CN108977660A - The method of fluorine removal in Zinc Hydrometallurgy Process - Google Patents
The method of fluorine removal in Zinc Hydrometallurgy Process Download PDFInfo
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- CN108977660A CN108977660A CN201810922428.XA CN201810922428A CN108977660A CN 108977660 A CN108977660 A CN 108977660A CN 201810922428 A CN201810922428 A CN 201810922428A CN 108977660 A CN108977660 A CN 108977660A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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Abstract
The invention discloses the methods of fluorine removal in Zinc Hydrometallurgy Process, it include: to contact the perchloric acid solution of zinc sulfate with aluminium sheet or aluminium skimmings to chemically react, to remove the fluorination aluminum precipitation of generation from solution, to reduce the content of fluoride ion in the perchloric acid solution of zinc sulfate.This method is using the fluorine ion in aluminium sheet or aluminium skimmings removing perchloric acid solution of zinc sulfate, without increasing specific impurity removal process and equipment, simultaneously without introducing new medicament and auxiliary material, not only simple process, cost of investment are low, and defluorination effect is good, can effectively avoid increasing impurity removal process caused by zinc metal loss, and make Zinc electrolysis production can it is continuous, be normally carried out.
Description
Technical field
The invention belongs to chemical fields, specifically, the method for relating generally to fluorine removal in Zinc Hydrometallurgy Process.
Background technique
In wet process zinc abstraction industry, the fluorine ion in solution of zinc sulfate is always the technological difficulties and forbidden zone of the sector.
And the excessively high cathode plate heavy corrosion during will lead to Zinc electrolysis of solution of zinc sulfate fluorinion concentration, so that cathode plate be made to use the longevity
Life, which declines, simultaneously causes to be precipitated the problems such as zinc removing is difficult, seriously affect Zinc electrolysis process it is continuous, be normally carried out.Currently, wet process
The common methods of separating fluoride ion have from solution of zinc sulfate in zinc abstraction industry: chemical precipitation method, ion-exchange and extraction
Separate fluorine chlorine method.Sedimentation fluorine removal, it is currently used have be added from fluorine removal in solution or in leaching process using the salt of thorium
A small amount of milk of lime or silica gel fluorine removal etc., wherein dilute thorium metal is more expensive, higher cost, should not use in industrial production, lime
Newborn fluorine removal, fluoride removing rate is low, silica gel fluorine removal be make fluorine ion absorption remove on silica gel, while fluorine removal the loss of zinc also compared with
Greatly；Ion-exchange mainly using ion exchange resin adsorb exchange solution in fluorine, chloride ion to reach removing fluorine, chlorine from
The purpose of son, but this method defluorinate, chlorine efficiency is less than 60%, and there are sulphate crystal fouling bring resin regeneration circulation benefits
With the problems such as rate is low, resin regeneration water consumption is big, the fluorine-containing chlorine ion concentration of recycled water is high, reused water processing is at high cost.And it extracts
Separation fluorine chlorine method has that extracting zinc equipment operation volume is big, investment height again, raffinate intermediate ion complicated component, fluorine chloride ion content
It is low, be unfavorable for separating and recovering, and be likely to occur fouling, salt crystallization the problems such as, for example, by using P204 extract zinc ion, use
Techniques fluorine removals such as the extraction of tertiary amine N 235, ammonium hydroxide back extraction, quick lime defluorinate etc..
In brief, removed in existing solution of zinc sulfate the technology of fluorine chloride ion there is also such-and-such insufficient or
Limitation, the technique of solution of zinc sulfate fluorine removal need to be further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is that the method for proposing fluorine removal in Zinc Hydrometallurgy Process, this method remove perchloric acid sulfuric acid using aluminium sheet or aluminium skimmings
Fluorine ion in zinc solution, without increasing specific impurity removal process and equipment, while without introducing new medicament and auxiliary material, not only
Simple process, cost of investment are low, and defluorination effect is good, zinc metal caused by increasing impurity removal process can effectively be avoided to damage
Lose, and make Zinc electrolysis production can it is continuous, be normally carried out.
According to an aspect of the present invention, the invention proposes a kind of methods of fluorine removal in Zinc Hydrometallurgy Process.According to this
The embodiment of invention chemically reacts this method comprises: contacting the perchloric acid solution of zinc sulfate with aluminium sheet or aluminium skimmings,
To remove the fluorination aluminum precipitation of generation from solution, so that the fluorine ion reduced in the perchloric acid solution of zinc sulfate contains
Amount.
