CN106282571B - A kind of comprehensive recycling process of tin copper gold and silver waste material - Google Patents
A kind of comprehensive recycling process of tin copper gold and silver waste material Download PDFInfo
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- CN106282571B CN106282571B CN201610668478.0A CN201610668478A CN106282571B CN 106282571 B CN106282571 B CN 106282571B CN 201610668478 A CN201610668478 A CN 201610668478A CN 106282571 B CN106282571 B CN 106282571B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 84
- 239000004332 silver Substances 0.000 title claims abstract description 84
- 239000002699 waste material Substances 0.000 title claims abstract description 72
- MPLZHWQMZBPGKJ-UHFFFAOYSA-N [Cu].[Sn].[Au] Chemical compound [Cu].[Sn].[Au] MPLZHWQMZBPGKJ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 44
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052737 gold Inorganic materials 0.000 claims abstract description 25
- 239000010931 gold Substances 0.000 claims abstract description 25
- 229910052718 tin Inorganic materials 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000011343 solid material Substances 0.000 claims description 95
- 239000000243 solution Substances 0.000 claims description 66
- 238000000926 separation method Methods 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 35
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 239000011344 liquid material Substances 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003350 kerosene Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 7
- 229910021538 borax Inorganic materials 0.000 claims description 7
- 238000005272 metallurgy Methods 0.000 claims description 7
- 239000004328 sodium tetraborate Substances 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229960004643 cupric oxide Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 230000002459 sustained effect Effects 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011135 tin Substances 0.000 abstract description 19
- 238000003912 environmental pollution Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 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
- 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
- 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
- C22B1/02—Roasting 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
- 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
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- 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 present invention relates to a kind of recovery process, more particularly to a kind of comprehensive recycling process of tin copper gold and silver waste material.The technical problem to be solved in the present invention is to provide it is a kind of reclaim product it is comprehensive, organic efficiency is high, do not easily cause environmental pollution tin copper gold and silver waste material comprehensive recycling process.The invention provides the comprehensive recycling process of such a tin copper gold and silver waste material, by step A N, by the extracting step by step of the tin copper gold and silver in tin copper gold and silver waste material.The present invention passes through the step of science and designed, tin copper gold and silver waste material is first passed through ball milling and dry the handling process for being calcined crush again again again, the tin copper gold and silver element in tin copper gold and silver waste material is set sufficiently to be separated, greatly improve the organic efficiency of tin copper gold and silver waste material, separated again by with different levels extraction, copper, tin, silver and gold are reclaimed respectively in order, make waste recovery comprehensively and thorough, do not allow to be also easy to produce waste, reached recovery product it is comprehensive, organic efficiency is high, does not easily cause the effect of environmental pollution.
Description
Technical field
The present invention relates to a kind of recovery process, more particularly to a kind of comprehensive recycling process of tin copper gold and silver waste material.
Background technology
Tin is a kind of metallic element, symbol of element Sn, atomic number 50, relative atomic mass 118.71, and fusing point is
231.89 DEG C, boiling point is 2260 DEG C, density 7.28g/cm3.Tin is a kind of low-melting-point metal for having silvery white metallic luster, pure
Tin matter is soft, and malleability is good under normal temperature, and chemical property is stable, is not easy to be oxidized, and often keeps the glittering gloss of silver.Tin is in the earth's crust
Content is 0.004%, is existed nearly all in the form of tin oxide, in addition with the sulfide mine of minimal amount of tin.As " five
One of gold " (gold, silver, copper, iron, tin), early in B.C. 2000, tin just had begun to be used by the mankind.Tin is main at present
For manufacturing scolding tin, tin plate, alloy, heavy chemicals etc., product be widely used in electronics, information, electrical equipment, chemical industry, metallurgy,
The industries such as building materials, packaging for foodstuff, machinery, atomic energy and aerospace industry.In addition, it is all common metallic iron, copper, Jin Heyin, just
It is more conventional, it is widely used in the various aspects of our daily lifes, the life to us plays the role of important.
Social development, various product change with each passing day now, the especially update of electronic product, and speed is fast
Allow people to be left speechless, just need various corresponding raw material to provide basis for the manufacture of electronic product for this, it is well known that electronics industry
All kinds of trace elements are often used, therefore, various micro- exploits in progress also like a raging fire, mining technique obtains
Further development, mining depth also enters a New step, but the problem of corresponding also occurs for this, is exactly mineral mining warp
Cross after processing obtains basic product, also contain a lot of other chemical elements in its waste material in fact, if be not used, will cause
Greatly waste.
