CN106834682A - A kind of method for extracting germanium dechlorination in solution of zinc sulfate - Google Patents
A kind of method for extracting germanium dechlorination in solution of zinc sulfate Download PDFInfo
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- CN106834682A CN106834682A CN201710041422.7A CN201710041422A CN106834682A CN 106834682 A CN106834682 A CN 106834682A CN 201710041422 A CN201710041422 A CN 201710041422A CN 106834682 A CN106834682 A CN 106834682A
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Abstract
A kind of method the invention discloses germanium dechlorination is extracted in solution of zinc sulfate, comprises the following steps：1）Complexing：Complexing agent is added to the solution of zinc sulfate of low germanium chlorine high, is sufficiently mixed, obtain mixed solution；2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into；3）Extraction：Mixed extractant is added in mixed solution, is sufficiently mixed, extracted, isolated organic phase and extraction raffinate；4）Washing back extraction：Organic phase is washed using diluted acid or clear water, is then stripped using back washing agent, strip liquor is obtained, then by strip liquor neutralization precipitation Ti recovery.The invention provides in the production process that electrolytic zinc or zinc sulfate are produced in a kind of system from zinc sulfate in solution of zinc sulfate extraction and recovery noble metal germanium, while the method for removing harmful element chlorion, effectively realize the harmful element chlorine in removing solution of zinc sulfate while extraction and recovery Ge element, process is simple, efficiency high.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to a kind of method for extracting germanium dechlorination in solution of zinc sulfate.
Background technology
During Non-ferrous Metallurgy, the raw material that sulfuric acid system legal system makes electrolytic zinc, zinc sulfate is used is particularly containing zinc
Often contain noble metal germanium and most harmful elemental chlorine, therefore the solution of zinc sulfate obtained in production process in the raw material of flue dust class
In often contain a small amount of germanium and substantial amounts of chlorion.Germanium is the indispensable material of contemporary new and high technology, in numerous areas
It is widely used.Due to germanium, content is very low in mineral, it is impossible to exploited as a kind of independent raw material of industry, therefore can only
In nonferrous metallurgical process as byproduct in carry out synthetical recovery.Because germanium enrichment difficulty is big, industrial Ti recovery
Influenceed very big by the germanium rate of recovery in raw material, and be subject to processing the restriction that mineral use technique.Traditional extraction germanium technique has heavy
Shallow lake method, alloyage, germanium method, the acid-hatching of young eggs, cracking process etc. are waved again.But mostly there is complex process, reclaim in these prior arts
Rate is not high, produce the shortcoming of secondary pollution.And in the electrolysis production of zinc hydrometallurgy, chlorine is absolute harmful element, chlorion
Alloy lead anode will be corroded, lead is entered electrolyte in lead dichloride form and is separated out in cathode zinc, so that cathode zinc contains
Lead is high, when serious, can cause lead anode short life, and cathode zinc quality is unqualified, in addition, chloride ion content is too high can also be to reaction
Equipment causes corrosion.At present, there be the method for removing chloride ion during sulfuric acid system legal system makes electrolytic zinc, zinc sulfate：Resin
Method, cuprous method, silver ion method, extraction etc..But it is low that these methods there is also removal efficiency, complex process cost grade one high is
Row problem.
Therefore for the acid zinc sulfate leaching liquid in electrolytic zinc or zinc sulfate production process, develop a kind of simple efficient,
And can simultaneously realize that the efficient extraction under conditions of low germanium chlorine high to germanium and the effective removing to chlorine turn into urgent need and solve
Problem.
The content of the invention
A kind of method it is an object of the invention to provide germanium dechlorination is extracted in solution of zinc sulfate.
The object of the present invention is achieved like this, comprises the following steps：
1）Complexing：Complexing agent is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10 ~ 100
G/l, obtains mixed solution；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 5 ~ 40%, the parts by volume of sec-octyl alcohol is 3 ~ 10%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 0.3 ~ 3 times of mixed liquor volume, institute
The extraction raffinate stated returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.
