CN1024203C - Purifying copper electrolyte by means of liquid-liquid extraction - Google Patents
Purifying copper electrolyte by means of liquid-liquid extraction Download PDFInfo
- Publication number
- CN1024203C CN1024203C CN90100691A CN90100691A CN1024203C CN 1024203 C CN1024203 C CN 1024203C CN 90100691 A CN90100691 A CN 90100691A CN 90100691 A CN90100691 A CN 90100691A CN 1024203 C CN1024203 C CN 1024203C
- Authority
- CN
- China
- Prior art keywords
- antimony
- bismuth
- arsenic
- liquid
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention uses a liquid-liquid extracting method to separate and extract the harmful elements of arsenic, antimony and bismuth from a copper electrolyte to improve the quality of electrolytic copper, and the purposes of turning the harmful into the beneficial and comprehensively recovering are achieved. The present invention is technically characterized in that the bismuth, the antimony and the arsenic are orderly and respectively extracted, back extracted and precipitated by the competitive extraction of extracting agents in the same composition under different comparison conditions. The extracting system is a kerosene solution prepared from organic amine and tributyl phosphate, and the speeds of extraction, back extraction and phase splitting are high.
Description
The invention belongs to the production or the refining field of metal, relate in particular to electrolytic copper refining.
When electrolytic refined copper, the contents level of the soluble impurity in the electrolytic solution (AS, Sb, Bi) also is important for the purity of decision cathode plate.These impurity can be deposited on the negative electrode with copper in a limited extent, but the more important thing is, some impurity often become entrained in wherein when settling generates.Therefore, need emit some refining electrolytic solution continuously to purification system, make that foreign matter content remains on admissible level in the electrolytic solution.
Remove harmful element from copper electrolyte, in the method for arsenic, antimony, bismuth, the method that obtains industrial application is the insoluble anode electrolytic process.[Australia] A.K. is than Shi Washi, " copper extracts metallurgical " of [Canada] W.G. literary composition baud work, and (metallurgical industry press, P252) has proposed this method at March in 1980 the 1st edition.The anode of its electrolyzer is the argentiferous stereotype, and negative electrode is a copper sheet, and electrolytic solution to be clean is distinguished output bismuth-containing 1-2%, the copper coin of cupric 85-90% and bismuth-containing 3-4%, the black copper powder of cupric 60-70% at first through two sections decopper(ing)s.These negative electrodes will be in the anode furnace remelting, and refining has again formed the closed cycle of impurity.At last, electrolytic solution behind the decopper(ing) (wherein cupric 8-0.2 grams per liter) will carry out degree of depth electrolysis, and not only wanting output to contain the extra high impure negative electrode of arsenic at negative electrode needs before going into the anode smelting furnace to purify, and need establish the negative electrode gas hood, to remove toxic gas, hydrogen arsenide (ASH
3), otherwise will produce harm to environment.
In recent years, there was the investigator to propose the solvent extration purifying copper electrolyte successively.People such as G.P.Giganov (Tsvetne Metallg, (8) 27-29,1978) propose, and with tributyl phosphate, TBP is that extraction agent extracts arsenic from electrolytic solution, and its concentration is higher, and viscosity is big, divide phase velocity slow; And can not extract antimony and bismuth.People such as S.Schulze (Germany Patent NO2515862) propose, and are that extraction agent extracts antimony from electrolytic solution with the di-(2-ethylhexyl)phosphoric acid ester, but can not extract arsenic, can not extract bismuth.J.M.Cohen(" international solvent extraction meeting collection of translations ", five of Ministries of Nuclear Industry, 1986, P.380) Beijing propose to use quaternary ammonium acid, and Aliquat336 extracts antimony and arsenic from electrolytic solution, but can not extract bismuth, and partition ratio is extremely low, is difficult to obtain the value of industrial application.
The object of the present invention is to provide a kind of new solvent extration, three kinds of impurity arsenic, antimony, the bismuth that can from copper electrolyte, will influence electrolytic copper quality quickly and efficiently extract respectively and in addition condensation reclaim, also can be used for from flash stove water absorption liquid, reclaiming arsenic, antimony, bismuth, it is short that it has flow process, equipment is few, cost is low, the characteristics that the rate of recovery is high.
