CN101886170A - Production process for isolating fluorine and chlorine by acid extraction during electrolytic zinc production - Google Patents
Production process for isolating fluorine and chlorine by acid extraction during electrolytic zinc production Download PDFInfo
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Abstract
The invention relates to the technology of hydrometallurgy, in particular to a production process for isolating fluorine and chlorine by acid extraction during electrolytic zinc production. The method comprises the following steps of: establishing an extraction working procedure between a leaching and purifying working procedure and an electrolyzing working procedure; extracting a new liquid obtained after purification by using acidic extractant, wherein anions such as fluorinion, chloridion and the like from raw materials are remained in raffinate, enter aqueous phase cycling and cannot enter organic phases; and performing back extraction on load organic phases with waste electrolyte when the extracted organic phases become the load organic phases containing cations such as metal zinc ions and the like to make the zinc ions enter the electrolyte so as to enter the electrolyzing working procedure, wherein the anions such fluorinion, chloridion and the like cannot enter the electrolyzing working procedure in the process so as to fulfill the aim of isolating the fluorinion and the chloridion from the electrolyzing working procedure.
Description
Technical field
The present invention relates to hydrometallurgical technology, specifically is to utilize acid extract to isolate the production technique of fluorine chlorine in electrolytic zinc production.
Background technology
In the electrolytic zinc production process, the fluorine chlorine in the electrolytic solution is mainly from raw material, after fluorine concentration reaches 200mg/l, can cause the serious haftplatte of negative plate and can not shell plate, causes the heavy corrosion of negative plate simultaneously, makes the electrolysis production difficulty continue to carry out.When cl concn reaches more than the 800mg/l, can cause institute's output cathode zinc percentage of product to descend, positive plate and equipment corrosion are serious, and production cost rises, and chlorine is separated out severe contamination electrolysis procedure space simultaneously, and the harm operator are healthy.In the zinc smelting technology, fluorine chlorion in the electrolytic solution all there be strict the qualification, the general provision fluorinion concentration is less than 50mg/l, and chlorine ion concentration is less than 100mg/l.At zinc ore concentrate is in the electrolytic zinc Production Flow Chart of raw material, raw material fluorine cl content seldom, the fluorine chlorine of trace can discharge system, thereby the consequence that is caused is not serious by system self cleaning action.
Adopt separately in secondary raw material (being mainly the zinc oxide fumes of iron and steel flue dust, the rotary kiln evaporation generation) production process, because the fluorine cl content is than higher in the raw material, fluorine content can reach more than 1%, and cl content can reach 8%, cause electrolysis liquid fluorine cl concn very high, production is difficult to continue.And the fluorine content in raw material is 0.02%, continues to produce just can make the fluorinion concentration of system reach 400mg/l in 5 days.When being raw materials for production with secondary zinc raw material, even carried out pre-treatment, remaining fluorine chlorine also can progressively accumulate in system and cause concentration to raise fast.
In traditional technology, general soda lye wash or the high temperature sublimation method of adopting carries out pre-treatment to fluorine-containing chlorine raw material, remove the fluorine chlorine in the raw material, these methods can remove part or most of fluorine chlorine, at less low fluorine chlorine secondary zinc oxide material rate (F＜0.02%, Cl＜0.05%, material rate＜20%) cooperate zinc ore concentrate to produce the electrolytic zinc flow process down, fluorine chlorine does not work the mischief basically, but these pretreatment processs can produce a large amount of heavy metal-containing waste waters or contain the heavy metal flue gas, the processing cost height, unfriendly to environment.
For chlorine, extensively adopt the dechlorination of cuprous chloride method at present, make chlorine and univalent copper ion generate Cu exactly
2Cl
2The precipitation and separate, this method can thoroughly remove the chlorion in the solution, makes solution reach the chlorine ion concentration of regulation.Part enterprise employing resin anion(R.A) switching method removes the chlorine in system's solution, and the removal effect of chlorine is limited, and the waste water that resin regeneration produced simultaneously has than higher sulfuric acid concentration and heavy metal concentration, brings than higher processing cost and environmental stress.As antichlor, the production cost height seldom has enterprise to adopt with silver salt.More than remove the way of chlorine, fluorine-based can not remove.
