CN106400050A - Method for preparing high-quality electro-deposited copper from waste copper liquid - Google Patents
Method for preparing high-quality electro-deposited copper from waste copper liquid Download PDFInfo
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- CN106400050A CN106400050A CN201610839512.6A CN201610839512A CN106400050A CN 106400050 A CN106400050 A CN 106400050A CN 201610839512 A CN201610839512 A CN 201610839512A CN 106400050 A CN106400050 A CN 106400050A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 79
- 229910052802 copper Inorganic materials 0.000 title claims description 79
- 239000010949 copper Substances 0.000 title claims description 79
- 238000000034 method Methods 0.000 title claims description 30
- 239000007788 liquid Substances 0.000 title claims description 27
- 239000002699 waste material Substances 0.000 title claims description 27
- 229910000838 Al alloy Inorganic materials 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 238000007711 solidification Methods 0.000 claims description 17
- 230000008023 solidification Effects 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 14
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000003350 kerosene Substances 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 244000269722 Thea sinensis Species 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 10
- 229930182490 saponin Natural products 0.000 claims description 10
- 150000007949 saponins Chemical class 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 6
- 229920002907 Guar gum Polymers 0.000 claims description 5
- 239000000665 guar gum Substances 0.000 claims description 5
- 229960002154 guar gum Drugs 0.000 claims description 5
- 235000010417 guar gum Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005363 electrowinning Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007714 electro crystallization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for preparing high-quality electro-deposited copper from waste copper liquid. The method comprises the following steps: stirring the waste copper liquid at the temperature of 30 to 50 DEG C or below for 6 to 10 hours, and filtering to obtain filtrate; adding LIX841, M5640, isooctyl alcohol and sulfonated kerosene into the filtrate according to a phase ratio O/W of 1 to (1 to 5), extracting for 1 to 2 hours to obtain a copper-loaded organic phase, and reversely extracting the copper-loaded organic phase with a sulfuric acid solution to obtain a copper sulfate solution; and adding the copper sulfate solution obtained in the last step into an electrolytic cell, adding gul glue, nano tea saponin, thiourea and a dispersing agent serving as an additive, and performing electrodeposition with an aluminum alloy plate serving as a positive electrode and a stainless steel plate serving as a negative electrode to obtain the electro-deposited copper. The electro-deposited copper prepared by the method is high in quality, high in copper recycling rate and low in cost.
Description
Technical field：
The present invention relates to electrochemical field of metallurgy, it is specifically related to a kind of side preparing high-quality electrowinning zinc from waste copper liquid
Method.
Background technology：
Electrodeposition technology due to energy consumption is low and can large-scale production high pure metal and occupy a tiny space in metallurgical industry.It
Can be used not only for producing the ultra-high purity metal copper of microelectronics industry, also can produce substantial amounts of crude product tough cathode.
In electrodeposition Copper Processing Industry, stainless steel cathode kind plate still can be used as substrate (factory's utilization rate of deposited metal copper
Bring up to 74% in 2007 from 63% in 1999), almost all of new plant all adopts high performance rustless steel at present
The cathode base and full-automatic copper-stripping technology quality and yield to improve copper.Additionally, almost all of factory all adopts
Gold-plated lead-calcium-tin anode (utilization rate is from 83% in 1999 94% utilization rate bringing up to 2007).But commonly use at present
The preparation technology of electro deposited copper in, the anode material mechanical strength of use effectively improves, but its service life is still deposited
In too short problem.And the electrowinning zinc for preparing is loose easy to fall off, quality is poor.
Content of the invention：
It is an object of the invention to provide a kind of method preparing high-quality electro deposited copper from waste copper liquid, the electricity that the method is obtained
Long-pending copper mass is high, and copper recovery is high, low cost.
For achieving the above object, the present invention employs the following technical solutions：
A kind of method preparing high-quality electro deposited copper from waste copper liquid, comprises the following steps：
(1) by waste copper liquid at 30-50 DEG C, stir 6-10 hour, filter, obtain filtrate；
(2) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：(1-5), extract 1-
2h, obtains copper load organic phases, obtains copper-bath with sulfuric acid solution back extraction copper load organic phases；
(3) add the copper-bath that step (2) is obtained in a cell, and add guar gum, nanometer tea saponin, sulfur
Urea, dispersant are additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum 0.5-
2.0wt%, calcium 0-0.15wt%, cobalt and aluminum 0-0.05wt%, remaining is lead.