Especially for the waste material containing tin copper gold and silver, internal metal has great economic value, if moreover, return
Receive it is improper will not only cause the wasting of resources can also generation environment pollution, therefore, just needing to carry out the waste material of tin copper gold and silver comprehensive
Recovery process, but the recovery process of existing tin copper gold and silver waste material exist recovery product it is single, organic efficiency is low, easily causes ring
The shortcomings that border is polluted, therefore, for the growing of electronics now and mineral mining industry, there is provided one kind recovery product comprehensively,
The comprehensive recycling process for the tin copper gold and silver waste material that organic efficiency is high, does not easily cause environmental pollution seems more next under current situation
It is more urgent.
The content of the invention
(1) technical problems to be solved
The recovery process of existing tin copper gold and silver waste material recovery product is single, organic efficiency is low, Yi Zao in order to overcome by the present invention
Into the shortcomings that environmental pollution, the technical problem to be solved in the present invention is to provide one kind recovery product is comprehensive, organic efficiency is high, is not easy
Cause the comprehensive recycling process of the tin copper gold and silver waste material of environmental pollution.
(2) technical scheme
In order to solve the above-mentioned technical problem, the invention provides the comprehensive recycling process of such a tin copper gold and silver waste material,
Specifically include following steps：
A. ball milling is carried out using ball mill to tin copper gold and silver waste material, material is ground；
B. the material treated through A is subjected to heating, drying, heating-up temperature is 300-400 DEG C, and the heat time is that 2-3 is small
When；
C. the material treated through B is calcined using rotary furnace, sintering temperature is 500-600 DEG C, and roasting time is
3-4 hours；
D. the material treated through C is crushed using pulverizer, material is thoroughly crushed；
E. the material treated through D is added into distilled water to be soaked, and adds sulfuric acid and be adjusted to soaking solution pH
The immersion solid-to-liquid ratio of 1.5-2, material and distilled water is 3.5-5：1, soaking temperature is reached 80-90 DEG C by steam heating, leaching
The bubble time is 4-5 hours, is filtered again afterwards, realizes separation of solid and liquid, separation draws solid material I and liquid material I, and divides
Do not continue to employ；
F. addition piece alkali in the liquid material I drawn is separated into E, pH value of solution is adjusted to 9.5-10.5, passes through steam
Heating makes solution temperature reach 80-90 DEG C, hour duration 1-2, is filtered again afterwards, realizes separation of solid and liquid, separated
To solid material II, solid material II is cupric oxide, that is, realizes the recovery to copper in tin copper gold and silver waste material；
G. separated into E and sodium chloride solution is added in the solid material I drawn, sodium chloride concentration 25%-35%, passed through
Add hydrochloric acid and pH value of solution is adjusted to 0.5-1, solid-to-liquid ratio 3.5-5：1, solution temperature is reached 80-90 by steam heating
DEG C, the duration is 3-4 hours, is filtered again afterwards, realizes separation of solid and liquid, and separation draws solid material III and liquid material
III, liquid material III is continued to employ, and solid material III is tin oxide, that is, realizes the recovery to tin element in tin copper gold and silver waste material；
H. the aluminium powder that 1-1.2 times of III weight of liquid material is added in the liquid material III drawn is separated into G, passes through steam
Heating makes solution temperature reach 45-55 DEG C, and the duration is 1-2 hours, is filtered again afterwards, realizes separation of solid and liquid, separation
Draw solid material IV；
I. the solid material IV that draws will be separated in H to add in intermediate frequency furnace, adds 0.1-0.14 times of IV weight of solid material
Carbon dust, add the soda ash of 0.12-0.18 times of solid material IV weight, the boron of 0.05-0.07 times of IV weight of addition solid material
Sand, heating-up temperature is 1200-1400 DEG C, and Continuous aeration, sustained response time are 1-2 hours, carries out melting；
J. using through the material that I is treated, as anode, the mixed solution of nitric acid and silver nitrate is added, is electrolysed, is mixed
The concentration of nitric acid is 3-5g/L in liquid, and the concentration of silver nitrate is 80-150g/L in mixed liquor, and after the completion of electrolysis, negative electrode obtains list
Matter silver, that is, realize the recovery to silver element in tin copper gold and silver waste material, and the undissolved solid of anode is filtered, and obtains solid
Material V；
K. the mixed solution that hydrochloric acid and sodium chlorate are added in the solid material V drawn is separated into J, hydrochloric acid in mixed liquor
