CN117587259A - Regeneration system of tin alloy waste - Google Patents
Regeneration system of tin alloy waste Download PDFInfo
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- CN117587259A CN117587259A CN202311570689.7A CN202311570689A CN117587259A CN 117587259 A CN117587259 A CN 117587259A CN 202311570689 A CN202311570689 A CN 202311570689A CN 117587259 A CN117587259 A CN 117587259A
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- tin
- alloy
- slag
- electrolyte
- water
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- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 230000008929 regeneration Effects 0.000 title abstract description 7
- 238000011069 regeneration method Methods 0.000 title abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002893 slag Substances 0.000 claims abstract description 58
- 239000003792 electrolyte Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002791 soaking Methods 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 229910001245 Sb alloy Inorganic materials 0.000 claims abstract description 17
- 239000002140 antimony alloy Substances 0.000 claims abstract description 17
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 11
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007654 immersion Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000007670 refining Methods 0.000 claims abstract description 8
- GSYZQGSEKUWOHL-UHFFFAOYSA-N arsenic calcium Chemical compound [Ca].[As] GSYZQGSEKUWOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 238000004064 recycling Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 9
- 235000019738 Limestone Nutrition 0.000 claims description 8
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 claims description 8
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000006028 limestone Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 230000009286 beneficial effect Effects 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001662 tin mineral Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- 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
- 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
-
- 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)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a regeneration system of tin alloy waste, which comprises the following technical scheme: s1: pretreatment; s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag; s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead; soaking the alloy slag in water to obtain soaking liquid and soaking slag; s4: carrying out arsenic precipitation treatment on the water immersion liquid to obtain arsenic-calcium slag; s5: electrolyzing and treating water leaching residues to obtain tin-containing filter residues and a tin-removed copper electrolyte; s6: heating tin-containing filter residues, separating and filtering to obtain tin; s7: and (3) electrolyzing the tin-removed copper electrolyte to obtain cathode copper and electrolyte. Compared with the prior art, the method combines the fire recovery, the wet recovery and the electrolysis, reduces the difficulty of extracting and separating the tin alloy through comprehensive recovery, improves the purity of the recovered valuable metal, and improves the recovery effect.
Description
Technical Field
The invention relates to the technical field of metal recovery, in particular to a regeneration system of tin alloy waste.
Background
The tin-containing alloy waste is various, and has various Babbitt bearing alloys, fusible alloys and solders, and the three are collectively called lead-tin alloys, tin bronze brass waste and the like, and generally contains 2-5% or more of tin and also contains components with recovery values such as lead, copper, antimony, zinc and the like. Tin is a rare and expensive heavy metal, and can be recovered from the tin-containing waste, so that the environment can be protected from pollution, and secondary resources of tin can be fully utilized to supplement the shortages of world primary tin mineral resources. The production cost of the regenerated tin is generally lower than that of the original tin, and the tin-containing waste sundries for producing the regenerated tin are continuously increased along with the development of economy. Therefore, the world places importance on tin regeneration, and the regenerated tin in industrially developed countries is about 40% of the original tin yield.
At present, in the prior art, waste tin alloy is mainly recovered by a fire method, a wet method or an electrolysis method, the fire method recovery mainly adopts high-temperature treatment, organic and volatile parts in the battery are evaporated, and then metal oxide components are reduced to form the alloy. However, the recovery of the differences of different valuable metals is difficult, and the energy waste is also easy to cause; the wet recovery can produce a large amount of acid-containing ammonia-alkali wastewater, which is not in accordance with the environmental protection concept; the electrolytic method for recovering the metal has the advantages of high purity, but the treatment process has the advantages of high energy consumption, long treatment time, toxicity and corrosiveness of part of metal ions and high operation difficulty.
Therefore, the field still lacks a tin alloy recovery system with low energy consumption, high yield, high purity and good comprehensive effect.
Disclosure of Invention
The invention aims to provide a regeneration system of tin alloy waste, which can be used for differentially extracting valuable metals from the tin alloy waste by a comprehensive recovery method, so that the recovery difficulty of the tin alloy is reduced, the recovery rate of each metal is improved, and the recovery income is improved.
A tin alloy scrap recycling system comprising the steps of:
s1: a pretreatment step;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking the alloy slag in water to obtain soaking liquid and soaking slag;
s4: carrying out arsenic precipitation treatment on the water immersion liquid to obtain arsenic-calcium slag;
s5: electrolyzing and treating water leaching residues to obtain tin-containing filter residues and a tin-removed copper electrolyte;
s6: heating tin-containing filter residues, separating and filtering to obtain tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte to obtain cathode copper and electrolyte.
Further, the pretreatment step in S1 is as follows: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm.
The beneficial effects of the technical scheme are that: according to the invention, the waste is crushed into the slag in the pretreatment step, so that the contact area of the tin alloy reaction can be increased, the tin alloy reaction is promoted, and the energy loss is reduced.
Further, the carbonaceous reducing agent in the S2 is one or more of coke and graphite;
the inert gas is one of helium, neon or argon.
The beneficial effects of the technical scheme are that: the carbonaceous reductant does not consume energy, but instead converts oxides to unoxidized, thereby reducing carbon emissions. And, the carbonaceous reducing agent can accelerate the chemical reaction, thereby further reducing the energy consumption.
The inert gas can keep a certain pressure in the heating furnace, and the vacuum degree in the furnace is adjusted, so that the volatilization of metal elements is prevented, and the metal recovery rate is improved.
Further, the operation method of water leaching in S3 specifically includes:
the ball milling-water leaching technology is utilized, the solid-liquid ratio is 1:5-10, the leaching temperature is 80-90 ℃, and the leaching liquid and the leaching slag are obtained.
The beneficial effects of the technical scheme are that: arsenic and metal parts in the alloy can be effectively separated through the water leaching process, so that the effect of differentially extracting different valuable metals and reducing impurities in the valuable metal extract is achieved.
Further, the operation method of S4 specifically includes:
adding sodium sulfide into the water leaching solution, stirring uniformly at 30-40 ℃ for reaction, and obtaining arsenic sulfide precipitate and arsenic removal liquid.
The beneficial effects of the technical scheme are that: the reaction between metals can be reduced by precipitating arsenic, and the arsenic precipitation is beneficial to the extraction of substances in the subsequent arsenic precipitation filtrate.
Further, the operation method of S5 specifically includes:
1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 1-2 g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.05-0.1% of the electrolyte, and the tin removal reaction time is 60min.
The beneficial effects of the technical scheme are that: the method has the advantages of simple operation, capability of separating copper from tin in the electrolyte, more thorough tin precipitation in the electrolyte by taking limestone powder and phosphoric acid as combined precipitants, capability of changing sediment slag type and easiness in filtering, thereby achieving the purpose of extracting tin.
Further, the operation method of S6 specifically includes:
heating the tin-containing filter residue to 210-230 ℃ to remove insoluble impurities, and obtaining tin.
Further, the operation method of S7 specifically includes:
and (3) electrolyzing the tin-removed copper electrolyte, wherein a titanium ruthenium-coated plate or a lead alloy plate is used as an anode, and copper is obtained through electrolysis.
Compared with the prior art, the invention has the following advantages and beneficial effects: according to the invention, through a comprehensive recovery method, the fire method, the wet method and the electrolytic method are combined and utilized, so that the energy consumption is reduced, valuable metals in tin alloy waste can be extracted in a distinguishing manner, the recovery difficulty of tin alloy is reduced, the recovery rate of each metal is improved, and the recovery income is improved.
Drawings
FIG. 1 is a flow chart of the invention for extracting different valuable metals from tin alloys.
Detailed Description
The invention provides a regeneration system of tin alloy scraps, which is used for making the purposes, technical schemes and advantages of the invention clearer and more definite, and further detailed description of the invention is carried out by combining the description of the drawings and the following reference examples. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and not limiting of the present invention, and that new embodiments may be formed by any combination of the various embodiments or technical features described below without conflict.
Example 1
A tin alloy scrap recycling system comprising the steps of:
s1: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag; the carbonaceous reducing agent is coke; the inert gas is helium;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking the alloy slag in water at the leaching temperature of 80 ℃ by using a ball milling-water leaching process, wherein the solid-liquid ratio is 1:5, so as to obtain water leaching liquid and water leaching slag;
s4: adding sodium sulfide into the water immersion liquid, uniformly stirring at 30 ℃ for reaction, and carrying out arsenic precipitation treatment to obtain arsenic sulfide precipitate and arsenic removal liquid;
s5: 1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 1g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.05% of the electrolyte, and the tin removal reaction time is 60min.
S6: heating tin-containing filter residues to 210 ℃, separating and filtering to remove insoluble impurities, and obtaining tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte, and using a titanium ruthenium-coated plate as an anode to obtain copper through electrolysis.
Example 2
A tin alloy scrap recycling system comprising the steps of:
s1: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag; the carbonaceous reducing agent is graphite; the inert gas is neon;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking alloy slag in water at 85 ℃ by using a ball milling-water soaking process, wherein the solid-liquid ratio is 1:7, so as to obtain water soaking liquid and water soaking slag;
s4: adding sodium sulfide into the water immersion liquid, uniformly stirring at 35 ℃ for reaction, and carrying out arsenic precipitation treatment to obtain arsenic sulfide precipitate and arsenic removal liquid;
s5: 1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 1.5g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.08% of the electrolyte, and the tin removal reaction time is 60min.
S6: heating tin-containing filter residues to 220 ℃, separating and filtering to remove insoluble impurities, and obtaining tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte, wherein a titanium ruthenium-coated plate or a lead alloy plate is used as an anode, and copper is obtained through electrolysis.
Example 3
A tin alloy scrap recycling system comprising the steps of:
s1: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag; the carbonaceous reducing agent is coke; the inert gas is argon;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking alloy slag in water at 90 deg.c to obtain water soaking liquid and water soaking slag in the solid-liquid ratio of 1 to 10;
s4: adding sodium sulfide into the water immersion liquid, uniformly stirring at 40 ℃ for reaction, and carrying out arsenic precipitation treatment to obtain arsenic sulfide precipitate and arsenic removal liquid;
s5: 1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 2g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.1% of the electrolyte, and the tin removal reaction time is 60min.
S6: heating tin-containing filter residues to 230 ℃, separating and filtering to remove insoluble impurities, and obtaining tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte, wherein a titanium ruthenium-coated plate or a lead alloy plate is used as an anode, and copper is obtained through electrolysis.
Comparative example 1
A tin alloy scrap recycling system comprising the steps of:
s1: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag; the carbonaceous reducing agent is coke and the inert gas is helium;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking the alloy slag in water at the leaching temperature of 80 ℃ by using a ball milling-water leaching process, wherein the solid-liquid ratio is 1:5, so as to obtain water leaching liquid and water leaching slag;
s4: adding sodium sulfide into the water immersion liquid, uniformly stirring at 30 ℃ for reaction, and carrying out arsenic precipitation treatment to obtain arsenic sulfide precipitate and arsenic removal liquid;
s5: heating the water-containing slag to 210 ℃, separating and filtering to remove insoluble impurities, and obtaining tin;
s6: and (3) electrolyzing the tin-removed copper electrolyte, and using a titanium ruthenium-coated plate as an anode to obtain copper through electrolysis.