Preferred as technique scheme, in step (2), described LIX841, M5640, isooctanol, the body of sulfonated kerosene
Long-pending ratio is (12-18)：(5-12)：(10-20)：(40-48).
Preferred as technique scheme, in step (2), the temperature of described extraction is 30-50 DEG C.
Preferred as technique scheme, in step (2), the copper content in described copper-bath is 20-30g/L.
Preferred as technique scheme, in step (3), in parts by weight, described guar gum, nanometer tea saponin, sulfur
Urea, the consumption of dispersant are respectively：10-23 part, 0.1-0.5 part, 5-15 part, 5-10 part.
Preferred as technique scheme, described dispersant is Polyethylene Glycol.
Preferred as technique scheme, in step (3), the condition of described electrodeposition is 300-500A/ for electric current density
m2, circulating load is 50-120m3/h.
Preferred as technique scheme, the preparation method of described lead alloy plate comprises the following steps：
A) in smelting furnace, lead is melted at 380-420 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, protect
Warm 20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, add lead calcium foundry alloy, stirs 10-20min,
It is cooled to 500-510 DEG C, stand 5-10min, obtain aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat the aluminium alloy top layer in water-cooled irony mould
Demoulding when solidifying completely, obtains half solidification state metal ingot；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate.
Preferred as technique scheme, in step a), purity >=99.9% of described lead, the purity of glass putty >=
99.8%, purity >=99.5% of calcium, purity >=99.5% of aluminium powder, purity >=99.5% of cobalt.
Preferred as technique scheme, in step b), the top layer of described half solidification state metal ingot solidifies completely, in
Center portion is divided into microstructure of semisolid, and top layer central area temperature is 150-230 DEG C.
Compared with prior art, the present invention has advantages below：
During preparing electro deposited copper, interpolation guar gum, nanometer tea saponin, thiourea, dispersant are additive to the present invention,
And rationally control its consumption, effectively changing cathodic polarization potential, thus changing electrocrystallization, controlling formation and the growth of nucleus
Speed, so that the electrowinning zinc of preparation is smooth, fine and close, quality is high；
On the other hand, the present invention rationally controls the preparation process condition of lead alloy plate and its constituent content so that lead closes
Jinyang pole plate obtains and uniformly divides less than hungry spherical non-dendritic structure, and it can significantly reduce sun during being used for preparing electro deposited copper
The corrosion rate of pole plate, significantly extends the service life of positive plate, thus reducing the production cost of electro deposited copper.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
Release the present invention, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of method preparing high-quality electro deposited copper from waste copper liquid, comprises the following steps：
(1) preparation of lead alloy plate
A) in smelting furnace, lead is melted at 380 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, insulation
20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, adds lead calcium foundry alloy, stirs 10-20min, fall
Temperature, to 500-510 DEG C, stands 5min, obtains aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat the aluminium alloy top layer in water-cooled irony mould
Demoulding when solidifying completely, obtains half solidification state metal ingot, its top layer solidifies completely, and core is microstructure of semisolid, top layer
Central area temperature is 150-230 DEG C；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate；
(2) by waste copper liquid at 30 DEG C, stir 10 hours, filter, obtain filtrate；
(3) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：Extract at 1,30 DEG C
2h, obtains copper load organic phases, obtains copper-bath with sulfuric acid solution back extraction copper load organic phases, wherein, LIX841,
M5640, isooctanol, the volume ratio of sulfonated kerosene are 12：5：10：40；
(4) add the copper-bath that step (3) is obtained in a cell, and add 10 parts of guar gums, 0.1 part of nanometer tea
Saponin, 5 parts of thiourea, 5 parts of dispersants are additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electric current density is
300A/m2, circulating load is 50m3Under conditions of/h, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum
0.5wt%, calcium 0.01wt%, cobalt and aluminum 0.01wt%, remaining is lead.