For fluorine, also there is not good method to remove at present, generally remove fluorine with Wingdale or calcium oxide, this method is difficult to reach effective defluorination effect under zinc smelting technology condition, cause productive capacity to descend simultaneously, is difficult to economically bear.The another one method is to adopt silica gel to remove fluorine, seldom is applied, and the removal effect of this method fluorine is limited, and the regeneration of silica gel also will produce a large amount of heavy metal and vitriolic waste water of containing, and brings than higher processing cost and environmental stress.Adopt rare earth can reach reasonable effect as defluorinating agent, but rare earth resources is rare, with high costs, regenerative power is poor, and a large amount of uses can cause the wasting of resources, is not suitable as heavy fluorine agent.Remove in the process of fluorine at these, can not remove chlorine basically.
In general,, fluorine chlorine is accumulated in system cause electrolytic process fluorine cl concn to raise, high fluorine chlorine raw material can not be effectively addressed though above fluorine chlorine removal methods can play the effect that part is taken off fluorine and chlorine removal.
Summary of the invention
The objective of the invention is to avoid the deficiencies in the prior art that a kind of production technique of utilizing acid extract to isolate fluorine chlorine in electrolytic zinc production is provided, this technology can stop the fluorine chlorine of bringing system into raw material to enter into electrowinning process, thereby stops the production technique of fluorine chlorine to the harm of electrolytic process.
For achieving the above object, the technical scheme that the present invention takes is: leach between purification and the electrowinning process in traditional electrolytic zinc Production Flow Chart and set up an extraction process, thereby be implemented in the purpose of isolating the fluorine chlorion in the electrolytic zinc production, this extraction process processing step is:
(1), with di-(2-ethylhexyl)phosphoric acid (trade(brand)name P204) by volume 10%-35% and kerosene by volume 65%-90% mix, be made into extracted organic phase;
(2), the new liquid after cleaning section handled enters the dosing chute and mixes with water, making mixed water zinc ion concentration is 7-30g/l, the pH value is 4-6, enters into extraction tank then;
(3), in extraction tank, extract, organic phase is in a ratio of 1/2-2/1 than water, and mixing time is 4-7 minute, and temperature is 0 ℃-35 ℃;
(4), after the raffinate that obtains of step (3) enters the water circulation groove, raffinate zinc ion concentration decline this moment 4-10g/l, the 4-5 of pH value before extract drops to 1-2, neutralizes in neutralizing well with calcium oxide or lime carbonate, accent raffinate pH value is 4-5;
(5), the raffinate after step (4) neutralization filters through chamber-type press filter, filters the suspended solid in the solution;
(6), the raffinate after step (5) is filtered returns the dosing chute to be mixed with the new liquid of allocating into, make zinc ion concentration reach 7-30g/l, repeating step (3)-(5) form the water circulation again, water process: add new liquid--extraction--in and raffinate-filtration--is added the cycle operation of new liquid, the zine ion in the new liquid constantly is brought into extraction tank extracts;
(7), the organic phase after step (3) extraction enters the back extraction groove, is that 140-200g/l, zinc ion concentration are the solution back extraction of 35-70g/l with sulfuric acid concentration, the back extraction of organic phase and this solution is in a ratio of 3/1-8/1, the back extraction temperature is 0 ℃-40 ℃;
(8), to turn back to extraction tank mixed with water for the unloading organic phase that obtains after step (7) back extraction, extract once more, form the organic phase circulation through step (3), (7), organic phase is passed through: extraction--back extraction cycle operation, the zine ion of aqueous phase constantly is brought in the electrolytic solution, finishes the transfer of zine ion from new liquid to electrolytic solution;
(9) solution after the back extraction enters adsorption tank, removes the organic phase of the organic phase reconciliation of being carried secretly, and the organic phase concentration that makes solution is less than 10
-5Mg/l enters electrowinning process then.
Described extraction process also is included in step (5) discharging operation afterwards: raffinate is after filtration operation, when wherein fluorinion concentration reaches more than the 400mg/l, chlorine ion concentration reaches more than the 800mg/l, just can enter the discharging extraction tank, thoroughly behind the heavy metal in the extraction raffinate, high fluorine chlorine water is discharged into heavy fluorine groove and calcium hydroxide reaction, make the pH value reach 11-12, all fluorion and calcium ion form the Calcium Fluoride (Fluorspan) precipitation, the also whole hydrolytic precipitations of remaining heavy metal ion, carry out the acid-alkali accommodation of water after the filtration, adjust pH 6-9 makes it qualified discharge or utilization again, and chlorion is discharging thereupon also.
Described discharging operation also be included in the circulation of the described organic phase of step (8) shunting partly organic phase carry out saponification: the organic phase after step (7) back extraction enters soap tank, sodium hydroxide solution with 20%-40% carries out saponification, alkalimetal ion in the alkali lye replaces the hydrogen ion in the organic phase, the acidity of water when the discharging extraction can not changed because of extraction to improve the percentage extraction of metal, organic phase after the saponification enters the discharging extraction tank again heavy metal is extracted, and turns back to then in the load organic phases storage tank and enters back extraction.
Described extraction process also comprise step (3) afterwards return the leaching operation: because the continuous adding of new liquid, water circulation volume constantly increases, and the equivalent volumes raffinate that circulation time will be brought new liquid into turns back to the leaching operation by the water circulation groove.
Described extraction process also comprises step (7) back extraction regeneration afterwards: organic phase is in extraction---can greater than 18% concentrated hydrochloric acid organic phase be carried out back extraction with concentration and regenerate because the extracting and enriching of impurity such as iron, cobalt wears out in the back extraction process.
Principle of the present invention is: between purification and electrowinning process an extraction process is set, because fluorine chlorine contained in the zinc metallurgy raw material is through after leaching and the cleaning section, be present in the ionic form in the new liquid of cleaning section gained, the present invention utilizes the principle of cationic exchange in the acid extract process, adopt acidic extractant to mix and extract, react and be with the new liquid that contains metal ion such as zinc:
HA represents extraction agent in the formula, M
2+Represent divalent-metal ion,
Be the organic phase composition.A replaces M
2+The inner coordination sphere water of hydration, extraction agent has entered the inner coordination sphere of metal, the title complex of generation is extracted to organic phase
After extraction, negatively charged ion such as fluorine, chlorine remain in and enter the water circulation in the raffinate, can not enter organic phase; Organic phase after the extraction becomes cationic load organic phases such as containing metallic zinc, with this load organic phases of waste electrolyte back extraction, make zine ion enter into electrolytic solution, thereby enter electrowinning process, in this process, negatively charged ion such as fluorine, chlorine is unapproachable, thereby reached fluorine, chlorion is isolated in purpose outside the electrowinning process.
The invention has the beneficial effects as follows: adopt this production technique, fluorine chlorine in the zinc metallurgy raw material can be isolated in outside the electrowinning process, make the solution fluorine cl content that enters electrowinning process less than 50mg/l, the fluorine chlorine that can effectively avoid being subjected in the electrolytic zinc production process endangers, and has solved the key issue that high fluorine chlorine zinc raw material smelting process is faced; The problem that the disposable solution fluorine chlorine of energy brings can make the technico-economical comparison of electrolytic zinc production technique obtain the essence improvement; When making high fluorine chlorine raw material, need not carry out fluorine chlorine and remove pre-treatment, can reduce every processing costs, energy consumption, effectively improve metal recovery rate, reduce pollutant emission as the electrolytic zinc raw materials for metallurgy; Can promote effectively that the secondary resource of zinc effectively utilizes, help eliminating the backward production facilities, realize the benign development of recycling economy.China is most of utilize the wet method electrolytic zinc plant of time tutanag raw material all exist small scale, processing method backwardness, enterprise's production energy consumption height, seriously polluted, level of resource utilization is poor, the problem of product hierarchy difference, belong to and be about to superseded backward production facilities, if utilizing this technology transforms, the backwardness of these enterprises is thoroughly changed, play an important role promoting local recycling economy development.