Concentration be 50-70g/L, the concentration of sodium chlorate is 90-110g/L in mixed liquor, reaches solution temperature by steam heating
80-90 DEG C, solid-to-liquid ratio 2.5-3.5：1, the duration is 0.8-1.2 hours, is added afterwards mixed with hydrochloric acid and sodium chlorate
Close the isometric tributyl phosphate of solution and kerosene mixture, tributyl phosphate and kerosene in tributyl phosphate and kerosene mixture
Volume ratio be 0.7-0.9：1, extracted and separated, isolated organic phase is continued to employ；
L. the organic 10- for being added in reactor, adding organic 0.4-0.6 times of phase volume drawn will be separated in K
The hydrochloric acid solution of 12% concentration, the oxalic acid solution of the 8-10% concentration of organic 0.2-0.4 times of phase volume is added, is heated by steam
Solution temperature is reached 60-80 DEG C, be stirred continuously, the duration is 0.5-0.7 hours, carries out back extraction reduction, carries out again afterwards
Filtering, realizes separation of solid and liquid, and separation draws solid material VI；
M. the distilled water that 2-2.4 times of VI weight of solid material is added in the solid material VI drawn is separated into L, and together
Heating is boiled, and is persistently boiled 10-20 minutes, is filtered again afterwards, realizes separation of solid and liquid, and separation draws solid material VII；
N. the solid material VII that draws will be separated in M to be added in crucible, and adds 0.2-0.4 times of VII weight of solid material
Borax, heating-up temperature be 1100-1300 DEG C, the duration be 15-25 minutes, and final product obtains elemental gold, i.e., realization pair
The recovery of gold element in tin copper gold and silver waste material.
Preferably, in step D, crushing is crushed using Raymond mill machine.
Preferably, in step E or step F or step G or step H or step J or step L or step M, filtering is to utilize railway carriage or compartment
Formula filter press is filtered.
Preferably, in step F, add piece alkali and pH value of solution is adjusted to 10, solution temperature is reached 85 by steam heating
DEG C, 1.5 hours duration.
Preferably, in step G, sodium chloride solution is added, sodium chloride concentration 30%, is adjusted pH value of solution by adding hydrochloric acid
Whole is 0.8, solid-to-liquid ratio 4：1, solution temperature is reached 85 DEG C by steam heating, the duration is 3.5 hours.
Preferably, in step N, the borax of 0.3 times of VII weight of solid material is added, heating-up temperature is 1200 DEG C, when continuing
Between be 20 minutes.
Preferably, in step N, heated by gold metallurgy flame gun.
(3) beneficial effect
The present invention compared with prior art, design, and tin copper gold and silver waste material is first passed through ball milling and dries again by the step of passing through science
It is dry to be calcined the handling process crushed again again, the tin copper gold and silver element in tin copper gold and silver waste material is sufficiently separated, and have
Beneficial to the progress of subsequent processing operations, the organic efficiency of tin copper gold and silver waste material is greatly improved, then, then by with different levels
Extraction separation, the copper in tin copper gold and silver waste material, tin, silver and gold are reclaimed respectively in order step by step, while reasonably
Removal process and accurate recovery condition is scheduled, not only makes waste recovery comprehensively and thorough, and organic efficiency is high, it is not easy to
Waste is produced, and the present invention limits the removal process of every kind of element in four steps, ensure that the controllable of recycled in its entirety
Property, it even if some small step is out of joint, can also be well solved on the whole, ensure that the continuity of recovery process, really
Protect and environmental pollution is not easily caused in removal process, also, passed through in the step E and step F and step G and step K of the present invention
Accurate solid-to-liquid ratio and reaction time, reactant is set to make generation fully complete to carry out within the most short time, while each step is led to
Steam heating is crossed, the present invention progress for the reaction being greatly promoted, is finally reached on the premise of reaction result is not influenceed
Recovery product is comprehensive, organic efficiency is high, does not easily cause the effect of environmental pollution.
In step D, crushing is crushed using Raymond mill machine, so tin copper gold and silver waste material can be crushed more thorough
Bottom, make the various products of later stage recovery more careful, make product precision height, purity high, need not can again purify and can directly make
Used for raw material.
Preferably, in step E or step F or step G or step H or step J or step L or step M, filtering is to utilize railway carriage or compartment
Formula filter press is filtered, and can so make filtering more thorough, is made the recovery of each element more efficient, is not produced waste.
In step N, heated by gold metallurgy flame gun, so heat quicker, the directly recovery of raising gold element
Speed, accelerate the progress of reaction, improve organic efficiency.
Embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples.