Major technique feature of the present invention is: adopt to form identical amine extractant, and primary, secondary, tertiary amine, utilize dexterously and compare the method for descending, in turn the bismuth in the electrolytic solution, antimony, arsenic are extracted, reached and turned bane into boon and the comprehensive purpose that reclaims.
The present invention proposes three extractions, extracts three kinds of elements successively: bismuth, antimony, arsenic.Extraction is to compare greatly for the first time, and promptly the water flow is fully to extract bismuth under 2.5～3.0: 1 condition with the ratio of organic phase flow; Then the raffinate water is compared medium with unloaded organic phase for the first time, and promptly the ratio of water and organic phase flow is condition under fully to extract antimony at 1: 1; With the raffinate water second time unloaded organic phase identical with composition, compare for a short time at last, promptly water is 0.5 with the ratio of organic phase flow: fully extract arsenic under the condition.
The present invention proposes three times and strips, and from load organic phases bismuth, antimony, arsenic back extraction are got off respectively: the bismuth that extracts in the gained load organic phases is for the first time stripped bismuth into water with the ammonium salt-containing diluted acid, obtains the bismuth strip liquor; Extract for the second time antimony in the gained load organic phases with containing complexing agent, as the dilute acid soln of tartrate or citric acid water is gone in the antimony back extraction, acquisition antimony strip liquor; Extract the arsenic in the gained load organic phases for the third time, with pure dilute acid soln water is gone in the arsenic back extraction and obtain the arsenic strip liquor.
The present invention proposes: precipitate from bismuth strip liquor, antimony strip liquor and arsenic strip liquor respectively and recovery bismuth, antimony and arsenic by the acidity of adjusting separately.Their acidity value, promptly pH is respectively the 2-2.5(arsenic precipitation), 4-4.5(precipitates antimony), the 6-6.5(precipitated bismuth).
Extract, the equipment of reextraction and reclaiming process, can be pulsed sieve-plate column, centrifugal extractor and mixing-settler.But preferably centrifugal extractor.This is because rate of extraction is very fast, divides phase velocity also very fast.But in order to reduce the loss of raffinate aqueous phase mechanical entrapment to organic extractant as far as possible, centrifugal extractor is more suitable.On the other hand, aqueous phase extracted proportion big (1,234g/cm
2), the big (p of two-phase difference in specific gravity
Water-p
Have=0.364g/cm
3), intense mixing benefits to improving stage efficiency.This is the advantage of centrifugal extractor just.
The present invention selects the foundation of amine extractant, and the imagination of theoretical aspect is not only arranged, and simulates the test-results of solution in addition.In copper electrolyte, the occurrence patterns of above-mentioned rare elements is multi-level dynamic balance structure.Promptly exist the chemical equilibrium of the mutual transfer that comprises positively charged ion, yin collaterals ion and neutral molecule.Therefore, various types of extraction agents all have the uneven extraction of degree to them.As mentioned above, TBP extraction AS, P-204 extraction Sb, and N-263 extraction arsenic and antimony.It now is example with the antimony element.Its dissolving and chemical equilibrium relation is described.
Test-results shows: adopt amine extractant, for example by the 25%(volume) kerosin formed of N-235 can extract bismuth quickly and effectively from electrolytic solution.Amine extractant has better selectivity to bismuth: copper is not had extracting power.Secondly to antimony, compare down medium; Arsenic all had selective extraction preferably down low comparing.
Temperature shows the result that influences of percentage extraction: low more to the percentage extraction of above-mentioned element though temperature is high more, for the actual needs of rapid phase-splitting, extraction temperature still is recommended as 35 ℃ and is advisable.
In order from load organic phases, above-mentioned rare elements to be stripped, tested alkalescence and acid two kinds of strippants, the result shows: the phase-splitting rapidly of acid stripping solution, and the organic phase solution loss is lower, and alkaline strippant is then opposite.The present invention is best strippant with acidic salt solution for this reason.