（One）Chemical equation of the invention：
1st, the complex reaction of tartaric acid and germanium：
3C4H6O6 + GeO2•OH+7H+ = H2Ge(C4H6O6)3+3H2O
2nd, the acidification reaction of N235：
R3N + H2SO4 = [R3NH] • [HSO4]
3rd, extraction germanium reaction：
2[R3NH] • [HSO4] + H2Ge(C4H6O6)3 = [R3NH]2 •[Ge(C4H6O6)3]
+2H2SO4
4th, it is stripped 1：
[R3NH]2 •[Ge(C4H6O6)3]+2NaOH = Na2[Ge(C4H6O6)3]+2R3N+2H2O
5th, 2 are stripped：
[R3NH] • [HSO4]+2NaOH = R3N + Na2SO4+ 2H2O
6th, extraction chlorine reaction：
R3N + HCL = R3N•HCL
7th, chlorine back extraction：
R3N•HCL + NaOH = R3N + NaCL + H2O
8th, heavy germanium：
Na2[Ge(C4H6O6)3] + H2SO4 → GeO2↓ + Na2SO4 + 3C4H6O6
（Two）The general principle of present invention process process：
The present invention produces tartaric acid germanium complex first with the germanium in tartaric acid complexing solution of zinc sulfate；Secondly, using mixing
Tartaric acid germanium complex and chlorion in extractant extraction solution of zinc sulfate；Again, dechlorination is washed using diluted acid or clear water；Most
Afterwards, it is stripped Ti recovery as back washing agent using sodium hydroxide solution to go forward side by side one-step removal chlorine, is finally reached Ti recovery and removes simultaneously
The purpose of the harmful element chlorine in solution of zinc sulfate.
Beneficial effects of the present invention：
1st, the invention provides molten in zinc sulfate in the production process that electrolytic zinc or zinc sulfate are produced in a kind of system from zinc sulfate
Extraction and recovery noble metal germanium in liquid, while the method for removing harmful element chlorion, solution of zinc sulfate germanic first and tartaric acid
Germanium complex is mixed to form, is then mixed using mixed extractant, separated, the chlorion in finally back extraction removal extract is simultaneously returned
Noble metal germanium is received, the harmful element chlorine in removing solution of zinc sulfate while extraction and recovery Ge element is realized, process is simple,
Efficiency high.
2nd, the present invention can match somebody with somebody synergic reagent/modification agent using N235, sec-octyl alcohol（Second octanol, TBP）, using sulfonated coal
Oil is mixed to get mixed extractant as solvent, using sec-octyl alcohol assistance N235 extracted germaniums, while sec-octyl alcohol and N235 extract jointly
The process of removing chlorine is taken, extraction efficiency is effectively improved, on the basis of the extraction yield high for ensureing germanium, while realizing harmful unit
The extraction removing of plain chlorine, so as to improve electrolytic zinc or zinc sulfate production efficiency, kills two birds with one stone.
3rd, the present invention extracts chlorion jointly while noble metal germanium is extracted using sec-octyl alcohol and N235, then by washing
Wash the impurity of the most chlorion of removing and entrainment；Finally using aqueous slkali be stripped Ti recovery while further remove chlorine from
Son.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is further illustrated, but the present invention is subject to never in any form
Limitation, based on present invention teach that any conversion or replacement made, belong to protection scope of the present invention.
The method for extracting germanium dechlorination in solution of zinc sulfate of the present invention, comprises the following steps：
1）Complexing：Complexing agent is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10 ~ 100
G/l, obtains mixed solution；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 5 ~ 40%, the parts by volume of sec-octyl alcohol is 3 ~ 10%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 0.3 ~ 3 times of mixed liquor volume, institute
The extraction raffinate stated returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.
Step（1）Described in germanic solution of zinc sulfate to be obtained in electrolytic zinc or zinc sulfate production process by purification
Germanic zinc sulfate leaching liquid after removal flocculate impurity.
Described flocculate impurity is iron, silicon flocculate impurity.
Step（1）Described in complexing agent be tartaric acid.
The usage amount of described tartaric acid is 5 ~ 15 times of Ge content in solution of zinc sulfate.
Step（2）Described in mixed extractant in also including 2 ~ 5% parts by volume modification agent.
Described modification agent is second octanol and/or TBP.
Step（4）Described in diluted acid be watery hydrochloric acid or dilute sulfuric acid.
Described dilute sulfuric acid is the dilute sulfuric acid of Solute mass fraction≤70%.
Step（4）Described in back washing agent for 4 ~ 8mol/L sodium hydroxide solution.
Step（4）Described in back washing agent addition for mixed extractant addition 30 ~ 90%.
Step（3）Described in extraction for flow for 2m3/h four-stage counter-current extract.
Step（4）Described in washing for flow for 2m3/h level Four wash.
Step（5）Described in back extraction for flow for 2m3/h level Four be stripped.
Described neutralization precipitation is neutralized using dilute sulfuric acid.
Embodiment 1
The method of the present invention is implemented in Yunnan Ye Sheng environmental resources Science and Technology Ltd., it is as a result as follows：
Raw material：Feed liquid 30m3, sulfur acid【H+】17.86g/l,【Cl-】819mg/l,【Ge4+】223.83mg/l。
Process：
1）Complexing：To germanic solution of zinc sulfate（Feed liquid）Middle addition complexing agent tartaric acid, addition is 10 times of Ge content, then
It is sufficiently mixed, control solution acidity obtains mixed solution in 10 ~ 100g/l；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 5%, the parts by volume of sec-octyl alcohol is 10%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row flow is the four-stage counter-current extraction of 2m3/h, isolated organic phase and extraction raffinate, and described mixed extractant addition is mixing
0.3 times of liquor capacity, described extraction raffinate returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, and described washing is that flow is 2m3/
The level Four washing of h, is then stripped using back washing agent, and described back extraction is the level Four back extraction that flow is 2m3/h, is stripped
Liquid, then by strip liquor neutralization precipitation Ti recovery, described back washing agent is the sodium hydroxide solution of 4mol/L, described back washing agent
Addition for mixed extractant addition 30%.
As a result：Extraction raffinate【H+】11.53g/l,【Cl-】129mg/l,【Ge4+】8.27mg/l；Extraction yield：Germanium 96.3%, chlorine
84.3%。
Embodiment 2
The method of the present invention is implemented in Yunnan Ye Sheng environmental resources Science and Technology Ltd., it is as a result as follows：
Raw material：200 cubic metres of feed liquid, sulfur acid【H+】15.25g/l,【Cl-】2460mg/l,【Ge4+】104.59mg/l。
Process：
1）Complexing：To germanic solution of zinc sulfate（Feed liquid）Middle addition complexing agent tartaric acid, addition is 8 times of Ge content, then
It is sufficiently mixed, control solution acidity obtains mixed solution in 10 ~ 100g/l；
2）The preparation of mixed extractant：N235, sec-octyl alcohol, modification agent and sulfonated kerosene are well mixed, hybrid extraction is prepared into
Agent, the parts by volume of N235 is 30% in described mixed extractant, and the parts by volume of sec-octyl alcohol is 8%, and the modification agent of 2% parts by volume is remaining
It is sulfonated kerosene to measure；Described modification agent is second octanol；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row flow is the four-stage counter-current extraction of 2m3/h, isolated organic phase and extraction raffinate, and described mixed extractant addition is mixing
1 times of liquor capacity, described extraction raffinate returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, and described washing is that flow is 2m3/
The level Four washing of h, is then stripped using back washing agent, and described back extraction is the level Four back extraction that flow is 2m3/h, is stripped
Liquid, then by strip liquor neutralization precipitation Ti recovery, described back washing agent is the sodium hydroxide solution of 6mol/L, described back washing agent
Addition for mixed extractant addition 60%.
As a result：Extraction raffinate【H+】10.52g/l,【Cl-】164mg/l,【Ge4+】7.26mg/l；Extraction yield：Germanium 93%, chlorine
93.3%。
Embodiment 3
The method of the present invention is implemented in Yunnan Ye Sheng environmental resources Science and Technology Ltd., it is as a result as follows：
Raw material：Feed liquid 500m3, sulfur acid【H+】72.3g/l,【Cl-】1670mg/l,【Ge4+】264.59mg/l。
Process：Tartaric acid is added by 10 times of amounts of germanium amount in feed liquid, is well mixed；Using 12 grades of mixing clarifying chambers, through stream
After measuring four-stage counter-current extraction, level Four washing and the level Four back extraction for 2m3/h, the strip liquor NaOH solution of 4-8mol/l concentration
Back extraction organic phase.
1）Complexing：To germanic solution of zinc sulfate（Feed liquid）Middle addition complexing agent tartaric acid, addition is 10 times of Ge content,
Then it is sufficiently mixed, control solution acidity obtains mixed solution in 10 ~ 100g/l；
2）The preparation of mixed extractant：N235, sec-octyl alcohol, modification agent and sulfonated kerosene are well mixed, hybrid extraction is prepared into
Agent, the parts by volume of N235 is 40% in described mixed extractant, and the parts by volume of sec-octyl alcohol is 3%, and the modification agent of 5% parts by volume is remaining
It is sulfonated kerosene to measure；Described modification agent is TBP；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, adopts
With 12 grades of mixing clarifying chambers, the four-stage counter-current extraction that flow is 2m3/h, isolated organic phase and extraction raffinate are carried out, described is mixed
Conjunction extractant addition is 3 times of mixed liquor volume, and described extraction raffinate returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, and described washing is that flow is 2m3/
The level Four washing of h, is then stripped using back washing agent, and described back extraction is the level Four back extraction that flow is 2m3/h, is stripped
Liquid, then by strip liquor neutralization precipitation Ti recovery, described back washing agent is the sodium hydroxide solution of 8mol/L, described back washing agent
Addition for mixed extractant addition 90%.
As a result：Extraction raffinate【H+】50.3g/l,【Cl-】184mg/l,【Ge4+】13.1mg/l；Extraction yield：Germanium 95%, chlorine 89%.
Embodiment 4
1）Complexing：Complexing agent tartaric acid is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10
~ 100 g/l, the usage amount of described tartaric acid is 5 times of Ge content in solution of zinc sulfate, obtains mixed solution；Described contains
Germanium solution of zinc sulfate is the germanic sulphur after purification removes flocculate impurity obtained in electrolytic zinc or zinc sulfate production process
Sour zinc lixiviating solution；Described flocculate impurity is iron, silicon flocculate impurity；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 5%, the parts by volume of sec-octyl alcohol is 3%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 0.5 times of mixed liquor volume, described
Extraction raffinate return zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.Described back washing agent is the sodium hydroxide solution of 4mol/L,
The addition of described back washing agent is the 30% of mixed extractant addition.
Harmful unit while the processing method of the present embodiment realizes extraction and recovery Ge element in removing solution of zinc sulfate
Plain chlorine, process is simple, and the germanium rate of recovery is more than 93%, while ensureing chlorion clearance high.
Embodiment 5
1）Complexing：Complexing agent tartaric acid is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10
~ 100 g/l, the usage amount of described tartaric acid is 6 times of Ge content in solution of zinc sulfate, obtains mixed solution；Described contains
Germanium solution of zinc sulfate is the germanic sulphur after purification removes flocculate impurity obtained in electrolytic zinc or zinc sulfate production process
Sour zinc lixiviating solution；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 10%, the parts by volume of sec-octyl alcohol is 4%, balance of sulfonated kerosene；Described mixing
Also include the second octanol and TBP of 3% parts by volume in extractant；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 1.5 times of mixed liquor volume, described
Extraction raffinate return zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.Described back washing agent is the sodium hydroxide solution of 5mol/L,
The addition of described back washing agent is the 40% of mixed extractant addition.
Harmful unit while the processing method of the present embodiment realizes extraction and recovery Ge element in removing solution of zinc sulfate
Plain chlorine, process is simple, and the germanium rate of recovery is more than 93%, while ensureing chlorion clearance high.
Embodiment 6
1）Complexing：Complexing agent tartaric acid is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10
~ 100 g/l, the usage amount of described tartaric acid is 9 times of Ge content in solution of zinc sulfate, obtains mixed solution；Described contains
Germanium solution of zinc sulfate is the germanic sulphur after purification removes flocculate impurity obtained in electrolytic zinc or zinc sulfate production process
Sour zinc lixiviating solution；Described flocculate impurity is iron, silicon flocculate impurity；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 20%, the parts by volume of sec-octyl alcohol is 5%, balance of sulfonated kerosene；Described mixing
Also include the modification agent of 4% parts by volume in extractant；Described modification agent is second octanol；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 2 times of mixed liquor volume, described
Extraction raffinate returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.Described back washing agent is the sodium hydroxide solution of 7mol/L,
The addition of described back washing agent is the 50% of mixed extractant addition.
Harmful unit while the processing method of the present embodiment realizes extraction and recovery Ge element in removing solution of zinc sulfate
Plain chlorine, process is simple, and the germanium rate of recovery is more than 93%, while ensureing chlorion clearance high.