Embodiment 1
A kind of comprehensive recycling process of tin copper gold and silver waste material, specifically includes following steps：
A. ball milling is carried out using ball mill to tin copper gold and silver waste material, material is ground；
B. the material treated through A is subjected to heating, drying, heating-up temperature is 300 DEG C, and the heat time is 3 hours；
C. the material treated through B is calcined using rotary furnace, sintering temperature is 500 DEG C, and roasting time is 4 small
When；
D. the material treated through C is crushed using Raymond mill machine, material is thoroughly crushed；
E. the material treated through D is added into distilled water to be soaked, and adds sulfuric acid and be adjusted to soaking solution pH
1.5, immersion solid-to-liquid ratio is 5：1, soaking temperature is reached 80 DEG C by steam heating, soak time is 5 hours, is passed through again afterwards
Chamber-type press filter is filtered, and realizes separation of solid and liquid, separation draws solid material I and liquid material I, and continues to employ respectively；
F. addition piece alkali in the liquid material I drawn is separated into E, pH value of solution is adjusted to 9.5, is made by steam heating
Solution temperature reaches 80 DEG C, 2 hours duration, is filtered again by chamber-type press filter afterwards, realizes separation of solid and liquid, separation
Solid material II is obtained, solid material II is cupric oxide, that is, realizes the recovery to copper in tin copper gold and silver waste material；
G. separated into E and sodium chloride solution is added in the solid material I drawn, sodium chloride concentration 25%, pass through addition
PH value of solution is adjusted to 0.5 by hydrochloric acid, solid-to-liquid ratio 3.5：1, solution temperature is reached 80 DEG C by steam heating, the duration is
4 hours, filtered again by chamber-type press filter afterwards, realize separation of solid and liquid, separation draws solid material III and liquid material
III, liquid material III is continued to employ, and solid material III is tin oxide, that is, realizes the recovery to tin element in tin copper gold and silver waste material；
H. the aluminium powder that 1 times of III weight of liquid material is added in the liquid material III drawn is separated into G, is heated by steam
Solution temperature is set to reach 55 DEG C, the duration is 1 hour, is filtered again by chamber-type press filter afterwards, realizes separation of solid and liquid,
Separation draws solid material IV；
I. the solid material IV that draws will be separated in H to add in intermediate frequency furnace, adds the carbon of 0.1 times of IV weight of solid material
Powder, the soda ash of 0.12 times of IV weight of solid material is added, add the borax of 0.05 times of IV weight of solid material, heating-up temperature is
1400 DEG C, and Continuous aeration, sustained response time are 1 hour, carry out melting；
J. using through the material that I is treated, as anode, the mixed solution of nitric acid and silver nitrate is added, is electrolysed, is mixed
The concentration of nitric acid is 3g/L in liquid, and the concentration of silver nitrate is 80g/L in mixed liquor, and after the completion of electrolysis, negative electrode obtains elemental silver, i.e.,
The recovery to silver element in tin copper gold and silver waste material is realized, and the undissolved solid of anode is filtered by chamber-type press filter,
Obtain solid material V；
K. the mixed solution that hydrochloric acid and sodium chlorate are added in the solid material V drawn is separated into J, hydrochloric acid in mixed liquor
Concentration be 50g/L, the concentration of sodium chlorate is 90g/L in mixed liquor, solution temperature is reached 90 DEG C by steam heating, solid-liquid
Than for 2.5：1, the duration is 0.8 hour, adds the tricresyl phosphate isometric with the mixed solution of hydrochloric acid and sodium chlorate afterwards
The volume ratio of tributyl phosphate and kerosene is 0.9 in butyl ester and kerosene mixture, tributyl phosphate and kerosene mixture：1, carry out
Extract and separate, isolated organic phase is continued to employ；
L. draw organic will be separated in K to be added in reactor, adds 12% concentration of organic 0.4 times of phase volume
Hydrochloric acid solution, the oxalic acid solution of 10% concentration of organic 0.2 times of phase volume is added, solution temperature is reached 80 by steam heating
DEG C, it is stirred continuously, the duration is 0.5 hour, carries out back extraction reduction, is filtered again by chamber-type press filter afterwards, is realized
Separation of solid and liquid, separation draw solid material VI；
M. the distilled water that 2 times of VI weight of solid material is added in the solid material VI drawn is separated into L, and is together heated
Boil, persistently boil 20 minutes, filtered again by chamber-type press filter afterwards, realize separation of solid and liquid, separation draws solids
Material VII；
N. the solid material VII that draws will be separated in M to be added in crucible, and adds the boron of 0.2 times of VII weight of solid material
Sand, and heated by gold metallurgy flame gun, heating-up temperature is 1300 DEG C, and the duration is 15 minutes, and final product obtains list
Matter gold, that is, realize the recovery to gold element in tin copper gold and silver waste material.