For precipitation from stripping solution and reclaim above-mentioned rare elements, the present invention recommends simple hydrolysis method, promptly regulates stripping solution pH value, and (to Bi is pH=6～6.5, to Sb is pH=4.0～4.5, is 2～2.5 to ASpH) can and reclaim their precipitations.
The invention has the advantages that:
(1) extraction agent is formed unified management and easy to operate;
(2) extraction and reextraction system are selected rationally, and mass transfer and branch phase velocity are fast;
(3) equipment is few, and flow process is short, and cost is low;
(4) rate of recovery height of purification efficiency and impurity element has been realized comprehensive recovery and impurity open circuit completely.
Fig. 1 is solvent extration purifies arsenic, antimony, bismuth from electrolytic solution a schema.
Further specify by reference to the accompanying drawings:
Bismuth, antimony, arsenic extractant are organic amine among Fig. 1, comprise, tertiary amine (N-235), secondary amine, primary amine (N-1923), wherein tertiary amine concentration is 25-35%, modifier is that neutral phosphorus extractant (concentration is 20-25%) is such as tributyl phosphate, trialkyl phosphorous oxides etc., diluent is sulfonated kerosene, two (2-ethylhexyls) alcohol etc. Extraction temperature is 30-40 ℃. The time of contacting is 2-4 minute; The phase-splitting time is 4-6 minute kind.
Strippant is dilute acid soln among Fig. 1, can be dilute sulfuric acid, rare nitric acid etc., and its concentration range is 0.4～0.6N. Additive component was different with element during diluted acid formed. For back extraction bismuth from load organic phases, then add ammonium nitrate in the diluted acid, its concentration range is 0.8～1.2M. For back extraction antimony from load organic phases, then add complexing agent in the diluted acid, tartaric acid, sodium potassium tartrate tetrahydrate, ammonium citrate etc. In order to get arsenic from load organic oppositing back-extraction, then can adopt pure diluted acid.
The method that reclaims bismuth, antimony, arsenic among Fig. 1 is to regulate Acid concentration of stripping solution, and the pH value of three kinds of elements of precipitation is different. The pH scope of precipitated bismuth is 6～6.5, and the pH scope of precipitation antimony is 4.0～4.5; The pH scope of arsenic precipitation is 2～2.5.
Embodiment 1:
250ml contacts (35 ℃) after 5 minutes by the kerosin that 25% N-235 and 25% TBP form with the 750ml copper electrolyte, bi concns is reduced to 13 milligrams every liter by 945 milligrams/L of raw material in the aqueous phase extracted.The single-stage extraction rate of bismuth is 98.63%; Antimony concentration is reduced to 485 milligrams every liter by 715 milligrams of every liter of raw material; The single-stage extraction rate of antimony is 32.2%.
Embodiment 2
Bi concns whenever is upgraded to 2.796 grams, and antimony concentration whenever is upgraded to 250 milliliters and 125 milliliters of 0.575 load organic phases that restrains, and by the strip liquor that 0.25M tartrate and 0.5 nitric acid are formed, jolting (35 ℃) is after 5 minutes, and the stripping rate of bismuth is 89.9%; The stripping rate of antimony is 88.6%.
By pH regulator, when the pH=4 filtration, the deposition rate of antimony is 97.5%, and when pH transferred to pH=6.5, the deposition rate of bismuth was 99.1%.
Claims (4)
1, a kind of method of liquid-liquid extraction purifying copper electrolyte is characterized in that:
(a) adopt the organic amine kerosin, comparing under the condition that falls progressively successively, promptly earlier at the ratio 2.5-3 of water:, from copper electrolyte, extract bismuth at 1 o'clock with the organic phase volume, the raffinate water is 1-1.5 at water with the organic phase ratio with unloaded organic phase for the first time then:, extract antimony at 1 o'clock from electrolytic solution; At last the second raffinate water and unloaded organic phase when being 0.5-1 with the organic phase ratio, water are extracted arsenic from electrolytic solution;
(b) the raffinate water is sent the electrorefining system back to after oil removing for the third time;
(c) bismuth in the load organic phases first time strips with the diluted acid that contains ammonium nitrate; The antimony in the load organic phases for the second time is with containing the chelating agent citric acid or tartaric dilute acid soln strips; Arsenic in the load organic phases strips with diluted acid for the third time;
(d) from each strip liquor by regulating acidity respectively, reclaim arsenic, antimony, bismuth, be pH=6.5 to bismuth liquid, be pH=4.5 to antimony liquid, to arsenic liquid pH=2.5.