Embodiment 2
A kind of method preparing high-quality electro deposited copper from waste copper liquid, comprises the following steps：
(1) preparation of lead alloy plate
A) in smelting furnace, lead is melted at 420 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, insulation
20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, adds lead calcium foundry alloy, stirs 10-20min, fall
Temperature, to 500-510 DEG C, stands 10min, obtains aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat the aluminium alloy top layer in water-cooled irony mould
Demoulding when solidifying completely, obtains half solidification state metal ingot, its top layer solidifies completely, and core is microstructure of semisolid, top layer
Central area temperature is 150-230 DEG C；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate；
(2) by waste copper liquid at 50 DEG C, stir 6 hours, filter, obtain filtrate；
(3) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：Extract at 5,50 DEG C
1h, obtains copper load organic phases, obtains copper-bath with sulfuric acid solution back extraction copper load organic phases, wherein, LIX841,
M5640, isooctanol, the volume ratio of sulfonated kerosene are 18：12：20：48；
(4) add the copper-bath that step (3) is obtained in a cell, and add 23 parts of guar gums, 0.5 part of nanometer tea
Saponin, 15 parts of thiourea, 10 parts of dispersants are additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electric current density is
500A/m2, circulating load is 120m3Under conditions of/h, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum
2.0wt%, calcium 0.15wt%, cobalt and aluminum 0.05wt%, remaining is lead.
Embodiment 3
A kind of method preparing high-quality electro deposited copper from waste copper liquid, comprises the following steps：
(1) preparation of lead alloy plate
A) in smelting furnace, lead is melted at 390 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, insulation
20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, adds lead calcium foundry alloy, stirs 10-20min, fall
Temperature, to 500-510 DEG C, stands 6min, obtains aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat the aluminium alloy top layer in water-cooled irony mould
Demoulding when solidifying completely, obtains half solidification state metal ingot, its top layer solidifies completely, and core is microstructure of semisolid, top layer
Central area temperature is 150-230 DEG C；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate；
(2) by waste copper liquid at 35 DEG C, stir 9 hours, filter, obtain filtrate；
(3) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：Extract at 2,35 DEG C
1.8h, obtains copper load organic phases, obtains copper-bath with sulfuric acid solution back extraction copper load organic phases, wherein, LIX841,
M5640, isooctanol, the volume ratio of sulfonated kerosene are 14：7：12：42；
(4) add the copper-bath that step (3) is obtained in a cell, and add 14 parts of guar gums, 0.2 part of nanometer tea
Saponin, 7 parts of thiourea, 6 parts of dispersants are additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electric current density is
350A/m2, circulating load is 80m3Under conditions of/h, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum
1wt%, calcium 0.05wt%, cobalt and aluminum 0.02wt%, remaining is lead.
Embodiment 4
A kind of method preparing high-quality electro deposited copper from waste copper liquid, comprises the following steps：
(1) preparation of lead alloy plate
A) in smelting furnace, lead is melted at 400 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, insulation
20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, adds lead calcium foundry alloy, stirs 10-20min, fall
Temperature, to 500-510 DEG C, stands 7min, obtains aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat the aluminium alloy top layer in water-cooled irony mould
Demoulding when solidifying completely, obtains half solidification state metal ingot, its top layer solidifies completely, and core is microstructure of semisolid, top layer
Central area temperature is 150-230 DEG C；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate；
(2) by waste copper liquid at 40 DEG C, stir 8 hours, filter, obtain filtrate；
(3) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：Extract at 3,40 DEG C
1.6h, obtains copper load organic phases, obtains copper-bath with sulfuric acid solution back extraction copper load organic phases, wherein, LIX841,
M5640, isooctanol, the volume ratio of sulfonated kerosene are 16：9：14：44；
(4) add the copper-bath that step (3) is obtained in a cell, and add 18 parts of guar gums, 0.3 part of nanometer tea
Saponin, 9 parts of thiourea, 8 parts of dispersants are additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electric current density is
400A/m2, circulating load is 100m3Under conditions of/h, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum
1.4wt%, calcium 0.1wt%, cobalt and aluminum 0.03wt%, remaining is lead.