Embodiment 2
A kind of comprehensive recycling process of tin copper gold and silver waste material, specifically includes following steps：
A. ball milling is carried out using ball mill to tin copper gold and silver waste material, material is ground；
B. the material treated through A is subjected to heating, drying, heating-up temperature is 350 DEG C, and the heat time is 2.5 hours；
C. the material treated through B is calcined using rotary furnace, sintering temperature is 550 DEG C, and roasting time is 3.5 small
When；
D. the material treated through C is crushed using Raymond mill machine, material is thoroughly crushed；
E. the material treated through D is added into distilled water to be soaked, and adds sulfuric acid and be adjusted to soaking solution pH
1.8, immersion solid-to-liquid ratio is 4：1, soaking temperature is reached 85 DEG C by steam heating, soak time is 4.5 hours, is led to again afterwards
Cross chamber-type press filter to be filtered, realize separation of solid and liquid, separation draws solid material I and liquid material I, and continues to employ respectively；
F. addition piece alkali in the liquid material I drawn is separated into E, pH value of solution is adjusted to 10, is made by steam heating
Solution temperature reaches 85 DEG C, 1.5 hours duration, is filtered again by chamber-type press filter afterwards, realizes separation of solid and liquid, point
From solid material II is obtained, solid material II is cupric oxide, that is, realizes the recovery to copper in tin copper gold and silver waste material；
G. separated into E and sodium chloride solution is added in the solid material I drawn, sodium chloride concentration 30%, pass through addition
PH value of solution is adjusted to 0.8 by hydrochloric acid, solid-to-liquid ratio 4：1, solution temperature is reached 85 DEG C by steam heating, the duration is
3.5 hours, filtered again by chamber-type press filter afterwards, realize separation of solid and liquid, separation draws solid material III and liquids
Material III, liquid material III is continued to employ, and solid material III is tin oxide, that is, realizes the recovery to tin element in tin copper gold and silver waste material；
H. the aluminium powder that 1.1 times of liquid material III weight is added in the liquid material III drawn is separated into G, by steam plus
Heat makes solution temperature reach 50 DEG C, and the duration is 1.5 hours, is filtered again by chamber-type press filter afterwards, realizes solid-liquid
Separation, separation draw solid material IV；
I. the solid material IV that draws will be separated in H to add in intermediate frequency furnace, adds the carbon of 0.12 times of IV weight of solid material
Powder, the soda ash of 0.15 times of IV weight of solid material is added, add the borax of 0.06 times of IV weight of solid material, heating-up temperature is
1300 DEG C, and Continuous aeration, sustained response time are 1.5 hours, carry out melting；
J. using through the material that I is treated, as anode, the mixed solution of nitric acid and silver nitrate is added, is electrolysed, is mixed
The concentration of nitric acid is 4g/L in liquid, and the concentration of silver nitrate is 110g/L in mixed liquor, and after the completion of electrolysis, negative electrode obtains elemental silver,
The recovery to silver element in tin copper gold and silver waste material is realized, and the undissolved solid of anode was carried out by chamber-type press filter
Filter, obtains solid material V；
K. the mixed solution that hydrochloric acid and sodium chlorate are added in the solid material V drawn is separated into J, hydrochloric acid in mixed liquor
Concentration be 60g/L, the concentration of sodium chlorate is 100g/L in mixed liquor, solution temperature is reached 85 DEG C by steam heating, Gu
Liquor ratio is 3：1, the duration is 1 hour, adds the tricresyl phosphate fourth isometric with the mixed solution of hydrochloric acid and sodium chlorate afterwards
The volume ratio of tributyl phosphate and kerosene is 0.8 in ester and kerosene mixture, tributyl phosphate and kerosene mixture：1, extracted
Take and separate, isolated organic phase is continued to employ；
L. draw organic will be separated in K to be added in reactor, adds 11% concentration of organic 0.5 times of phase volume
Hydrochloric acid solution, the oxalic acid solution of 9% concentration of organic 0.3 times of phase volume is added, solution temperature is reached 70 by steam heating
DEG C, it is stirred continuously, the duration is 0.6 hour, carries out back extraction reduction, is filtered again by chamber-type press filter afterwards, is realized
Separation of solid and liquid, separation draw solid material VI；
M. the distilled water that 2.2 times of VI weight of solid material is added in the solid material VI drawn is separated into L, and is together added
Heat is boiled, and is persistently boiled 15 minutes, is filtered again by chamber-type press filter afterwards, realizes separation of solid and liquid, and separation draws solid
Material VII；
N. the solid material VII that draws will be separated in M to be added in crucible, and adds the boron of 0.3 times of VII weight of solid material
Sand, and heated by gold metallurgy flame gun, heating-up temperature is 1200 DEG C, and the duration is 20 minutes, and final product obtains list
Matter gold, that is, realize the recovery to gold element in tin copper gold and silver waste material.