The method of fluorine removal in Zinc Hydrometallurgy Process according to the above embodiment of the present invention, inventor is dexterously with aluminium sheet or aluminium
Fluorine ion in bits removing solution of zinc sulfate, i.e., by being arranged in perchloric acid solution of zinc sulfate storage facilities and relay device
Aluminium sheet or aluminium skimmings contact fluorine-containing high solution with aluminium sheet or aluminium skimmings and react, and aluminium sheet or aluminium skimmings destroy surface by chloride ion
Aluminium, which directly contacts to react and be dissolved with acid solution, after oxide layer generates Al3+, Al3+With the F in solution?It reacts
Generate AlF3, AlF3Solubility is lower in acid solution and sedimentation removes.I.e. in the Zinc Hydrometallurgy Process of the above embodiment of the present invention
The method of fluorine removal only needs to increase aluminium sheet and aluminium skimmings on the basis of original technique, without increase specific impurity removing process and
Equipment, and aluminium sheet can also use for a long time, fluorine removal product AlF3Solubility in acid solution is extremely low, is not easy to be returned molten circulation,
It is permanently removed so as to directly stay in slag phase.Not only simple process, cost of investment are low as a result, defluorination effect is good, Er Qie
Also without new medicament and auxiliary material is added during fluorine removal, it can effectively avoid introducing other impurity elements and increase except general labourer
Zinc metal loss caused by skill.
In addition, the method for fluorine removal can also have following add in Zinc Hydrometallurgy Process according to the above embodiment of the present invention
Technical characteristic:
In some embodiments of the invention, chloride ion content is not less than 900mg/ in the perchloric acid solution of zinc sulfate
L, content of fluoride ion are not less than 70mg/L.Thus, it is possible to significantly improve the efficiency and effect of fluorine removal.
In some embodiments of the invention, chloride ion content is not less than in the perchloric acid solution of zinc sulfate
1200mg/L, content of fluoride ion are not less than 70mg/L.Thus, it is possible to further increase the efficiency and effect of fluorine removal.
In some embodiments of the invention, the perchloric acid solution of zinc sulfate is the acid generated in Zinc Hydrometallurgy Process
Property zinc sulfate leaching liquid and/or Zinc electrolysis waste liquid.
In some embodiments of the invention, the aluminium sheet scraps cathode plate, the aluminium for what is generated during Zinc electrolysis
Bits are that the clast that cathode plate or aluminum material generate is scrapped described in cutting and polishing.Zinc electrolysis process can not only be made as a result,
The aluminum cathode plate scrapped is fully used, and fluorine removal cost can also be further decreased.
In some embodiments of the invention, in the fluid storage equipment of the chemical reaction in Zinc Hydrometallurgy Process into
Row.Therefore without the specific impurity removing process of increase and equipment.
In some embodiments of the invention, the fluorination aluminum precipitation passes through in Zinc Hydrometallurgy Process from removing in solution
Sedimentation and filter progress are completed.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the flow chart of the method for fluorine removal in Zinc Hydrometallurgy Process according to an embodiment of the invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
The present invention is proposed based on following problems: fluorine quilt of Zinc hydrometallurgy process during sulfuric acid leaching, in raw material
It is leached into solution, the loss of entire wet method system fluorine only leans on system dilution under conditions of not specific defluorination process
Balance system fluorine content.If the fluorine total amount that raw material is carried along into exceeds the entire wet method system fluorine content of fluorine total amount of system dilution
To persistently it rise, the rolled tin removing that just will affect Zinc electrolysis process when system fluorine content is excessively high is difficult, corroding cathode plate speed
Aggravation.In order to solve the above-mentioned technical problem the present inventor and overcomes process flow in current solution of zinc sulfate defluorination technology
The problems such as complexity, reagent cost are high, defluorinate rate is low, fluorine ion can cause the life of corrosion to cathode plate during to Zinc electrolysis
It produces under practice, dexterously with the fluorine ion in aluminium sheet (aluminium skimmings) removing solution of zinc sulfate, i.e., in the acid sulfuric acid containing chloride ion
Aluminium sheet or aluminium skimmings are impregnated in zinc solution to remove fluorine ion contained in institute in solution, make fluorine ion and dissolved aluminium ion
In conjunction with generation AlF3Sediment enters solid phase and is separated.