Embodiment 5
A kind of method preparing high-quality electro deposited copper from waste copper liquid, comprises the following steps：
(1) preparation of lead alloy plate
A) in smelting furnace, lead is melted at 410 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, insulation
20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, adds lead calcium foundry alloy, stirs 10-20min, fall
Temperature, to 500-510 DEG C, stands 9min, obtains aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat the aluminium alloy top layer in water-cooled irony mould
Demoulding when solidifying completely, obtains half solidification state metal ingot, its top layer solidifies completely, and core is microstructure of semisolid, top layer
Central area temperature is 150-230 DEG C；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate；
(2) by waste copper liquid at 45 DEG C, stir 7 hours, filter, obtain filtrate；
(3) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：Extract at 4,45 DEG C
1.4h, obtains copper load organic phases, obtains copper-bath with sulfuric acid solution back extraction copper load organic phases, wherein, LIX841,
M5640, isooctanol, the volume ratio of sulfonated kerosene are 17：11：16：46；
(4) add the copper-bath that step (3) is obtained in a cell, and add 20 parts of guar gums, 0.4 part of nanometer tea
Saponin, 13 parts of thiourea, 9 parts of dispersants are additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electric current density is
450A/m2, circulating load is 110m3Under conditions of/h, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum
1.8wt%, calcium 0.12wt%, cobalt and aluminum 0.04wt%, remaining is lead.
Claims (10)
1. a kind of method preparing high-quality electro deposited copper from waste copper liquid is it is characterised in that comprise the following steps：
(1) by waste copper liquid at 30-50 DEG C, stir 6-10 hour, filter, obtain filtrate；
(2) LIX841, M5640, isooctanol, sulfonated kerosene are added in filtrate, comparing O/W is 1：(1-5), extract 1-2h, obtain
To copper load organic phases, obtain copper-bath with sulfuric acid solution back extraction copper load organic phases；
(3) add the copper-bath that step (2) is obtained in a cell, and add guar gum, nanometer tea saponin, thiourea, divide
Powder is additive, and with aluminium alloy plate as anode, with corrosion resistant plate as negative electrode, electrodeposition is obtained electro deposited copper；
Wherein, when described metal is as positive plate, its composition by weight percentage, including following components：Stannum 0.5-
2.0wt%, calcium 0-0.15wt%, cobalt and aluminum 0-0.05wt%, remaining is lead.
2. as claimed in claim 1 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step
(2), in, described LIX841, M5640, isooctanol, the volume ratio of sulfonated kerosene are (12-18)：(5-12)：(10-20)：(40-
48).
3. as claimed in claim 1 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step
(2), in, the temperature of described extraction is 30-50 DEG C.
4. as claimed in claim 1 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step
(2), in, the copper content in described copper-bath is 20-30g/L.
5. as claimed in claim 1 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step
(3) in, in parts by weight, described guar gum, nanometer tea saponin, thiourea, the consumption of dispersant are respectively：10-23 part, 0.1-
0.5 part, 5-15 part, 5-10 part.
6. as claimed in claim 5 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Described point
Powder is Polyethylene Glycol.
7. as claimed in claim 1 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step
(3), in, the condition of described electrodeposition is 300-500A/m for electric current density2, circulating load is 50-120m3/h.
8. as claimed in claim 1 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that described lead
The preparation method of alloy sheets comprises the following steps：
A) in smelting furnace, lead is melted at 380-420 DEG C, add glass putty, cobalt powder, start to stir, be warming up to 600 DEG C, insulation
20-30min, is subsequently adding aluminium powder, starts to stir, is cooled to 540-550 DEG C, adds lead calcium foundry alloy, stirs 10-20min, fall
Temperature, to 500-510 DEG C, stands 5-10min, obtains aluminium alloy；
B) aluminium alloy that step a) obtains is injected in water-cooled irony mould, treat that the aluminium alloy top layer in water-cooled irony mould is complete
Demoulding during solidification, obtains half solidification state metal ingot；
C) carry out multi-pass using the half solidification state metal ingot that double-roll rolling mill obtains to step b) to push, overall reduction >=
70%, obtain lead alloy plate.
9. as claimed in claim 7 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step a)
In, purity >=99.9% of described lead, purity >=99.8% of glass putty, purity >=99.5% of calcium, the purity of aluminium powder >=
99.5%, purity >=99.5% of cobalt.
10. as claimed in claim 7 a kind of method preparing high-quality electro deposited copper from waste copper liquid it is characterised in that：Step
B), in, the top layer of described half solidification state metal ingot solidifies completely, and core is microstructure of semisolid, top layer central area temperature
For 150-230 DEG C.
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