Comparative example 2
A tin alloy scrap recycling system comprising the steps of:
s1: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm;
s2: roasting the slag obtained in the step S1, and filtering insoluble matters to obtain alloy liquid;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking alloy slag in water at 85 ℃ by using a ball milling-water soaking process, wherein the solid-liquid ratio is 1:7, so as to obtain water soaking liquid and water soaking slag;
s4: adding sodium sulfide into the water immersion liquid, uniformly stirring at 35 ℃ for reaction, and carrying out arsenic precipitation treatment to obtain arsenic sulfide precipitate and arsenic removal liquid;
s5: 1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 1.5g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.08% of the electrolyte, and the tin removal reaction time is 60min.
S6: heating tin-containing filter residues to 220 ℃, separating and filtering to remove insoluble impurities, and obtaining tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte, wherein a titanium ruthenium-coated plate or a lead alloy plate is used as an anode, and copper is obtained through electrolysis.
Comparative example 3
A tin alloy scrap recycling system comprising the steps of:
s1: collecting tin alloy waste slag, and crushing the waste into slag with the size of 6 mm;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag; the carbonaceous reducing agent is graphite; the inert gas is neon;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking alloy slag in water at a solid-liquid ratio of 1:15 and a leaching temperature of 50 ℃ by using a ball milling-water leaching process to obtain water leaching liquid and water leaching slag;
s4: adding sodium sulfide into the water immersion liquid, uniformly stirring at 35 ℃ for reaction, and carrying out arsenic precipitation treatment to obtain arsenic sulfide precipitate and arsenic removal liquid;
s5: 1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 0.5g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.03% of the electrolyte, and the tin removal reaction time is 30min.
S6: heating tin-containing filter residues to 220 ℃, separating and filtering to remove insoluble impurities, and obtaining tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte, wherein a titanium ruthenium-coated plate or a lead alloy plate is used as an anode, and copper is obtained through electrolysis.
Test example 1
300g of tin alloy was recovered by applying the technical schemes in examples 1-3 and comparative examples 1-3 of the present invention, the content of each metal component in the tin alloy is shown in Table 1, and the recovery results are shown in Table 2.
Description: since the lead oxide is added as a reaction raw material in the processing process, the yield of lead is affected, and therefore, the yield of lead metal is not counted.
TABLE 1 content of Metal Components in tin alloys
| Tin content (%) | Antimony content (%) | Copper content (%) | |
| Tin alloy | 24.8％ | 7.2％ | 9.5％ |
Note that: the units in Table 1 are mass percent
Table 2 recovery for each experimental procedure
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tin yield (%) | 92.89 | 95.15 | 94.96 | 25.61 | 56.20 | 83.74 |
| Antimony yield (%) | 90.97 | 92.74 | 91.37 | 50.16 | 73.67 | 54.59 |
| Copper yield (%) | 98.54 | 99.21 | 98.93 | 32.13 | 63.48 | 47.28 |
As shown in Table 2, the recovery rate of each valuable metal in the tin alloy is over 90% by applying the technical scheme disclosed in the embodiment of the invention. The electrolysis step was omitted in comparative example 1; comparative example 2 is not limited to the addition of a carbonaceous reducing agent and is not limited to processing under an inert atmosphere; the values in comparative example 3 were set outside the scope of the present invention, and it was found from the results that the recovery rate of each valuable metal in the tin alloy was reduced after the adjustment of comparative examples 1 to 3 was made.
Test example two
300g of tin alloy with a metal raw material ratio different from that of the test example is recovered by using the technical schemes in the examples 1-3 and the comparative examples 1-3, wherein the content of each metal component in the tin alloy is shown in the table 3, and the recovery result is shown in the table 4.
Description: since the lead oxide is added as a reaction raw material in the processing process, the yield of lead is affected, and therefore, the yield of lead metal is not counted.