2,, it is characterized in that organic amine is respectively tertiary amine, primary amine, secondary amine according to the said extraction process of claim 1.
3,, it is characterized in that said diluted acid is dilute sulphuric acid or the rare nitric acid of 0.2-0.5M according to the said extraction process of claim 1.
4, method according to claim 1 is characterized in that said complexing agent is a tartrate, also can be citric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90100691A CN1024203C (en) | 1990-02-15 | 1990-02-15 | Purifying copper electrolyte by means of liquid-liquid extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90100691A CN1024203C (en) | 1990-02-15 | 1990-02-15 | Purifying copper electrolyte by means of liquid-liquid extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044128A CN1044128A (en) | 1990-07-25 |
| CN1024203C true CN1024203C (en) | 1994-04-13 |
Family
ID=4876761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90100691A Expired - Fee Related CN1024203C (en) | 1990-02-15 | 1990-02-15 | Purifying copper electrolyte by means of liquid-liquid extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024203C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2015225908A1 (en) * | 2014-03-07 | 2016-09-22 | Basf Se | Methods and systems for controlling impurity metal concentration during metallurgic processes |
| CN103849902A (en) * | 2014-03-25 | 2014-06-11 | 金隆铜业有限公司 | Recovery process of stibium and bismuth in copper electrolyte |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
-
1990
- 1990-02-15 CN CN90100691A patent/CN1024203C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044128A (en) | 1990-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102851693B (en) | Technology for recovering production of electrolytic copper and zinc from smelting ash | |
| CN102140580B (en) | Multi-metal recycling method of electric furnace tin-smelting dust | |
| CN102061382A (en) | Method for recycling zinc from zinc leaching slag cleaning solution | |
| CN110184464B (en) | Extraction separation method of thorium | |
| CN1837380A (en) | Wet-method process for reclaiming zinc from zinc leaching residue | |
| CN103160689A (en) | Method of iron extraction and removal with solvent extraction agent | |
| NO172652B (en) | PROCEDURE FOR SIMILAR SEPARATION OF DISPOSABLE ELEMENTS FROM ELECTROLYTE SOLUTIONS OF VALUE METALS | |
| CN105018753B (en) | A kind of method of composite extractant and the composite extractant extract and separate recovery indium | |
| CN1786226A (en) | Trentment method of tin copper slag | |
| CN100443604C (en) | Extraction and separation technology for reclaiming main impurity in indium in hydrochloric acid system | |
| CN102061398B (en) | Separating and recycling method of indium in hydrochloric acid system | |
| CN100383262C (en) | Method for increasing metal-extracting efficiency of 1,, (2-ethyl-hexyl) phosphate | |
| CN114572949A (en) | Production process of lithium dihydrogen phosphate | |
| US3104971A (en) | Copper recovery process | |
| CN1024203C (en) | Purifying copper electrolyte by means of liquid-liquid extraction | |
| CN108220631A (en) | A kind of method using aluminum-extracted pulverized fuel ash process condensing crystallizing mother liquor scandium | |
| CN1049642A (en) | Stone coal ash sulfuric acid is mixed the acid slaking water logging of heating and is extracted the vanadium pentoxide technical process | |
| CN1087354C (en) | Solvent extraction process for improving purity of strontium and barium salts | |
| CN1099072A (en) | Extraction process extracts the method for rare earth from the rare-earth mineral leach liquor | |
| Fletcher et al. | Combining sulfate electrowinning with chloride leaching | |
| CN109133178B (en) | Production process of manganese sulfate | |
| CN115094250A (en) | Method for recovering hafnium and other metals from hafnium-containing waste residues | |
| CN108265176A (en) | The method that lithium is extracted from flyash | |
| CN111118313B (en) | Impurity removal and recovery method for rare earth extraction emulsified organic phase | |
| US3615171A (en) | Process of separating yttrium from lanthanide rare earths |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |