushed material of the electronic chip by a fine crusher for secondary crushing, and conveying the crushed material after fine crushing to a vibrating screen;
s4, after the crushed material enters a feed inlet of a vibrating screen, dividing the crushed material into four mixed powders with different meshes by the vibrating screen;
s5, respectively conveying the four mixed powders with different fineness to a storage bin, conveying the mixed powders to an air separator by a vibration feeder, separating metal powder and non-metal powder by the air separator, and discharging dust generated by the air separator after being treated by a dust removal system;
s6, separating the non-metal powder into large-diameter particles by a cyclone separator, recovering the large-diameter particles, and discharging generated dust-containing waste gas after being treated by a bag-type dust collector;
s7, sintering the metal powder in the S5 to obtain a sintered metal material;
s8, adding the metal materials sintered in the step into a nitric acid solution, and filtering and separating leaching solution containing copper and aluminum and acid leaching filter residues;
s9, adding 0.1-0.5mol/L NaOH solution into the copper and aluminum containing leachate obtained in the step, adjusting the pH value to 5-6, and filtering and separating to obtain aluminum hydroxide and copper hydroxide;
s10, adding aqua regia into the acid leaching filter residue in the S8 for dissolving, wherein the solid-to-liquid ratio is 1:40, and soaking for 4-8 hours at the temperature of 60-80 ℃ to obtain aqua regia solution containing gold, palladium and platinum;
s11, evaporating and concentrating the aqua regia solution containing gold, palladium and platinum, and then precipitating gold in the aqua regia filtrate by using a reducing agent;
s12, adding the aqua regia filtrate into a saturated ammonia water solution, reacting for 6-8 hours, filtering, refining the filter residue to obtain spongy platinum;
s13, adding formic acid into the filtrate, and reacting for 1-2 hours under the condition of strong stirring to obtain crude palladium powder.
Further optimizing the technical scheme, in the step S2, the broken materials of the electronic chip are conveyed to a storage bin through an air blower, and then conveyed to the inlet of the fine crusher through a vibration feeder to prepare for secondary crushing.
Further optimizing the technical scheme, in the step S3, the material crushed by the fine crusher is powder with 30-100 meshes.
Further optimizing the technical scheme, in the step S4, the four mixed powders with different mesh numbers comprise 30-40 mesh mixed powder, 40-50 mesh mixed powder, 50-60 mesh mixed powder and 60-100 mesh mixed powder.
Further optimizing the technical scheme, in the step S5-S6, the dust removal system is composed of a negative pressure air suction pipe and a bag-type dust remover, the negative pressure air suction pipes are arranged at the feed bin and the feed inlet for suction and are connected into the bag-type dust remover for treatment, the exhaust gas of the air separator and the waste gas generated by the cyclone separator are also treated by the bag-type dust remover, and the waste gas is discharged in the upper air through the induced draft fan after the treatment is finished.
Further optimizing the technical scheme, in the S7, when the metal powder is sintered, the temperature is maintained within the range of 450-550 ℃ in the sintering process, and the sintering time is 2-3 hours, so that the metal powder is used for oxidizing metals including copper, aluminum, antimony and lead.
Further optimizing the technical scheme, in the S9, the obtained aluminum hydroxide and the copper hydroxide are calcined at the temperature of 1000-1200 ℃ for 2-4 hours to obtain the aluminum oxide and the copper oxide.
Further optimizing the technical scheme, in the step S11, the reducing agent is sodium sulfite or one of oxalic acid, formic acid and ferrous sulfate.
Further optimizing the technical scheme, when the reducing agent is ferrous sulfate, the oxidation-reduction reaction of the ferrous sulfate and the aqua regia solution is as follows:
3FeSO4+HAuCl4 HCl→FeCl3+Fe2(S04)3+Au↓
when the reducing agent is sodium sulfite, the redox reaction of the sodium sulfite and aqua regia solution is as follows:
Na2SO3+2HCI→SO2+2NaCl+H2O
2SO2+2HAuCl4+6H2O→2Au↓+8HCl+3H2SO4
further optimizing the technical scheme, the mass ratio of the filtrate to the formic acid is 2: 1, the formic acid is added, the stirring temperature is in the range of 60-90 ℃, and the pH value is controlled to be 7.0-9.0.