For this purpose, the invention proposes a kind of methods of fluorine removal in Zinc Hydrometallurgy Process.According to an embodiment of the invention, the party
Method includes: to contact perchloric acid solution of zinc sulfate with aluminium sheet or aluminium skimmings to chemically react, so that the aluminum fluoride of generation sinks
Shallow lake is removed from solution, to reduce the content of fluoride ion in perchloric acid solution of zinc sulfate.
The method of fluorine removal in Zinc Hydrometallurgy Process according to the above embodiment of the present invention, inventor is dexterously with aluminium sheet or aluminium
Fluorine ion in bits removing solution of zinc sulfate, i.e., by being arranged in perchloric acid solution of zinc sulfate storage facilities and relay device
Aluminium sheet or aluminium skimmings contact fluorine-containing high solution with aluminium sheet or aluminium skimmings and react, and aluminium sheet or aluminium skimmings destroy surface by chloride ion
Aluminium, which directly contacts to react and be dissolved with acid solution, after oxide layer generates Al3+, Al3+With the F in solution?It reacts
Generate AlF3, AlF3Solubility is lower in acid solution and sedimentation removes.I.e. in the Zinc Hydrometallurgy Process of the above embodiment of the present invention
The method of fluorine removal only needs to increase aluminium sheet and aluminium skimmings on the basis of original technique, without increase specific impurity removing process and
Equipment, and aluminium sheet can also use for a long time, fluorine removal product AlF3Solubility in acid solution is extremely low, is not easy to be returned molten circulation,
It is permanently removed so as to directly stay in slag phase.Not only simple process, cost of investment are low as a result, defluorination effect is good, Er Qie
Also without new medicament and auxiliary material is added during fluorine removal, it can effectively avoid introducing other impurity elements and increase except general labourer
Zinc metal loss caused by skill.
According to a particular embodiment of the invention, perchloric acid solution of zinc sulfate is the acid leaching generated in Zinc Hydrometallurgy Process
Liquid and/or Zinc electrolysis waste liquid out.Wherein, it is not less than inventors have found that working as chloride ion content in perchloric acid solution of zinc sulfate
900mg/L can significantly improve the efficiency and effect of fluorine removal when content of fluoride ion is not less than 70mg/L.Preferably, perchloric acid
Chloride ion content can be not less than 1200mg/L in solution of zinc sulfate, and content of fluoride ion can be not less than 70mg/L, thus, it is possible to
Further increase the efficiency and effect of fluorine removal.Further, the haptoreaction of perchloric acid solution of zinc sulfate and aluminium sheet or aluminium skimmings
It can be carried out in the fluid storage equipment in Zinc Hydrometallurgy Process, fluorination aluminum precipitation is removed from solution through zinc hydrometallurgy mistake
Sedimentation and filter progress in journey are completed.
Embodiment according to the present invention carries out defluorinate processing to acid zinc sulfate leaching liquid, with reference to Fig. 1, treatment process
In make acid zinc sulfate leaching liquid flow through concentration basin to contact with aluminium sheet, to generate containing fluorination aluminum precipitation, make acid zinc sulfate
Fluorine ion in leachate is converted into AlF3Sediment enters solid phase and is separated.Wherein, sour sulfur in the treatment process
Sour zinc lixiviating solution Cl-Content is not less than 900mg/L, F-Content is not less than 70mg/L, thus can add under conditions of high chlorinity
The speed that fast surface of aluminum plate chemically reacts, improves defluorination effect.Preferably, acid zinc sulfate leaching liquid in the treatment process
Cl-Content is not less than 1200mg/L, F-Content is not less than 70mg/L, it is possible thereby to which further speeding up surface of aluminum plate occurs chemistry instead
The speed answered improves defluorination effect.
A specific embodiment according to the present invention, connects acid zinc sulfate leaching liquid with aluminium sheet
Touching mode is not particularly restricted, and those skilled in the art can select according to actual needs.For example, can be by by aluminium
Plate, which hangs and immerses in acid zinc sulfate leaching liquid, realizes that contact of the acid zinc sulfate leaching liquid with aluminium sheet can specifically make
Aluminium sheet hangs on the top of concentration basin and protrudes into acid zinc sulfate leaching liquid.The acidity of fluoride ion can not only be made as a result,
Solution of zinc sulfate, which is in contact in concentration basin with aluminium sheet, to react, and then achievees the purpose that fluorine removal, and by hanging aluminium sheet
In concentration basin, the aluminium sheet of suspension can with long duration of action, can also effectively avoid due to replace often aluminium sheet cause to operate it is numerous
Trivial and then influence production efficiency and wasting manpower and material resources' resource.