Description of drawings
Fig. 1 is traditional electrolytic zinc technological process of production figure
Fig. 2 is technological process of production figure of the present invention
Fig. 3 is an extraction process schema in the production technique of the present invention
Embodiment
Below principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1:
Enterprise for--purification---electrolysis flow process (see figure 1) that in zinc hydrometallurgy, adopted leaching, only need near original system, set up the corresponding extracting system of a cover according to design, original new liquid pipeline is introduced extracting system water recycle system liquid pool, by back extraction institute requirement flow circular electrolyte being introduced the back extraction system can realize, can not do any change for original system.For newly-built system, can carry out system design according to traditional electrolytic zinc production technique, only need between cleaning section and electrowinning process, to increase extracting system and can realize (see figure 2).
Concrete steps are as follows: (seeing Fig. 2, Fig. 3).
1, be raw material with zinc baking sand or zinc oxide ore, contain zinc oxide with sulphuric acid soln or waste electrolyte leaching, formation contains the solution that zinc is 100-170g/l, and necessary deironing is controlled at the total iron concentration of this solution in the 30mg/l in leaching process.
2, the solution that step 1 is obtained adds zinc powder at low temperatures, removes copper and cadmium in the solution by replacement(metathesis)reaction, at high temperature adds zinc powder after the filtration again and removes contained cobalt and nickel, obtains new liquid after the filtration, and the zinc ion concentration of new liquid is 100-170g/l.
3, with di-(2-ethylhexyl)phosphoric acid (trade(brand)name P204) by volume 10% and kerosene 90% mix by volume, be made into extracted organic phase and add extraction tank.
4, the new liquid that obtains of step 2 enters the dosing chute and mixes with water, and to make mixed water zinc ion concentration be 7-10g/l by regulating new flow quantity, and adjust pH is 4, enters into extraction tank then.
5, extract in extraction tank, organic phase is in a ratio of 2/1 than water, and mixing time is 4 minutes, and temperature is controlled to be 0 ℃-10 ℃, through the extraction of three stage countercurrents, Zn
+Percentage extraction is 60-70%.
6, step 5 obtain raffinate enter the water circulation groove after, raffinate zinc ion concentration decline this moment 4-6g/l, the 4-5 of pH value before extract drops to 1-2, neutralizes in neutralizing well with calcium oxide or lime carbonate, accent raffinate pH value is 4.
7, in the step 6 and after raffinate filter through chamber-type press filter, filter the suspended solid in the solution.
8, the raffinate after step 7 is filtered returns the dosing chute to be mixed with the new liquid of allocating into, make zinc ion concentration reach 7-10g/l, repeating step 5-8 forms the water circulation again, water process: add new liquid--extraction--in and raffinate-filtration--is added the cycle operation of new liquid, the zine ion in the new liquid constantly is brought into extraction tank extracts; Because the continuous adding of new liquid, water circulation volume constantly increases, and the equivalent volumes raffinate that circulation time will be brought new liquid into turns back to the leaching operation by the water circulation groove; Raffinate is in the cycle operation process, when wherein fluorinion concentration reaches 400mg/l, chlorine ion concentration reaches 800mg/l, enter the discharging extraction tank, thoroughly behind the heavy metal in the extraction raffinate, high fluorine chlorine water is discharged into heavy fluorine groove and calcium hydroxide reaction, make the pH value reach 11-12, all fluorion and calcium ion form the Calcium Fluoride (Fluorspan) precipitation, remaining heavy metal ion is whole hydrolytic precipitations also, carry out the acid-alkali accommodation of water after the filtration, adjust pH 6-9, make it qualified discharge or utilization again, chlorion is discharging thereupon also, after testing, and Cd≤0.1mg/l in the water; Pb≤1.0mg/l; Hg≤0.05mg/l; Cu≤0.5mg/l; Zn≤2.0mg/l; As≤0.5mg/l; F≤10mg/l.