Compared with the prior art, the invention provides a metal refining and recycling method based on waste electronic chip crushing materials, which has the following beneficial effects:
according to the metal refining and recycling method based on the waste electronic chip crushing materials, the waste electronic chips are recycled and purified through the processes of sorting, crushing, screening, metal layering refining and the like, the process flow is shortened, the processing time is shortened, the refining of precious metals is accelerated, and the recycling efficiency is improved. Meanwhile, by adopting the process method, the corresponding equipment and device system of the process is simple, the input cost is low, and the cost is further saved.
Drawings
Fig. 1 is a schematic flow chart of a metal refining and recycling method based on a waste electronic chip crushed material provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
referring to fig. 1, a metal refining and recycling method based on waste electronic chip crushed materials includes the following steps:
s1, cleaning and drying the waste electronic products, crushing the shells of the products, and sorting out the electronic chip parts in the products;
s2, crushing the sorted electronic chips by a coarse crusher into electronic chip crushed materials with the diameter of 0.5-2 cm;
s3, crushing the crushed material of the electronic chip by a fine crusher for secondary crushing, and conveying the crushed material after fine crushing to a vibrating screen;
s4, after the crushed material enters a feed inlet of a vibrating screen, dividing the crushed material into four mixed powders with different meshes by the vibrating screen;
s5, respectively conveying the four mixed powders with different fineness to a storage bin, conveying the mixed powders to an air separator by a vibration feeder, separating metal powder and non-metal powder by the air separator, and discharging dust generated by the air separator after being treated by a dust removal system;
s6, separating the non-metal powder into large-diameter particles by a cyclone separator, recovering the large-diameter particles, and discharging generated dust-containing waste gas after being treated by a bag-type dust collector;
s7, sintering the metal powder in the S5 to obtain a sintered metal material;
s8, adding the metal materials sintered in the step into a nitric acid solution, and filtering and separating leaching solution containing copper and aluminum and acid leaching filter residues;
s9, adding 0.1-0.5mol/L NaOH solution into the copper and aluminum containing leachate obtained in the step, adjusting the pH value to 5-6, and filtering and separating to obtain aluminum hydroxide and copper hydroxide;
s10, adding aqua regia into the acid leaching filter residue in the S8 for dissolving, wherein the solid-to-liquid ratio is 1:40, and soaking for 4-8 hours at the temperature of 60-80 ℃ to obtain aqua regia solution containing gold, palladium and platinum;
s11, evaporating and concentrating the aqua regia solution containing gold, palladium and platinum, and then precipitating gold in the aqua regia filtrate by using a reducing agent;
s12, adding the aqua regia filtrate into a saturated ammonia water solution, reacting for 6-8 hours, filtering, refining the filter residue to obtain spongy platinum;
s13, adding formic acid into the filtrate, and reacting for 1-2 hours under the condition of strong stirring to obtain crude palladium powder.
Specifically, in S2, the crushed electronic chip material is conveyed to a bin by an air blower, and then conveyed to the inlet of a fine crusher by a vibration feeder to prepare for secondary crushing.
Specifically, in S3, the material pulverized by the fine pulverizer is 30-100 mesh powder.
Specifically, in S4, the four different mesh mixed powders include 30-40 mesh mixed powder, 40-50 mesh mixed powder, 50-60 mesh mixed powder, and 60-100 mesh mixed powder.
Specifically, in S5-S6, the dust removal system is composed of a negative pressure air suction pipe and a bag-type dust collector, the negative pressure air suction pipe is arranged at the feed bin and the feed inlet for suction and is connected to the bag-type dust collector for treatment, the exhaust gas of the air separator and the exhaust gas generated by the cyclone separator are also treated by the bag-type dust collector, and the exhaust gas is discharged in the upper air through the induced draft fan after the treatment.
Specifically, in the step S7, when the metal powder is sintered, the temperature is maintained within the range of 450-550 ℃ during the sintering process, and the sintering time is 2-3 hours, so as to be used for oxidizing metals including copper, aluminum, antimony and lead.
Specifically, in S9, the obtained aluminum hydroxide and copper hydroxide are calcined at 1000-1200 ℃ for 2-4 hours to obtain aluminum oxide and copper oxide.
Specifically, in S11, the reducing agent is sodium sulfite or one of oxalic acid, formic acid and ferrous sulfate.
Specifically, formic acid is added into the filtrate and the formic acid according to the mass ratio of 2: 1, the stirring temperature is in the range of 60-90 ℃, and the pH value is controlled to be 7.0-9.0.
Example two:
a metal refining and recycling method based on waste electronic chip crushing materials comprises the following steps:
s1, cleaning and drying the waste electronic products, crushing the shells of the products, and sorting out the electronic chip parts in the products;
s2, crushing the sorted electronic chips by a coarse crusher into electronic chip crushed materials with the diameter of 1-2cm, conveying the electronic chip crushed materials to a storage bin by an air blower, conveying the electronic chip crushed materials to an inlet of a fine crusher by a vibration feeder, and preparing for secondary crushing;
s3, crushing the crushed material of the electronic chip by a fine crusher for secondary crushing, conveying the crushed material after the fine crushing to a vibrating screen, wherein the crushed material of the fine crusher is powder of 30-100 meshes;
s4, after the crushed material enters a feeding hole of a vibrating screen, dividing the crushed material into four mixed powders with different meshes by the vibrating screen, wherein the four mixed powders with different meshes comprise 30-50 meshes of mixed powder, 50-60 meshes of mixed powder, 60-80 meshes of mixed powder and 80-100 meshes of mixed powder;
s5, respectively conveying the four mixed powders with different fineness to a storage bin, conveying the mixed powders to an air separator by a vibration feeder, separating metal powder and non-metal powder by the air separator, and discharging dust generated by the air separator after being treated by a dust removal system;
s6, separating the non-metal powder into large-diameter particles by a cyclone separator, recovering the large-diameter particles, and discharging generated dust-containing waste gas after being treated by a bag-type dust collector;
the dust removal system comprises a negative pressure air suction pipe and a bag-type dust remover, the negative pressure air suction pipe is arranged at the position of a storage bin and a feeding port for suction and is connected into the bag-type dust remover for treatment, the exhaust gas of the air separator and the waste gas generated by the cyclone separator are also treated by the bag-type dust remover, and the waste gas is discharged in the high air through the induced draft fan after the treatment is finished.
S7, sintering the metal powder in the S5 to obtain a sintered metal material, wherein when the metal powder is sintered, the temperature is maintained within the range of 500-550 ℃ in the sintering process, and the sintering time is 3 hours, so that the metal powder is used for oxidizing metals including copper, aluminum, antimony and lead;
s8, adding the metal materials sintered in the step into a nitric acid solution, and filtering and separating leaching solution containing copper and aluminum and acid leaching filter residues;
s9, adding 0.3mol/L NaOH solution into the leachate containing copper and aluminum in the step, adjusting the pH value to 5-6, filtering and separating to obtain aluminum hydroxide and copper hydroxide, and calcining the obtained aluminum hydroxide and copper hydroxide at 1100-1200 ℃ for 4 hours to obtain aluminum oxide and copper oxide;
s10, adding aqua regia into the acid leaching filter residue in the S8 for dissolving, wherein the solid-to-liquid ratio is 1:40, and soaking for 5 hours at the temperature of 60-80 ℃ to obtain aqua regia solution containing gold, palladium and platinum;
when the reducing agent is sodium sulfite, the redox reaction of the sodium sulfite and aqua regia solution is as follows:
Na2S03+2HCI→S02+2NaCl+H20
2SO2+2HAuCl4+6H20→2Au↓+8HCl+3H2S04
s11, evaporating and concentrating aqua regia solution containing gold, palladium and platinum, and then precipitating gold in aqua regia filtrate by using a reducing agent, wherein the reducing agent is one of sodium sulfite or oxalic acid, formic acid and ferrous sulfate;
s12, adding the aqua regia filtrate into a saturated ammonia water solution, reacting for 8 hours, filtering, refining the filter residue to obtain spongy platinum;
s13, adding formic acid into the filtrate, wherein the mass ratio of the filtrate to the formic acid is 1: 1, adding the formic acid into the filtrate, stirring the mixture at the temperature of 60-90 ℃, controlling the pH value to be 7.0-9.0, and reacting the mixture for 1-2 hours under the condition of strong stirring to obtain crude palladium powder.
Example three:
a metal refining and recycling method based on waste electronic chip crushing materials comprises the following steps:
s1, cleaning and drying the waste electronic products, crushing the shells of the products, and sorting out the electronic chip parts in the products;
s2, crushing the sorted electronic chips by a coarse crusher into electronic chip crushed materials with the diameter of 0.5-2cm, conveying the electronic chip crushed materials to a storage bin by an air blower, conveying the electronic chip crushed materials to an inlet of a fine crusher by a vibration feeder, and preparing for secondary crushing;
s3, crushing the crushed material of the electronic chip by a fine crusher for secondary crushing, conveying the crushed material after the fine crushing to a vibrating screen, wherein the crushed material of the fine crusher is powder of 30-100 meshes;
s4, after the crushed material enters a feeding hole of a vibrating screen, dividing the crushed material into four mixed powders with different meshes by the vibrating screen, wherein the four mixed powders with different meshes comprise 30-40 mesh mixed powder, 40-50 mesh mixed powder, 50-60 mesh mixed powder and 60-100 mesh mixed powder;
s5, respectively conveying the four mixed powders with different fineness to a storage bin, conveying the mixed powders to an air separator by a vibration feeder, separating metal powder and non-metal powder by the air separator, and discharging dust generated by the air separator after being treated by a dust removal system;
s6, separating the non-metal powder into large-diameter particles by a cyclone separator, recovering the large-diameter particles, and discharging generated dust-containing waste gas after being treated by a bag-type dust collector;
the dust removal system comprises a negative pressure air suction pipe and a bag-type dust remover, the negative pressure air suction pipe is arranged at the position of a storage bin and a feeding port for suction and is connected into the bag-type dust remover for treatment, the exhaust gas of the air separator and the waste gas generated by the cyclone separator are also treated by the bag-type dust remover, and the waste gas is discharged in the high air through the induced draft fan after the treatment is finished.
S7, sintering the metal powder in the S5 to obtain a sintered metal material, wherein the sintering temperature is maintained within the range of 500-530 ℃ in the sintering process and the sintering time is 2-3 hours when the metal powder is sintered, and the metal powder is used for oxidizing metals including copper, aluminum, antimony and lead;
s8, adding the metal materials sintered in the step into a nitric acid solution, and filtering and separating leaching solution containing copper and aluminum and acid leaching filter residues;
s9, adding 0.1-0.5mol/L NaOH solution into the leachate containing copper and aluminum in the step, adjusting the pH value to 5-6, filtering and separating to obtain aluminum hydroxide and copper hydroxide, and calcining the obtained aluminum hydroxide and copper hydroxide at the temperature of 1000-1200 ℃ for 3 hours to obtain aluminum oxide and copper oxide;
s10, adding aqua regia into the acid leaching filter residue in the S8 for dissolving, wherein the solid-to-liquid ratio is 1:40, and soaking for 6 hours at 70 ℃ to obtain aqua regia solution containing gold, palladium and platinum;
when the reducing agent is ferrous sulfate, the redox reaction between the ferrous sulfate and aqua regia solution is as follows:
3FeSO4+HAuCl4 HCl→FeCl3+Fe2(SO4)3+Au↓
s11, evaporating and concentrating aqua regia solution containing gold, palladium and platinum, and then precipitating gold in aqua regia filtrate by using a reducing agent, wherein the reducing agent is sodium sulfite;
s12, adding the aqua regia filtrate into a saturated ammonia water solution, reacting for 7 hours, filtering, refining the filter residue to obtain spongy platinum;
and S13, adding formic acid into the filtrate, wherein the mass ratio of the filtrate to the formic acid is 3: 1, adding the formic acid into the filtrate, stirring the mixture at the temperature of 70-80 ℃, controlling the pH value to be 7.5-8.5, and reacting the mixture for 1-2 hours under the condition of strong stirring to obtain crude palladium powder.