Embodiment 7
1）Complexing：Complexing agent tartaric acid is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10
~ 100 g/l, the usage amount of described tartaric acid is 11 times of Ge content in solution of zinc sulfate, obtains mixed solution；Described contains
Germanium solution of zinc sulfate is the germanic sulphur after purification removes flocculate impurity obtained in electrolytic zinc or zinc sulfate production process
Sour zinc lixiviating solution；Described flocculate impurity is iron, silicon flocculate impurity；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 30%, the parts by volume of sec-octyl alcohol is 7%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed,
Extracted, isolated organic phase and extraction raffinate, described mixed extractant addition is 2.5 times of mixed liquor volume, institute
The extraction raffinate stated returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.Described back washing agent is the sodium hydroxide solution of 8mol/L,
The addition of described back washing agent is the 70% of mixed extractant addition.
Harmful unit while the processing method of the present embodiment realizes extraction and recovery Ge element in removing solution of zinc sulfate
Plain chlorine, process is simple, and the germanium rate of recovery is more than 93%, while ensureing chlorion clearance high.
Embodiment 8
1）Complexing：Complexing agent tartaric acid is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10
~ 100 g/l, the usage amount of described tartaric acid is 12 times of Ge content in solution of zinc sulfate, obtains mixed solution；Described contains
Germanium solution of zinc sulfate is the germanic sulphur after purification removes flocculate impurity obtained in electrolytic zinc or zinc sulfate production process
Sour zinc lixiviating solution；Described flocculate impurity is iron, silicon flocculate impurity；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 25%, the parts by volume of sec-octyl alcohol is 9%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 1.2 times of mixed liquor volume, described
Extraction raffinate return zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.Described back washing agent is molten for the NaOH of 6.5mol/L
Liquid, the addition of described back washing agent is the 55% of mixed extractant addition.
Harmful unit while the processing method of the present embodiment realizes extraction and recovery Ge element in removing solution of zinc sulfate
Plain chlorine, process is simple, and the germanium rate of recovery is more than 93%, while ensureing chlorion clearance high.
Claims (9)
1. a kind of method for extracting germanium dechlorination in solution of zinc sulfate, it is characterised in that comprise the following steps：
1）Complexing：Complexing agent is added to germanic solution of zinc sulfate, is then sufficiently mixed, control solution acidity is 10 ~ 100
G/l, obtains mixed solution；
2）The preparation of mixed extractant：N235, sec-octyl alcohol and sulfonated kerosene are well mixed, mixed extractant is prepared into, it is described
Mixed extractant in the parts by volume of N235 be 5 ~ 40%, the parts by volume of sec-octyl alcohol is 3 ~ 10%, balance of sulfonated kerosene；
3）Extraction：By step（2）The mixed extractant of preparation is added to step（1）In the mixed solution for obtaining, it is sufficiently mixed, enters
Row extraction, isolated organic phase and extraction raffinate, described mixed extractant addition are 0.3 ~ 3 times of mixed liquor volume, institute
The extraction raffinate stated returns to zinc sulfate or electrolysis Zn system；
4）Washing back extraction：By step（3）The organic phase for obtaining is washed using diluted acid or clear water, is then carried out instead using back washing agent
Extraction, obtains strip liquor, then by strip liquor neutralization precipitation Ti recovery.
2. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 1, it is characterised in that step（1）Described in
Germanic solution of zinc sulfate is germanic after purification removes flocculate impurity for what is obtained in electrolytic zinc or zinc sulfate production process
Zinc sulfate leaching liquid.
3. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 1, it is characterised in that step（1）Described in
Complexing agent is tartaric acid.
4. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 3, it is characterised in that described tartaric acid
Usage amount is 5 ~ 15 times of Ge content in solution of zinc sulfate.
5. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 1, it is characterised in that step（2）Described in
Also include the modification agent of 2 ~ 5% parts by volume in mixed extractant.
6. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 5, it is characterised in that described modification agent is
Second octanol and/or TBP.
7. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 1, it is characterised in that step（4）Described in
Diluted acid is watery hydrochloric acid or dilute sulfuric acid.
8. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 1, it is characterised in that step（4）Described in
Back washing agent is the sodium hydroxide solution of 4 ~ 8mol/L.
9. the method for extracting germanium dechlorination in solution of zinc sulfate according to claim 1, it is characterised in that step（4）Described in
The addition of back washing agent is the 30 ~ 90% of mixed extractant addition.
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