Embodiment 3
A kind of comprehensive recycling process of tin copper gold and silver waste material, specifically includes following steps：
A. ball milling is carried out using ball mill to tin copper gold and silver waste material, material is ground；
B. the material treated through A is subjected to heating, drying, heating-up temperature is 400 DEG C, and the heat time is 2 hours；
C. the material treated through B is calcined using rotary furnace, sintering temperature is 600 DEG C, and roasting time is 3 small
When；
D. the material treated through C is crushed using Raymond mill machine, material is thoroughly crushed；
E. the material treated through D is added into distilled water to be soaked, and adds sulfuric acid and soaking solution pH is adjusted to 2,
It is 3.5 to soak solid-to-liquid ratio：1, soaking temperature is reached 90 DEG C by steam heating, soak time is 4 hours, passes through railway carriage or compartment again afterwards
Formula filter press is filtered, and realizes separation of solid and liquid, separation draws solid material I and liquid material I, and continues to employ respectively；
F. addition piece alkali in the liquid material I drawn is separated into E, pH value of solution is adjusted to 10.5, heated by steam
Solution temperature is reached 90 DEG C, 1 hour duration, filtered again by chamber-type press filter afterwards, realize separation of solid and liquid, point
From solid material II is obtained, solid material II is cupric oxide, that is, realizes the recovery to copper in tin copper gold and silver waste material；
G. separated into E and sodium chloride solution is added in the solid material I drawn, sodium chloride concentration 35%, pass through addition
PH value of solution is adjusted to 1 by hydrochloric acid, solid-to-liquid ratio 5：1, solution temperature is reached 90 DEG C by steam heating, the duration is 3 small
When, to be filtered again by chamber-type press filter afterwards, realize separation of solid and liquid, separation draws solid material III and liquid material III,
Liquid material III is continued to employ, and solid material III is tin oxide, that is, realizes the recovery to tin element in tin copper gold and silver waste material；
H. the aluminium powder that 1 times of III weight of liquid material is added in the liquid material III drawn is separated into G, is heated by steam
Solution temperature is set to reach 45 DEG C, the duration is 2 hours, is filtered again by chamber-type press filter afterwards, realizes separation of solid and liquid,
Separation draws solid material IV；
I. the solid material IV that draws will be separated in H to add in intermediate frequency furnace, adds the carbon of 0.14 times of IV weight of solid material
Powder, the soda ash of 0.18 times of IV weight of solid material is added, add the borax of 0.07 times of IV weight of solid material, heating-up temperature is
1200 DEG C, and Continuous aeration, sustained response time are 2 hours, carry out melting；
J. using through the material that I is treated, as anode, the mixed solution of nitric acid and silver nitrate is added, is electrolysed, is mixed
The concentration of nitric acid is 5g/L in liquid, and the concentration of silver nitrate is 150g/L in mixed liquor, and after the completion of electrolysis, negative electrode obtains elemental silver,
The recovery to silver element in tin copper gold and silver waste material is realized, and the undissolved solid of anode was carried out by chamber-type press filter
Filter, obtains solid material V；
K. the mixed solution that hydrochloric acid and sodium chlorate are added in the solid material V drawn is separated into J, hydrochloric acid in mixed liquor
Concentration be 70g/L, the concentration of sodium chlorate is 110g/L in mixed liquor, solution temperature is reached 80 DEG C by steam heating, Gu
Liquor ratio is 3.5：1, the duration is 1.2 hours, adds the phosphoric acid isometric with the mixed solution of hydrochloric acid and sodium chlorate afterwards
The volume ratio of tributyl phosphate and kerosene is 0.7 in tributyl and kerosene mixture, tributyl phosphate and kerosene mixture：1, enter
Row is extracted and separated, and isolated organic phase is continued to employ；
L. draw organic will be separated in K to be added in reactor, adds 10% concentration of organic 0.6 times of phase volume
Hydrochloric acid solution, the oxalic acid solution of 8% concentration of organic 0.4 times of phase volume is added, solution temperature is reached 60 by steam heating
DEG C, it is stirred continuously, the duration is 0.7 hour, carries out back extraction reduction, is filtered again by chamber-type press filter afterwards, is realized
Separation of solid and liquid, separation draw solid material VI；
M. the distilled water that 2.4 times of VI weight of solid material is added in the solid material VI drawn is separated into L, and is together added
Heat is boiled, and is persistently boiled 10 minutes, is filtered again by chamber-type press filter afterwards, realizes separation of solid and liquid, and separation draws solid
Material VII；
N. the solid material VII that draws will be separated in M to be added in crucible, and adds the boron of 0.4 times of VII weight of solid material
Sand, and heated by gold metallurgy flame gun, heating-up temperature is 1100 DEG C, and the duration is 25 minutes, and final product obtains list
Matter gold, that is, realize the recovery to gold element in tin copper gold and silver waste material.
The present invention compared with prior art, design, and tin copper gold and silver waste material is first passed through ball milling and dries again by the step of passing through science
It is dry to be calcined the handling process crushed again again, the tin copper gold and silver element in tin copper gold and silver waste material is sufficiently separated, and have
Beneficial to the progress of subsequent processing operations, the organic efficiency of tin copper gold and silver waste material is greatly improved, then, then by with different levels
Extraction separation, the copper in tin copper gold and silver waste material, tin, silver and gold are reclaimed respectively in order step by step, while reasonably
Removal process and accurate recovery condition is scheduled, not only makes waste recovery comprehensively and thorough, and organic efficiency is high, it is not easy to
Waste is produced, and the present invention limits the removal process of every kind of element in four steps, ensure that the controllable of recycled in its entirety
Property, it even if some small step is out of joint, can also be well solved on the whole, ensure that the continuity of recovery process, really
Protect and environmental pollution is not easily caused in removal process, also, passed through in the step E and step F and step G and step K of the present invention
Accurate solid-to-liquid ratio and reaction time, reactant is set to make generation fully complete to carry out within the most short time, while each step is led to
Steam heating is crossed, the present invention progress for the reaction being greatly promoted, is finally reached on the premise of reaction result is not influenceed
Recovery product is comprehensive, organic efficiency is high, does not easily cause the effect of environmental pollution.
The rate of recovery of tin copper gold and silver waste material is under existing general process conditions：Tin -88%, copper -83%, gold -93%, silver
91%.The rate of recovery of tin copper gold and silver waste material is under the conditions of present invention process：Tin -93%, copper -91%, gold -98%, silver 97%.Number
According to showing, the present invention can improve the organic efficiency of each metal really, and reclaim product comprehensively, do not easily cause environmental pollution.
Embodiment described above only expresses the preferred embodiment of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformations can also be made, improves and substitutes, these belong to this hair
Bright protection domain.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (7)
1. a kind of comprehensive recycling process of tin copper gold and silver waste material, it is characterised in that specifically include following steps：
A. ball milling is carried out using ball mill to tin copper gold and silver waste material, material is ground；
B. the material treated through A is subjected to heating, drying, heating-up temperature is 300-400 DEG C, and the heat time is 2-3 hours；
C. the material treated through B is calcined using rotary furnace, sintering temperature is 500-600 DEG C, and roasting time is that 3-4 is small
When；
D. the material treated through C is crushed using pulverizer, material is thoroughly crushed；
E. the material treated through D is added into distilled water to be soaked, and adds sulfuric acid and soaking solution pH is adjusted to 1.5-2,
The immersion solid-to-liquid ratio of material and distilled water is 3.5-5：1, soaking temperature is reached 80-90 DEG C by steam heating, soak time
For 4-5 hours, filtered again afterwards, realize separation of solid and liquid, separation draws solid material I and liquid material I, and stays respectively
With；
F. addition piece alkali in the liquid material I drawn is separated into E, pH value of solution is adjusted to 9.5-10.5, heated by steam
Solution temperature is reached 80-90 DEG C, hour duration 1-2, filtered again afterwards, realize separation of solid and liquid, it is isolated solid
Body material II, solid material II are cupric oxide, that is, realize the recovery to copper in tin copper gold and silver waste material；
G. separated into E and sodium chloride solution is added in the solid material I drawn, sodium chloride concentration 25%-35%, pass through addition
PH value of solution is adjusted to 0.5-1, solid-to-liquid ratio 3.5-5 by hydrochloric acid：1, solution temperature is reached 80-90 DEG C by steam heating, hold
The continuous time is 3-4 hours, is filtered again afterwards, realizes separation of solid and liquid, and separation draws solid material III and liquid material III, liquid
Body material III is continued to employ, and solid material III is tin oxide, that is, realizes the recovery to tin element in tin copper gold and silver waste material；
H. the aluminium powder that 1-1.2 times of III weight of liquid material is added in the liquid material III drawn is separated into G, is heated by steam
Solution temperature is set to reach 45-55 DEG C, the duration is 1-2 hours, is filtered again afterwards, realizes separation of solid and liquid, separation is drawn
Solid material IV；
