CN104805287B - A kind of CP180 copper extractants renovation process - Google Patents
A kind of CP180 copper extractants renovation process Download PDFInfo
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- CN104805287B CN104805287B CN201510191564.2A CN201510191564A CN104805287B CN 104805287 B CN104805287 B CN 104805287B CN 201510191564 A CN201510191564 A CN 201510191564A CN 104805287 B CN104805287 B CN 104805287B
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Abstract
The present invention relates to technical field of wet metallurgy, especially a kind of CP180 copper extractants renovation process, traditional cleaning solution is replaced to carry out regenerated from washing Returning utilization to the CP180 of poisoning by using ammonium hydroxide or ammonium hydrogen carbonate, CP180 is returned to the effect that uses constant, solve Cp180 separation and Extraction Ge, Cu, Zn organic phases from the H2SO4 solution containing Ge, Cu, Zn be easily poisoned aging the problem of；Promote CP180 to return to being smoothed out for extracting copper, reduce CP180 usage amount, reduce the discharge capacity of waste liquid, reduce environmental pollution, but also enabling to the split-phase in washing process easy, the difficulty of reduction CP180 regeneration recyclings reduces the cost of CP180 regeneration treatments.Reduce the cost that Ge, Cu are purified when solution containing Zn is sent into electrolysis production Zn.
Description
Technical field
The present invention relates to technical field of wet metallurgy, especially a kind of CP180 copper extractants renovation process.
Background technology
In the prior art, for being typically using N235- kerosene systems extraction after being leached through H2SO4 containing Ge, Cu, Zn material
Ge, then Cu is extracted using Cp180, and the electric zinc production system of extraction copper raffinate feeding is reclaimed into Zn, and then reach Ge, Cu, Zn are divided
From.But, Cp180 is in Cu extraction processes are carried out, aging of being easily poisoned, and then causes the consumption of CP180 extractants higher, extracts
Take cost larger, and also result in the extraction process of copper and be difficult to smoothly go on, cause the discharge of substantial amounts of waste liquid, make
Into the pollution of environment.
Therefore, in the prior art, someone uses HF, NH4F or (NH4)2SO4The aqueous solution is carried out to the Cp180 for aging of being poisoned
After regenerated from washing processing, recover CP180 to the extraction function of copper, so CP180 returned carry out copper in extracting system enter one
The extraction processing of step, and then reduce the discharge capacity of waste liquid, reduce environment pollution rate and to containing Ge in Ge, Cu, Zn material, Cu,
The cost of Zn separation；But, fluorine element will be brought into using this technology regeneration treatment, and then cause a small amount of waste liquid of exclusion
Also environment can be polluted, and washs the cleaning solution after CP180 and be difficult to carry out circulation washing again using processing, in turn resulted in
The new pollution of environment, meanwhile, the extracting power of the CP180 after being handled using this regeneration treatment technology can only reach
Recover 50-80%, and then cause the number of times for carrying out recycled for multiple times relatively low, finally still can also update CP180 extractants, enter
And cause CP180 regeneration not thorough；Then, the NaOH aqueous solution or NaOH and (NH4) 2SO4 of someone again using 1~3%
Mixed solution carries out regenerated from washing, but the treatment technology produces serious emulsification in washing section, and split-phase is difficult, and regeneration
The ability that Cp180 recovers extracting Cu can only achieve 80% or so.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of CP180 copper extractants regeneration
Method, CP180 can be promoted to return, and the effect used is constant, promotes CP180 to return to being smoothed out for extracting copper, reduces CP180
Usage amount, reduce the discharge capacity of waste liquid, reduce environmental pollution, but also enable to split-phase in washing process easily, drop
The difficulty of low CP180 regeneration recycling, reduces the cost of CP180 regeneration treatments.
It is achieved particular by following technical scheme：
A kind of CP180 copper extractants renovation process, will be carried out after copper extraction using the agent of CP180- kerosene extractions, obtain extraction copper
Raffinate and cupric CP180- kerosene mixed liquors；The electric zinc production system of extraction copper raffinate feeding is reclaimed into zinc processing again, and by cupric
CP180- kerosene mixed liquor is handled using sulfuric acid back extraction, obtains organic phase and inorganic phase；Inorganic phase is copper-containing sulfuric acid solution, feeding
Electrolytic cell carries out electrolysis processing, you can obtain copper simple substance and electrolytic copper raffinate；Organic phase is CP180- kerosene systems, using containing ammonium root
Solion carrying out washing treatment, you can obtain CP180- kerosene extraction agent.
It is three-level extraction that described CP180- kerosene extractions agent, which carries out copper extraction,.
Described uses the CP180- kerosene extractions agent that the agent of CP180- kerosene extractions carries out copper extraction for by mass percent
The mixture of CP180 and 70% kerosene for 30%.
The described sulfuric acid concentration used cupric CP180- kerosene mixed liquors in sulfuric acid back extraction processing is 250~300g/
L。
Described solution containing ammonium ion is one kind in Ammonia or ammonium bicarbonate soln.
The mass fraction of described Ammonia is 5-15%.
The mass fraction of described ammonium bicarbonate soln is 10-15%.
The described sulfuric acid used cupric CP180- kerosene mixed liquor in sulfuric acid back extraction processing is using electrolytic copper raffinate come generation
Replace, sulfuric acid concentration is 250~280g/L in electrolytic copper raffinate, and the concentration of copper is 10~20g/L.
Described back extraction is processed as two grades of back extraction.
Described carrying out washing treatment is two grades of washings.
The present invention is to be regenerated the CP180 used when separation Cu is extracted from dilute H2SO4 solution containing Ge, Cu, Zn
The method of processing, and accounted for using CP180 and kerosene according to CP180 after 30%, kerosene accounts for 70% composition extractant system, then
Add it in dilute H2SO4 solution containing Ge, Cu, Zn, and then reach the extract and separate purpose to copper, extraction one at this moment
As use three-level extraction processing；And the organic phase after extracting copper is come out again is further carried out at back extraction using sulfuric acid
Reason, and then cause in organic phase, i.e., the copper in CP180- kerosene systems is stripped out, and stripping process is generally adopted by two
Level processing, and then after using sulfuric acid back extraction processing, the CP180- kerosene systems being poisoned are obtained, and then, in order that
CP180- kerosene systems can regenerate, and can lift extraction of the CP180- kerosene systems to copper after its regeneration rate and regeneration
Rate, and then two grades of carrying out washing treatment are carried out to the CP180- kerosene systems being poisoned using solution containing ammonium ion, and then cause it
Purified, improve the regeneration rate of CP180- kerosene systems and regenerate extraction energy of the next CP180- kerosene systems to copper
Power.
The present invention is before copper extraction is carried out, in its dilute H2SO4 solution containing Ge, Cu, Zn, containing Cu5~20g/L, and Ge100~
50~120g/L of 200mg/L, Zn50~100g/L, H2SO4.
The Ammonia or quality that the solution containing ammonium ion that the present invention is used is 5-15% for mass fraction point
Number is 10-15% ammonium bicarbonate soln.
The present invention is usually that dilute H2SO4 solution containing Ge, Cu, Zn is first used into N235- kerosene in specific processing step
System extracts Ge, and extraction Ge raffinates use Cp180- kerosene system extracting Cus again, and extraction Cu raffinate power transmission Zn production systems are reclaimed into Zn,
Therefore it is required that extraction Ge, extraction Cu efficiency is as high as possible, Ge and Cu remaining quantity is as low as possible in raffinate, during the Zn productions of reduction Zn power transmissions
Purification Ge, Cu cost.
Furthermore, the present invention is anti-when being stripped using sulfuric acid or by sulfuric acid is obtained after initial sulfuric acid back extraction
Extract liquid and carry out electrolysis processing, and then obtain electrolytic copper raffinate, and electrolytic copper raffinate is returned into back extraction process step and carry out CP180- kerosene
The back extraction processing of copper in system；And in electrolytic copper raffinate, Cu is 10~20g/L, H2SO4250~280g/L.
The present invention carries out CP180- kerosene systems using ammonium ion solution, i.e. ammonium hydroxide or ammonium bicarbonate soln
Regenerated from washing, its cost is relatively low, and the contaminated wastewater of generation is small.
Compared with prior art, technique effect of the invention is embodied in：
Washed again come the CP180 to poisoning instead of traditional cleaning solution by using ammonium hydroxide or ammonium hydrogen carbonate
Raw Returning utilization, the effect for using CP180 returns is constant, solves Cp180 and is separated from the H2SO4 solution containing Ge, Cu, Zn
Extract Ge, Cu, Zn organic phase be easily poisoned aging the problem of；CP180 is promoted to return to being smoothed out for extracting copper, reduction CP180's
Usage amount, reduces the discharge capacity of waste liquid, reduces environmental pollution, but also enables to the split-phase in washing process easy, reduction
The difficulty of CP180 regeneration recyclings, reduces the cost of CP180 regeneration treatments.Reduction will contain Zn solution feeding electrolysis production Zn
When purify Ge, Cu cost.And use ammonium hydroxide and ammonium hydrogen carbonate it is cheap, and then promote to CP180 wash
The use cost of liquid is relatively low, and waste liquid discharging amount is smaller, with the significant value of environmental protection and economic benefit.
Embodiment
Limited with reference to specific embodiment technical scheme is further, but claimed
Scope is not only limited to made description.
Embodiment 1
A kind of CP180 copper extractants renovation process, will be carried out after copper extraction using the agent of CP180- kerosene extractions, obtain extraction copper
Raffinate and cupric CP180- kerosene mixed liquors；The electric zinc production system of extraction copper raffinate feeding is reclaimed into zinc processing again, and by cupric
CP180- kerosene mixed liquor is handled using sulfuric acid back extraction, obtains organic phase and inorganic phase；Inorganic phase is copper-containing sulfuric acid solution, feeding
Electrolytic cell carries out electrolysis processing, you can obtain copper simple substance and electrolytic copper raffinate；Organic phase is CP180- kerosene systems, using containing ammonium root
Solion carrying out washing treatment, you can obtain CP180- kerosene extraction agent.
It is three-level extraction that described CP180- kerosene extractions agent, which carries out copper extraction,.
Described uses the CP180- kerosene extractions agent that the agent of CP180- kerosene extractions carries out copper extraction for by mass percent
The mixture of CP180 and 70% kerosene for 30%.
The described sulfuric acid concentration used cupric CP180- kerosene mixed liquors in sulfuric acid back extraction processing is 250g/L.
Described solution containing ammonium ion is Ammonia.Mass fraction is 5%.
Described back extraction is processed as two grades of back extraction.
Described carrying out washing treatment is two grades of washings
Embodiment 2
A kind of CP180 copper extractants renovation process, will be carried out after copper extraction using the agent of CP180- kerosene extractions, obtain extraction copper
Raffinate and cupric CP180- kerosene mixed liquors；The electric zinc production system of extraction copper raffinate feeding is reclaimed into zinc processing again, and by cupric
CP180- kerosene mixed liquor is handled using sulfuric acid back extraction, obtains organic phase and inorganic phase；Inorganic phase is copper-containing sulfuric acid solution, feeding
Electrolytic cell carries out electrolysis processing, you can obtain copper simple substance and electrolytic copper raffinate；Organic phase is CP180- kerosene systems, using containing ammonium root
Solion carrying out washing treatment, you can obtain CP180- kerosene extraction agent.
It is three-level extraction that described CP180- kerosene extractions agent, which carries out copper extraction,.
Described uses the CP180- kerosene extractions agent that the agent of CP180- kerosene extractions carries out copper extraction for by mass percent
The mixture of CP180 and 70% kerosene for 30%.
The described sulfuric acid concentration used cupric CP180- kerosene mixed liquors in sulfuric acid back extraction processing is 300g/L.
Described solution containing ammonium ion is ammonium bicarbonate soln.
The mass fraction of described ammonium bicarbonate soln is 10%.
Described back extraction is processed as two grades of back extraction.
Described carrying out washing treatment is two grades of washings
Embodiment 3
A kind of CP180 copper extractants renovation process, will be carried out after copper extraction using the agent of CP180- kerosene extractions, obtain extraction copper
Raffinate and cupric CP180- kerosene mixed liquors；The electric zinc production system of extraction copper raffinate feeding is reclaimed into zinc processing again, and by cupric
CP180- kerosene mixed liquor is handled using sulfuric acid back extraction, obtains organic phase and inorganic phase；Inorganic phase is copper-containing sulfuric acid solution, feeding
Electrolytic cell carries out electrolysis processing, you can obtain copper simple substance and electrolytic copper raffinate；Organic phase is CP180- kerosene systems, using containing ammonium root
Solion carrying out washing treatment, you can obtain CP180- kerosene extraction agent.
It is three-level extraction that described CP180- kerosene extractions agent, which carries out copper extraction,.
Described uses the CP180- kerosene extractions agent that the agent of CP180- kerosene extractions carries out copper extraction for by mass percent
The mixture of CP180 and 70% kerosene for 30%.
The described sulfuric acid concentration used cupric CP180- kerosene mixed liquors in sulfuric acid back extraction processing is 280g/L.
Described solution containing ammonium ion is Ammonia.
The mass fraction of described Ammonia is 15%.
Described back extraction is processed as two grades of back extraction.
Described carrying out washing treatment is two grades of washings
Embodiment 4
A kind of CP180 copper extractants renovation process, will be carried out after copper extraction using the agent of CP180- kerosene extractions, obtain extraction copper
Raffinate and cupric CP180- kerosene mixed liquors；The electric zinc production system of extraction copper raffinate feeding is reclaimed into zinc processing again, and by cupric
CP180- kerosene mixed liquor is handled using sulfuric acid back extraction, obtains organic phase and inorganic phase；Inorganic phase is copper-containing sulfuric acid solution, feeding
Electrolytic cell carries out electrolysis processing, you can obtain copper simple substance and electrolytic copper raffinate；Organic phase is CP180- kerosene systems, using containing ammonium root
Solion carrying out washing treatment, you can obtain CP180- kerosene extraction agent.
It is three-level extraction that described CP180- kerosene extractions agent, which carries out copper extraction,.
Described uses the CP180- kerosene extractions agent that the agent of CP180- kerosene extractions carries out copper extraction for by mass percent
The mixture of CP180 and 70% kerosene for 30%.
The described sulfuric acid concentration used cupric CP180- kerosene mixed liquors in sulfuric acid back extraction processing is 260g/L.
Described solution containing ammonium ion is ammonium bicarbonate soln.
The mass fraction of described ammonium bicarbonate soln is 15%.
Described back extraction is processed as two grades of back extraction.
Described carrying out washing treatment is two grades of washings
Embodiment 5
On the basis of embodiment 1, a kind of other step be the same as Examples 1, CP180 copper extractants renovation process is described
Sulfuric acid during cupric CP180- kerosene mixed liquor is handled using sulfuric acid back extraction is replaced using electrolytic copper raffinate, sulphur in electrolytic copper raffinate
Acid concentration is 250g/L, and the concentration of copper is 10g/L.
Embodiment 6
On the basis of embodiment 1, a kind of other step be the same as Examples 1, CP180 copper extractants renovation process is described
Sulfuric acid during cupric CP180- kerosene mixed liquor is handled using sulfuric acid back extraction is replaced using electrolytic copper raffinate, sulphur in electrolytic copper raffinate
Acid concentration is 280g/L, and the concentration of copper is 20g/L.
Embodiment 7
On the basis of embodiment 1, a kind of other step be the same as Examples 1, CP180 copper extractants renovation process is described
Sulfuric acid during cupric CP180- kerosene mixed liquor is handled using sulfuric acid back extraction is replaced using electrolytic copper raffinate, sulphur in electrolytic copper raffinate
Acid concentration is 250g/L, and the concentration of copper is 20g/L.
Embodiment 8
On the basis of embodiment 1, a kind of other step be the same as Examples 1, CP180 copper extractants renovation process is described
Sulfuric acid during cupric CP180- kerosene mixed liquor is handled using sulfuric acid back extraction is replaced using electrolytic copper raffinate, sulphur in electrolytic copper raffinate
Acid concentration is 280g/L, and the concentration of copper is 10g/L.
Embodiment 9
On the basis of embodiment 1, a kind of other step be the same as Examples 1, CP180 copper extractants renovation process is described
Sulfuric acid during cupric CP180- kerosene mixed liquor is handled using sulfuric acid back extraction is replaced using electrolytic copper raffinate, sulphur in electrolytic copper raffinate
Acid concentration is 270g/L, and the concentration of copper is 15g/L.
Embodiment 10
A kind of CP180 copper extractants renovation process, will contain Cu5g/L, Ge100mg/L, Zn50g/L, H2SO450g/L, first
The N235- kerosene extractions agent constituted with 30% N235 and 70% kerosene is carried out after 4 grades of extracted germaniums handle, then with 30%
The CP180- kerosene extractions agent of Cp180 and 70% kerosene composition carries out 3 grades of extraction Cu processing, and raffinate is detected,
Containing Ge2.5mg/L, Cu880mg/L, Zn65.2g/L, the system of feeding electrolytic recovery of zinc reclaims zinc processing；Again by after extracting copper
The agent of CP180- kerosene extractions uses 250g/L H2SO4Two grades of back extraction processing, then two grades of washings are carried out using solution containing ammonium ion
CP180- kerosene extraction agent, you can obtain regeneration CP180- kerosene extraction agent.
Embodiment 11
A kind of CP180 copper extractants renovation process, will contain Cu20g/L, Ge200mg/L, Zn100g/L, H2SO4120g/L,
The N235- kerosene extractions agent first constituted with 30% N235 and 70% kerosene is carried out after 7 grades of extracted germaniums handle, then with 30%
The CP180- kerosene extractions agent of Cp180 and 70% kerosene composition carries out 3 grades of extraction Cu processing, and raffinate is detected,
Containing Ge2.3mg/L, Cu881mg/L, Zn64.9g/L, the system of feeding electrolytic recovery of zinc reclaims zinc processing；Again by after extracting copper
The agent of CP180- kerosene extractions uses 280g/L H2SO4Two grades of back extraction processing, then two grades of washings are carried out using solution containing ammonium ion
CP180- kerosene extraction agent, you can obtain regeneration CP180- kerosene extraction agent.
Embodiment 12
A kind of CP180 copper extractants renovation process, will contain Cu15g/L, Ge150mg/L, Zn80g/L, H2SO4100g/L,
The N235- kerosene extractions agent first constituted with 30% N235 and 70% kerosene is carried out after 6 grades of extracted germaniums handle, then with 30%
The CP180- kerosene extractions agent of Cp180 and 70% kerosene composition carries out 3 grades of extraction Cu processing, and raffinate is detected,
Containing Ge2.9mg/L, Cu876mg/L, Zn65.7g/L, the system of feeding electrolytic recovery of zinc reclaims zinc processing；Again by after extracting copper
The agent of CP180- kerosene extractions uses 270g/L H2SO4Two grades of back extraction processing, then two grades of washings are carried out using solution containing ammonium ion
CP180- kerosene extraction agent, you can obtain regeneration CP180- kerosene extraction agent.
Embodiment 13
A kind of CP180 copper extractants renovation process, will contain Ge120mg/L, Cu13g/L, Zn65g/L, H2SO480g/L, first
The N235- kerosene extractions agent constituted with 30% N235 and 70% kerosene is carried out after 5 grades of extracted germaniums handle, then with 30%
The CP180- kerosene extractions agent of Cp180 and 70% kerosene composition carries out 3 grades of extraction Cu processing, and raffinate is detected,
Containing Ge2.5mg/L, Cu880mg/L, Zn65.2g/L, the system of feeding electrolytic recovery of zinc reclaims zinc processing；Again by after extracting copper
The agent of CP180- kerosene extractions uses 250g/L H2SO4Two grades of back extraction processing, then two grades of washings are carried out using solution containing ammonium ion
CP180- kerosene extraction agent, you can obtain regeneration CP180- kerosene extraction agent.
Test example：
(1) it is prepared by poisoning CP180- kerosene extractions agent：
Ge120mg/L, Cu13g/L, Zn65g/L, H will be contained2SO480g/L, first with 30% N235 and 70% kerosene group
Into the agent of N235- kerosene extractions carry out after the processing of 6 grades of extracted germaniums, then the kerosene of Cp180 and 70% with 30% is constituted
The agent of CP180- kerosene extractions carries out 3 grades of extraction Cu processing, and raffinate is detected, containing Ge2.5mg/L, Cu880mg/L,
Zn65.2g/L, then the CP180- kerosene extractions agent after extracting copper is handled using bis- grades of back extraction of 250g/L H2SO4, it is poisoned
CP180- kerosene extraction agent afterwards.
A, by above-mentioned (1) be poisoned after the agent of CP180- kerosene extractions using 10% HF carry out two grades washing after, then by its
Return in the extraction processing that copper is carried out in (1), the raffinate for obtaining copper, containing Cu2.4g/L, extraction yield is dropped to by 93.2%
81.5%.
B, the CP180- kerosene extractions agent after above-mentioned (1) is poisoned first washed once with H2SO4, then be washed with 10% NH4F
Once, then with H2SO4 wash once, then return it into (1) in the extraction processing for carrying out copper, the raffinate for obtaining copper, contain
Cu1.2g/L, extraction yield drops to 90.8% by 93.2%；Continue according to aforesaid operations step, extraction back extraction regenerative operation to the 8th
It is secondary, show that extraction raffinate contains Cu1.58g/L, proceed to the 11st time, extraction raffinate contains Cu3.5g/L, Cu extraction yield drops to 73.07%.
C, the CP180- kerosene extractions agent after above-mentioned B is poisoned washs secondary with the 10% NH4OH aqueous solution, then is returned
Return in (1) and carry out the extraction processing of copper, persistent loop is carried out to during the 15th circulation, and the 15th extraction raffinate contains Cu344mg/L, extraction
Rate is taken to go back up to 97.35%；Lasting progress extraction back extraction processing is to during the 19th circulation, and extraction raffinate is containing Cu179mg/L, extraction yield
Rise to 98.62%.
D, the CP180- kerosene systems of the 19th circulation poisoning in C are used for containing Cu16.68g/L, Ge151mg/L,
Zn75.2g/L, H2SO4116.3g/L solution carries out extraction back extraction processing according to (1), and the NH4OH of acidification in C is washed
Liquid adds NH4OH to more than PH14 or changes NH4OH cleaning solutions, proceeds Cu extraction, is stripped regenerated from washing cyclic test
To 31 times, extraction raffinate contains Cu228mg/L, extraction yield 98.63%.
E, using new CP180- kerosene extractions to containing Cu16.68g/L, Ge151mg/L, Zn75.2g/L, H2SO4
116.3g/L solution carries out extraction back extraction processing according to (1), and back extraction regeneration treatment is carried out to the agent of CP180- kerosene extractions, and will
NH in D4OH regenerated from washing solution is replaced by the 3% NaOH aqueous solution, and to be tested to proceed to the 32nd time, two grades of washings are all emulsified
Seriously, split-phase is slow；Proceed, when experiment proceeds to 33 times, extraction raffinate rises to 1.65g/L containing Cu, and extraction yield drops to
90.1%.Again by regenerated from washing fluid exchange be 10% (NH4)2SO4NaOH mixed liquors with 1% proceed Cp180 Cu extractions
Take, be stripped, regeneration test strip liquor uses copper electrolyte (Cu11.65g/L, H2SO4286.7g/L).Proceed to the 37th time,
Extraction raffinate contains Cu3.27g/L, and the regenerated from washing liquid of extraction yield 80.4% is neutral, mends NaOH and is allowed to more than PH14, is further continued for carrying out
To the 39th time, extraction raffinate contains Cu1.17g/L, and extraction yield is 92.9%, from the 34th to 39 median extraction rate 85.57%.
F, on E basis, using the CP180- kerosene extraction agent of the 39th circular treatment poisoning in E, and to washing
Fluid exchange is 10% NH4OH solution, continues to carry out circulate operation according to the operating method of (1), operation to be recycled is to the 41st time
When, extraction raffinate contains Cu66mg/L, and extraction yield is 99.6%, is proceeded to the 49th time, and extraction raffinate contains Cu524mg/L, extraction yield
96.04%.And continue to carry out, when regenerated from washing liquid pH value is dropped to below 7, supplement NH4OH is allowed in alkaline (PH14 or so),
Proceed Cp180 Cu extractions, be stripped, regenerated from washing is to the 97th time, and extraction raffinate contains Cu280mg/L, extraction yield 98.3%.
G, contains Cu18.9g/L using liquid before extraction, and H2SO4 118g/L, Ge201mg/L proceed Cp180 extractions, back extraction
Cu, changes the NH4HCO3 aqueous solution that NH4OH regenerated from washing liquid is 10% to 15%..When experiment proceeds to 101 times, extraction raffinate contains
Cu109mg/L, extraction yield 99.5%.When proceeding to 108 times, the aobvious neutrality of regenerated from washing liquid, extraction raffinate contains Cu1.25g/L, extraction
Rate 93.3%.Thereafter adding NH4HCO3 makes regenerated from washing liquid PH14 or so, proceeds to be tested to 115 times, extraction raffinate contains
Cu393.7mg/L, extraction yield 98%.NH4HCO3 (concentration is 15%) the regenerated from washing liquid more renewed proceeds Cp180 extraction
Take, be stripped, regenerated from washing is tested to the 123rd time, extraction raffinate contains Cu242mg/L, extraction yield 98.36%.
The present invention is extracted using ammonium hydroxide or ammonium bicarbonate soln to CP180- kerosene it can be seen from above-mentioned test example
Take agent to carry out regeneration treatment, enable to CP180 extracting power to be restored, and circulation that can be long-term is washed under application
Go, reduce the cost during the Extraction and back extraction of the copper in carrying out cupric, germanium, zinc sulfuric acid solution, reduce waste liquid
Discharge capacity, reduces environmental pollution rate, with the significant value of environmental protection and economic benefit.
It is necessary explanation herein, above example and test example are only limitted to do further technical scheme
Elaboration and explanation, be not the further limitation to technical scheme, those skilled in the art are on this basis
The improvement of the essential characteristics and non-significant progress of the non-protruding made, belongs to the protection category of the present invention.
Claims (10)
1. a kind of CP180 copper extractants renovation process, it is characterised in that by dilute H containing Ge, Cu, Zn2SO4Solution first uses N235-
Kerosene system extracts Ge, and extraction Ge raffinates are carried out after copper extraction using the agent of CP180- kerosene extractions, obtain extraction copper raffinate and cupric
CP180- kerosene mixed liquors；The electric zinc production system of extraction copper raffinate feeding is reclaimed into zinc processing again, and cupric CP180- kerosene is mixed
Close liquid to handle using sulfuric acid back extraction, obtain organic phase and inorganic phase；Inorganic phase is copper-containing sulfuric acid solution, and feeding electrolytic cell carries out electricity
Solution processing, you can obtain copper simple substance and electrolytic copper raffinate；Organic phase is CP180- kerosene systems, is washed using solution containing ammonium ion
Processing, you can obtain CP180- kerosene extraction agent；Wherein, in dilute H containing Ge, Cu, Zn2SO4In solution, containing Cu5 ~ 20g/L,
Ge100 ~ 200mg/L, Zn50 ~ 100g/L, H2SO450~120g/L。
2. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described CP180- kerosene extractions
It is three-level extraction that agent, which carries out copper extraction,.
3. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described use CP180- kerosene
The CP180- kerosene extractions agent that extractant carries out copper extraction is the CP180 and 70% kerosene that are 30% by mass percent mixing
Thing.
4. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described by cupric CP180- coals
Oily mixed liquor uses the sulfuric acid concentration in sulfuric acid back extraction processing for 250 ~ 300g/L.
5. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described solution containing ammonium ion
For one kind in Ammonia or ammonium bicarbonate soln.
6. CP180 copper extractants renovation process as claimed in claim 5, it is characterised in that described Ammonia
Mass fraction is 5-15%.
7. CP180 copper extractants renovation process as claimed in claim 5, it is characterised in that described ammonium bicarbonate soln
Mass fraction is 10-15%.
8. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described by cupric CP180- coals
Sulfuric acid during oily mixed liquor is handled using sulfuric acid back extraction is replaced using electrolytic copper raffinate, in electrolytic copper raffinate sulfuric acid concentration for 250 ~
280g/L, the concentration of copper is 10 ~ 20g/L.
9. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described back extraction is processed as two grades
Back extraction.
10. CP180 copper extractants renovation process as claimed in claim 1, it is characterised in that described carrying out washing treatment is two grades
Washing.
Priority Applications (1)
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| CN105331814B (en) * | 2015-11-28 | 2017-09-29 | 贵州宏达环保科技有限公司 | It is a kind of high containing Cu, Ge separation method in Cu, Ge raw material |
| CN106086406B (en) * | 2016-08-28 | 2018-05-29 | 中铝广西有色金源稀土有限公司 | A kind of renovation process of organic extractant |
| CN106282558B (en) * | 2016-08-28 | 2018-08-14 | 中铝广西有色金源稀土有限公司 | A kind of processing method of organic extractant |
| CN112250207A (en) * | 2020-08-21 | 2021-01-22 | 广东臻鼎环境科技有限公司 | Method for extracting copper ion extractant from waste liquid |
| CN118064718B (en) * | 2024-04-17 | 2024-06-18 | 生态环境部南京环境科学研究所 | Method for recycling copper by double extraction of aluminum trichloride copper-containing wastewater |
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| US4194905A (en) * | 1976-03-29 | 1980-03-25 | King Industries, Inc. | Solvent-extraction process for recovery and separation of metal values |
| US6177055B1 (en) * | 1998-09-14 | 2001-01-23 | Henkel Corporation | Process for extracting and recovering copper |
| CN101008052A (en) * | 2006-11-15 | 2007-08-01 | 长沙绿铱环保科技有限公司 | Method for recovering copper from PCB copper etching liquor separated by solvent extraction technology |
| CN101024546B (en) * | 2007-01-31 | 2010-10-06 | 何剑波 | Copper etching liquid regeneration circulation method and apparatus |
| CN101676229A (en) * | 2008-09-20 | 2010-03-24 | 涂方祥 | Fully closed system for regenerating alkaline etching liquid and recovering copper in PCB |
| CN102251244B (en) * | 2011-07-13 | 2013-07-31 | 重庆浩康医药化工集团有限公司 | Cyclic regeneration and copper extraction process for printed circuit board etching waste solution |
| CN102534213B (en) * | 2012-02-17 | 2014-01-22 | 云南五鑫实业有限公司 | Method for carrying out normalized treatment on P204 extraction poisoning |
| CN103320612B (en) * | 2013-06-26 | 2015-07-01 | 中国科学院过程工程研究所 | Tungsten-molybdenum separation method for extracting solution containing tungsten-molybdenum acid salt employing serotonin-hydroximic extractant |
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