The invention has the beneficial effects that: according to the metal refining and recycling method based on the waste electronic chip broken materials, the waste electronic chips are recycled and purified through the processes of sorting, breaking, screening, metal layered refining and the like, the process flow is shortened, the processing time is shortened, the precious metal refining is accelerated, and the recycling efficiency is improved. Meanwhile, by adopting the process method, the corresponding equipment and device system of the process is simple, the investment cost is low, and the cost is further saved.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without conflicting disclosure.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A metal refining and recycling method based on waste electronic chip crushed materials is characterized by comprising the following steps:
s1, cleaning and drying the waste electronic products, crushing the shells of the products, and sorting out the electronic chip parts in the products;
s2, crushing the sorted electronic chips by a coarse crusher into electronic chip crushed materials with the diameter of 0.5-2 cm;
s3, crushing the crushed material of the electronic chip by a fine crusher for secondary crushing, and conveying the crushed material after fine crushing to a vibrating screen;
s4, after the crushed material enters a feed inlet of a vibrating screen, dividing the crushed material into four mixed powders with different meshes by the vibrating screen;
s5, respectively conveying the four mixed powders with different fineness to a storage bin, conveying the mixed powders to an air separator by a vibration feeder, separating metal powder and non-metal powder by the air separator, and discharging dust generated by the air separator after being treated by a dust removal system;
s6, separating the non-metal powder into large-diameter particles by a cyclone separator, recovering the large-diameter particles, and discharging generated dust-containing waste gas after being treated by a bag-type dust collector;
s7, sintering the metal powder in the S5 to obtain a sintered metal material;
s8, adding the metal materials sintered in the step into a nitric acid solution, and filtering and separating out leachate containing copper and aluminum and acid leaching filter residues;
s9, adding 0.1-0.5mol/L NaOH solution into the copper and aluminum containing leachate obtained in the step, adjusting the pH value to 5-6, and filtering and separating to obtain aluminum hydroxide and copper hydroxide;
s10, adding aqua regia into the acid leaching filter residue in the S8 for dissolving, wherein the solid-to-liquid ratio is 1:40, and soaking for 4-8 hours at the temperature of 60-80 ℃ to obtain aqua regia solution containing gold, palladium and platinum;
s11, evaporating and concentrating aqua regia solution containing gold, palladium and platinum, and precipitating gold in aqua regia filtrate by using a reducing agent;
s12, adding the aqua regia filtrate into a saturated ammonia water solution, reacting for 6-8 hours, filtering, refining the filter residue to obtain spongy platinum;
s13, adding formic acid into the filtrate, and reacting for 1-2 hours under the condition of strong stirring to obtain crude palladium powder.
2. The method for refining and recycling metals based on broken materials of waste electronic chips as claimed in claim 1, wherein in S2, the broken materials of electronic chips are sent to a bin by an air blower and then sent to the inlet of the fine crusher by a vibration feeder to prepare for secondary crushing.
3. The method for refining and recycling metals based on broken materials of waste electronic chips as claimed in claim 1, wherein in the step S3, the materials broken by the fine crusher are 30-100 mesh powders.
4. The method for refining and recycling metals based on waste electronic chip crushed materials as claimed in claim 1, wherein in S4, the four mixed powders with different mesh numbers include 30-40 mesh mixed powder, 40-50 mesh mixed powder, 50-60 mesh mixed powder and 60-100 mesh mixed powder.
5. The metal refining and recycling method based on waste electronic chip crushing materials as claimed in claim 1, wherein in S5-S6, the dust removal system is composed of a negative pressure air suction pipe and a bag-type dust remover, the negative pressure air suction pipe is arranged at the bin and the feeding port for suction and is connected into the bag-type dust remover for treatment, the exhaust gas of the air separator and the exhaust gas generated by the cyclone separator are also treated by the bag-type dust remover, and the exhaust gas is discharged in the upper air through the induced draft fan after the treatment.
6. The method as claimed in claim 1, wherein in the step S7, the temperature of the metal powder is maintained within the range of 450-550 ℃ during the sintering process, and the sintering time is 2-3 hours, so as to oxidize metals including Cu, Al, Sb and Pb.
7. The method as claimed in claim 1, wherein the aluminum hydroxide and the copper hydroxide obtained in S9 are calcined at 1000-1200 ℃ for 2-4 hours to obtain aluminum oxide and copper oxide.
8. The method as claimed in claim 1, wherein in S11, the reducing agent is sodium sulfite or one of oxalic acid, formic acid and ferrous sulfate.
9. The method for refining and recovering metal based on the crushed waste electronic chip as claimed in claim 8, wherein when the reducing agent is ferrous sulfate, the redox reaction between the ferrous sulfate and aqua regia solution is as follows:
3FeSO4+HAuCI4 HCI→FeCI3+Fe2(SO4)3+Au↓
when the reducing agent is sodium sulfite, the redox reaction of the sodium sulfite and aqua regia solution is as follows:
Na2SO3+2HCI→SO2+2NaCI+H2O
2SO2+2HAuCI4+6H2O→2Au↓+8HCI+3H2SO4。
10. the method for extracting and recovering metals based on waste electronic chip crushed materials as claimed in claim 1, wherein the formic acid is added into the filtrate at a mass ratio of 2: 1, the stirring temperature is in the range of 60-90 ℃, and the pH value is controlled at 7.0-9.0.
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