9, the organic phase after step 5 extraction enters the back extraction groove, is that 140-160g/l, zinc ion concentration are the solution back extraction of 35-45g/l with sulfuric acid concentration, and the back extraction of organic phase and this solution is in a ratio of 3/1, and the back extraction temperature is 0 ℃-10 ℃; It is that 20% sodium hydroxide solution carries out saponification that the unloading organic phase some that obtains after the back extraction is entered soap tank concentration, purpose is can not change because of extraction to improve the percentage extraction of metal for the acidity that makes water when discharging extracts, organic phase after the saponification enters the discharging extraction tank again heavy metal is extracted, and turns back to then in the load organic phases storage tank and enters back extraction; Meanwhile, it is mixed with water that another of the unloading organic phase that obtains after the back extraction partly turns back to extraction tank, extracts once more, and organic phase is passed through: extraction--back extraction cycle operation, the zine ion of aqueous phase constantly is brought in the electrolytic solution, finishes the transfer of zine ion from new liquid to electrolytic solution;
10, after the back extraction solution enter adsorption tank by the back extraction liquid bath, remove the organic phase and the dissolved organic phase of being carried secretly, the organic phase concentration that makes solution is less than 10
-5Mg/l enters electrowinning process then, and electrowinning process gets final product according to a conventional method, after testing, the solution that enters electrowinning process wherein the fluorine cl content less than 50mg/l;
11, organic phase is in extraction---and when the extracting and enriching of impurity such as iron, cobalt wore out, the concentrated hydrochloric acid of usable concentration 18% carried out back extraction regeneration in the back extraction process.
Produce 20000 tons of electrolytic zincs, extraction section metal recovery rate 96%, new liquid Zn per year
+170g/l, new flow quantity are 15.5m
3/ h, then
The water circulation: aqueous-phase concentration is 10g/l, percentage extraction 70%, and raffinate pH1.3, circular flow are 376m
3/ h, wherein new liq is long-pending is 15.47m
3/ h.
The organic phase circulation: the organic phase working concentration is 7.0g/l, and back extraction ratio is 95%, and the organic phase internal circulating load is 395.49m
3/ h, comparing (O/A) is 1.05.
The back extraction circulation: utilize waste electrolyte as strip liquor, be in a ratio of 6, back extraction ratio 95%, the waste electrolyte internal circulating load is 66m
3/ h, waste liquid zinc ion concentration increment 39.85g/l.
Embodiment 2
Repeat by embodiment 1 described same steps as, still, it is as follows that processing parameter is adjusted: di-(2-ethylhexyl)phosphoric acid (trade(brand)name P204) by volume 10-19% and kerosene by volume 81-89% mix and be made into extracted organic phase; Control water zinc ion concentration is 10-20g/l, and adjust pH is 5; Extraction conditions: organic phase is in a ratio of 1/1 than water, and mixing time is 5 minutes, and temperature is controlled to be 10 ℃-15 ℃, transfers raffinate pH value 5; The back extraction condition: with sulfuric acid concentration is the waste electrolyte back extraction of 160-180g/l, zinc ion concentration 45-55g/l, and the back extraction of organic phase and waste electrolyte is in a ratio of 4/1, and the back extraction temperature is 10 ℃-20 ℃; With concentration is that 25% sodium hydroxide solution carries out saponification; Concentrated hydrochloric acid with concentration 19-25% carries out back extraction regeneration.
Embodiment 3
Repeat by embodiment 1 described same steps as, still, it is as follows that processing parameter is adjusted: di-(2-ethylhexyl)phosphoric acid (trade(brand)name P204) by volume 19-25% and kerosene by volume 75-81% mix and be made into extracted organic phase; Control water zinc ion concentration is 20-30g/l, and adjust pH is 6; Extraction conditions: organic phase is in a ratio of 1/2 than water, and mixing time is 7 minutes, and temperature is controlled to be 15 ℃-25 ℃, and transferring raffinate pH value is 5; The back extraction condition: with sulfuric acid concentration is the waste electrolyte back extraction of 180-200g/l, zinc ion concentration 55-70g/l, and the back extraction of organic phase and waste electrolyte is in a ratio of 5/1-7/1, and the back extraction temperature is 20 ℃-30 ℃; With concentration is that 35% sodium hydroxide solution carries out saponification; Concentrated hydrochloric acid with concentration 25-32% carries out back extraction regeneration.
Embodiment 4
Repeat by embodiment 1 described same steps as, still, it is as follows that processing parameter is adjusted: di-(2-ethylhexyl)phosphoric acid (trade(brand)name P204) by volume 25-35% and kerosene by volume 65-75% mix and be made into extracted organic phase; Control water zinc ion concentration is 30g/l, and adjust pH is 5.5; Extraction conditions: organic phase is in a ratio of 1.5/1 than water, and mixing time is 6 minutes, and temperature is controlled to be 25 ℃-35 ℃, and transferring raffinate pH value is 4.5; The back extraction condition: with sulfuric acid concentration is the waste electrolyte back extraction of 200g/l, zinc ion concentration 70g/l, and the back extraction of organic phase and waste electrolyte is in a ratio of 7/1-8/1, and the back extraction temperature is 30 ℃-40 ℃; With concentration is that 40% sodium hydroxide solution carries out saponification; Concentrated hydrochloric acid with concentration 32-37% carries out back extraction regeneration.
The above only is preferred embodiment of the present invention, in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is not equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. utilize acid extract to isolate the production technique of fluorine chlorine in electrolytic zinc production, it is characterized in that being provided with the extraction process that can isolate the fluorine chlorion between cleaning section and electrowinning process, concrete steps are:
(1), with di-(2-ethylhexyl)phosphoric acid by volume 10%-35% and kerosene by volume 65%-90% mix, be made into extracted organic phase;
(2), the new liquid after cleaning section handled enters the dosing chute and mixes with water, making mixed water zinc ion concentration is 7-30g/l, the pH value is 4-6, enters into extraction tank then;
(3), in extraction tank, extract, organic phase is in a ratio of 1/2-2/1 than water, and mixing time is 4-7 minute, and temperature is 0 ℃-35 ℃;
(4), after the raffinate that obtains of step (3) enters the water circulation groove, in neutralizing well, neutralize, transferring raffinate pH value is 4-5 with calcium oxide or lime carbonate;
(5), the raffinate after step (4) neutralization filters through chamber-type press filter, filters the suspended solid in the solution;
(6), the raffinate of step (5) after filtering return the dosing chute and mix with the new liquid of allocating into, makes zinc ion concentration reach 7-30g/l, repeating step (3)-(5) form water and circulate again, the zine ion in the new liquid constantly is brought into extraction tank extracts;
(7), the organic phase after step (3) extraction becomes load organic phases, load organic phases is entered the back extraction groove, with sulfuric acid concentration is that 140-200g/l, zinc ion concentration are the solution back extraction of 35-70g/l, and the back extraction of load organic phases and this solution is in a ratio of 3/1-8/1, and the back extraction temperature is 0 ℃-40 ℃;
(8), that the unloading organic phase that obtains after step (7) back extraction turns back to extraction tank is mixed with water, extracts once more, forms the organic phase circulation through step (3), (7), finishes the transfer of zine ion from new liquid to electrolytic solution;
(9) solution after the back extraction enters adsorption tank, removes the organic phase and the dissolved organic phase of being carried secretly, and the organic phase concentration that makes solution is less than 10
-5Mg/l enters electrowinning process then.
2. the production technique of in electrolytic zinc production, utilizing acid extract to isolate fluorine chlorine as claimed in claim 1, it is characterized in that described extraction process also is included in step (5) discharging operation afterwards: raffinate is after filtration operation, when wherein fluorinion concentration reaches more than the 400mg/l, chlorine ion concentration reaches more than the 800mg/l, just can enter the discharging extraction tank, thoroughly behind the heavy metal in the extraction raffinate, high fluorine chlorine water is discharged into heavy fluorine groove and calcium hydroxide reaction, make the pH value reach 11-12, all fluorion and calcium ion form the Calcium Fluoride (Fluorspan) precipitation, the also whole hydrolytic precipitations of remaining heavy metal ion, carry out the acid-alkali accommodation of water after the filtration, adjust pH 6-9, make it qualified discharge or utilization again, chlorion is discharging thereupon also.
3. the production technique of in electrolytic zinc production, utilizing acid extract to isolate fluorine chlorine as claimed in claim 2, it is characterized in that described extraction process also is included in the described organic phase circulation of step (8), saponification is carried out in shunting partly organic phase: the organic phase after step (7) back extraction enters soap tank, sodium hydroxide solution with concentration 20%-40% carries out saponification, organic phase after the saponification enters the discharging extraction tank again heavy metal is extracted, and turns back to then in the load organic phases storage tank and enters back extraction.
4. the production technique of in electrolytic zinc production, utilizing acid extract to isolate fluorine chlorine as claimed in claim 1, it is characterized in that described extraction process also comprise step (3) afterwards return the leaching operation.
5. the production technique of utilizing acid extract to isolate fluorine chlorine in electrolytic zinc production as claimed in claim 1 is characterized in that described extraction process also comprises step (7) back extraction regeneration afterwards: greater than 18% concentrated hydrochloric acid organic phase is carried out back extraction with concentration and regenerate.
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Cited By (6)
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| CN102021336A (en) * | 2010-12-12 | 2011-04-20 | 昆明理工大学 | Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution |
| CN102031366A (en) * | 2010-12-15 | 2011-04-27 | 浙江海尚环境科技有限公司 | Extractive preparation method of high-purity zinc oxide |
| CN102477488A (en) * | 2010-11-29 | 2012-05-30 | 厦门紫金矿冶技术有限公司 | Method for fractional neutralization and extraction of zinc |
| CN102517609A (en) * | 2012-01-13 | 2012-06-27 | 株洲圣达资源循环科技有限公司 | Method and equipment for removing fluorine and chlorine from zinc electrolyte |
| CN107523689A (en) * | 2017-08-10 | 2017-12-29 | 云南龙蕴科技环保股份有限公司 | A kind of method of dechlorination in organic phase |
| CN107675212A (en) * | 2017-10-18 | 2018-02-09 | 江西理工大学 | A kind of Zinc electrolysis fluorine-resistant lead base composite anode and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361295A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院化工冶金研究所 | Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation |
| CN1837380A (en) * | 2006-04-18 | 2006-09-27 | 祥云县飞龙实业有限责任公司 | Wet-method process for reclaiming zinc from zinc leaching residue |
| CN1858272A (en) * | 2006-06-07 | 2006-11-08 | 祥云县飞龙实业有限责任公司 | Combined process for organic solvent extracting zinc and wet zinc refining |
| CN101041520A (en) * | 2007-03-23 | 2007-09-26 | 长沙矿冶研究院 | Treatment method for recycling zinc electrolysis washing wastewater |
-
2010
- 2010-06-29 CN CN2010102163433A patent/CN101886170B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361295A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院化工冶金研究所 | Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation |
| CN1837380A (en) * | 2006-04-18 | 2006-09-27 | 祥云县飞龙实业有限责任公司 | Wet-method process for reclaiming zinc from zinc leaching residue |
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