TABLE 3 content of Metal Components in tin alloys
| Tin content (%) | Antimony content (%) | Copper content (%) | |
| Tin alloy | 23.2％ | 10.3％ | 9.8％ |
Table 4 recovery for each experimental procedure
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tin yield (%) | 93.36 | 95.42 | 94.22 | 27.28 | 59.30 | 82.15 |
| Antimony yield (%) | 90.97 | 93.22 | 91.86 | 53.18 | 71.81 | 54.10 |
| Copper yield (%) | 98.77 | 99.18 | 99.10 | 32.41 | 65.94 | 48.37 |
As shown in Table 4, the recovery rate of each valuable metal in the tin alloy was over 90% by applying the technical scheme disclosed in the examples of the present invention. After the adjustment of comparative examples 1 to 3, the recovery rate of each valuable metal in the tin alloy was reduced.
Thus, in view of the many possible embodiments that may be applied to the principles disclosed, it should be recognized that the above-described embodiments are merely examples and should not be taken as limiting in scope. Accordingly, we reserve all rights to the subject matter disclosed herein, including claims that claim any and all combinations of the subject matter disclosed herein, including but not limited to all within the scope and spirit of the claims.
Claims (8)
1. A tin alloy scrap recycling system, comprising the steps of:
s1: a pretreatment step;
s2: adding a carbonaceous reducing agent, roasting in an inert atmosphere, filtering insoluble substances, and carrying out oxidation refining to obtain refined antimony alloy and alloy slag;
s3: the refined antimony alloy reacts with lead oxide under vacuum condition to obtain antimony and lead;
soaking the alloy slag in water to obtain soaking liquid and soaking slag;
s4: carrying out arsenic precipitation treatment on the water immersion liquid to obtain arsenic-calcium slag;
s5: electrolyzing and treating water leaching residues to obtain tin-containing filter residues and a tin-removed copper electrolyte;
s6: heating tin-containing filter residues, separating and filtering to obtain tin;
s7: and (3) electrolyzing the tin-removed copper electrolyte to obtain cathode copper and electrolyte.
2. The recycling system of tin alloy scrap according to claim 1, wherein the pretreatment step in S1 is: collecting tin alloy waste slag, and crushing the waste into slag with the size of 3 mm.
3. The tin alloy scrap recycling system according to claim 1, wherein the carbonaceous reducing agent in S2 is one or more of coke and graphite;
the inert gas is one of helium, neon or argon.
4. The tin alloy scrap recycling system according to claim 1, wherein said S3 water leaching operation method comprises:
the ball milling-water leaching technology is utilized, the solid-liquid ratio is 1:5-10, the leaching temperature is 80-90 ℃, and the leaching liquid and the leaching slag are obtained.
5. The tin alloy scrap recycling system according to claim 1, wherein said S4 operation method specifically comprises:
adding sodium sulfide into the water leaching solution, stirring uniformly at 30-40 ℃ for reaction, and obtaining arsenic sulfide precipitate and arsenic removal liquid.
6. The tin alloy scrap recycling system according to claim 1, wherein said S5 operation method specifically comprises:
1) Adding the water leaching slag into an initial electrolyte, wherein the H+ concentration in the initial electrolyte is 1-2 g/L;
2) The limestone powder is used for neutralizing the copper-tin-containing electrolyte, and the reaction time is 30min;
3) Adding phosphoric acid to remove tin to obtain tin-containing filter residues and a tin-removed copper electrolyte;
the addition amount of the phosphoric acid is 0.05-0.1% of the electrolyte, and the tin removal reaction time is 60min.
7. The tin alloy scrap recycling system according to claim 1, wherein said S6 operation method specifically comprises:
heating the tin-containing filter residue to 210-230 ℃ to remove insoluble impurities, and obtaining tin.
8. The tin alloy scrap recycling system according to claim 1, wherein said S7 operating method specifically comprises:
and (3) electrolyzing the tin-removed copper electrolyte, wherein a titanium ruthenium-coated plate or a lead alloy plate is used as an anode, and copper is obtained through electrolysis.
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| CN202311570689.7A CN117587259A (en) | 2023-11-23 | 2023-11-23 | Regeneration system of tin alloy waste |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311570689.7A CN117587259A (en) | 2023-11-23 | 2023-11-23 | Regeneration system of tin alloy waste |
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