I. the solid material IV that draws will be separated in H to add in intermediate frequency furnace, adds the carbon of 0.1-0.14 times of IV weight of solid material
Powder, the soda ash of 0.12-0.18 times of IV weight of solid material is added, add the borax of 0.05-0.07 times of IV weight of solid material, add
Hot temperature is 1200-1400 DEG C, and Continuous aeration, sustained response time are 1-2 hours, carries out melting；
J. using through the material that I is treated, as anode, the mixed solution of nitric acid and silver nitrate is added, is electrolysed, in mixed liquor
The concentration of nitric acid is 3-5g/L, and the concentration of silver nitrate is 80-150g/L in mixed liquor, and after the completion of electrolysis, negative electrode obtains elemental silver,
The recovery to silver element in tin copper gold and silver waste material is realized, and the undissolved solid of anode is filtered, obtains solid material
Ⅴ；
K. the mixed solution that hydrochloric acid and sodium chlorate are added in the solid material V drawn is separated into J, hydrochloric acid is dense in mixed liquor
Spend for 50-70g/L, the concentration of sodium chlorate is 90-110g/L in mixed liquor, solution temperature is reached 80-90 by steam heating
DEG C, solid-to-liquid ratio 2.5-3.5：1, the duration is 0.8-1.2 hours, adds the mixed solution with hydrochloric acid and sodium chlorate afterwards
The volume of tributyl phosphate and kerosene in isometric tributyl phosphate and kerosene mixture, tributyl phosphate and kerosene mixture
Than for 0.7-0.9：1, extracted and separated, isolated organic phase is continued to employ；
L. draw organic will be separated in K to be added in reactor, the 10-12% for adding organic 0.4-0.6 times of phase volume is dense
The hydrochloric acid solution of degree, the oxalic acid solution of the 8-10% concentration of organic 0.2-0.4 times of phase volume is added, solution is made by steam heating
Temperature reaches 60-80 DEG C, is stirred continuously, and the duration is 0.5-0.7 hours, carries out back extraction reduction, is filtered again afterwards, real
Existing separation of solid and liquid, separation draw solid material VI；
M. the distilled water that 2-2.4 times of VI weight of solid material is added in the solid material VI drawn is separated into L, and is together heated
Boil, persistently boil 10-20 minutes, filtered again afterwards, realize separation of solid and liquid, separation draws solid material VII；
N. the solid material VII that draws will be separated in M to be added in crucible, and adds the boron of 0.2-0.4 times of VII weight of solid material
Sand, heating-up temperature are 1100-1300 DEG C, and the duration is 15-25 minutes, and final product obtains elemental gold, that is, realized to tin copper
The recovery of gold element in gold and silver waste material.
A kind of 2. comprehensive recycling process of tin copper gold and silver waste material according to claim 1, it is characterised in that in step D, powder
Broken crushed using Raymond mill machine.
3. the comprehensive recycling process of a kind of tin copper gold and silver waste material according to claim 1, it is characterised in that step E or step
In rapid F or step G or step H or step J or step L or step M, filtering is filtered using chamber-type press filter.
4. the comprehensive recycling process of a kind of tin copper gold and silver waste material according to claim 1, it is characterised in that in step F, add
Enter piece alkali and pH value of solution is adjusted to 10, solution temperature is reached 85 DEG C by steam heating, 1.5 hours duration.
5. the comprehensive recycling process of a kind of tin copper gold and silver waste material according to claim 1, it is characterised in that in step G, add
Enter sodium chloride solution, sodium chloride concentration 30%, pH value of solution is adjusted to 0.8 by adding hydrochloric acid, solid-to-liquid ratio 4：1, pass through
Steam heating makes solution temperature reach 85 DEG C, and the duration is 3.5 hours.
6. the comprehensive recycling process of a kind of tin copper gold and silver waste material according to claim 1, it is characterised in that in step N, add
Enter the borax of 0.3 times of VII weight of solid material, heating-up temperature is 1200 DEG C, and the duration is 20 minutes.
7. the comprehensive recycling process of a kind of tin copper gold and silver waste material according to claim 1, it is characterised in that in step N, lead to
Gold metallurgy flame gun is crossed to be heated.
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| CN110724827A (en) * | 2019-10-23 | 2020-01-24 | 金川集团股份有限公司 | Method for enriching precious metals from sponge copper leaching residues |
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Denomination of invention: A Comprehensive Recycling Process for Tin, Copper, Gold, and Silver Scrap Effective date of registration: 20230823 Granted publication date: 20180202 Pledgee: Ganzhou branch of Jiujiang Bank Co.,Ltd. Pledgor: JIANGXI GANXI INDUSTRY AND TRADE Co.,Ltd. Registration number: Y2023980053625 |
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