Another specific embodiment according to the present invention, when the aluminium sheet being arranged in concentration basin, aluminium sheet immerses zinc sulfate leaching
The volume ratio of the surface area in liquid and zinc sulfate leaching liquid is not less than 10cm out2/ L, such as can be 12cm2/L、15cm2/L、
18cm2/L、23cm2/ L etc..Inventors have found that when the surface area in aluminium sheet immersion zinc sulfate leaching liquid is too small, aluminium sheet and zinc sulfate
The contact of leachate is not enough, and influences the reaction rate of aluminium sheet and zinc sulfate leaching liquid, and then influence to zinc sulfate leaching liquid
Fluorine removing rate and defluorination effect.Zinc sulfate leaching is protruded by the number and aluminium sheet of control setting aluminium sheet in the present invention as a result,
The volume ratio of length in liquid out, surface area and zinc sulfate leaching liquid that aluminium sheet can be made to immerse in zinc sulfate leaching liquid is not less than
10cm2/ L, and then dramatically increase fluorine removing rate and defluorination effect to zinc sulfate leaching liquid.
Another specific embodiment according to the present invention, the time that zinc sulfate leaching liquid is contacted with aluminium sheet can for 16~
For 24 hours, for example, 17h, 18h, 19h, 20h, 21h, 22h, 23h, for 24 hours.Inventors have found that if zinc sulfate leaching liquid is contacted with aluminium sheet
Time it is too short, it is not significant to the defluorination effect of zinc sulfate leaching liquid, and if time that zinc sulfate leaching liquid is contacted with aluminium sheet
It is too long, and will affect production efficiency.Inventor has found through a large number of experiments, when the time that control zinc sulfate leaching liquid is contacted with aluminium sheet
For 16~for 24 hours when, the defluorination effect to zinc sulfate leaching liquid can be significantly improved on the basis of ensuring production efficiency, goes forward side by side one
Step improves the removal efficiency of fluorine.Further, zinc sulfate leaching liquid and the catalytic temperature of aluminium sheet can be 40-70 DEG C, for example,
50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, it is possible thereby to further increase the defluorination effect and defluorination effect to zinc sulfate leaching liquid.According to
A specific example of the invention, the time that zinc sulfate leaching liquid is contacted with aluminium sheet can be 17.5h, zinc sulfate leaching liquid and aluminium
The catalytic temperature of plate can be preferably 50-70 DEG C, thus, it is possible to further increase while reaching significant defluorination effect
Production efficiency.
Another specific embodiment according to the present invention, the source of aluminium sheet are not particularly restricted, those skilled in the art
It can be selected according to actual needs, for example, specific example according to the present invention, aluminium sheet can be scrapped for electrodeposition treatment process
Aluminum cathode plate, the aluminum cathode plate that not only Zinc electrolysis process can be made to scrap as a result, is fully used, can also be into one
Step reduces fluorine removal cost.
According to an embodiment of the invention, inventors have found that fluorine ion can be enriched with and enter electricity in zinc wet smelting process
Product waste liquid, finally makes the content of fluoride ion in electrodeposition waste liquid exceeded, accelerates the corrosion rate of cathode plate, increases zinc metal sheet removing
Difficulty.For this purpose, can have been carried out at fluorine removal according to the identical fluorine removal mechanism of acid zinc sulfate leaching liquid to Zinc electrolysis waste liquid
Reason specifically with reference to Fig. 1, aluminium sheet can be hung into the liquid waste tank of the storage facility of Zinc electrolysis waste liquid while aluminium skimmings are added
It being impregnated, waste liquid flows through liquid waste tank and contacts the generation fluorination aluminum precipitation that reacts with the aluminium skimmings of the aluminium sheet of suspension and immersion,
To remove the F in Zinc electrolysis waste liquid-。
A specific embodiment according to the present invention, carrying out fluorine removal processing to Zinc electrolysis waste liquid can give up to Zinc electrolysis first
Aluminium skimmings are added in liquid while hanging aluminium sheet and are impregnated, waste liquid is made to contact realization with aluminium sheet and aluminium skimmings in liquid waste tank.Specifically
Ground can be added aluminium skimmings in Zinc electrolysis liquid waste tank and be impregnated, to dramatically increase contact of the Zinc electrolysis waste liquid with aluminium skimmings
Area, and then aluminium skimmings are improved to Zinc electrolysis waste liquid fluorine removing rate and defluorination effect；Aluminium sheet is further hung, aluminium sheet is hung on
The top of liquid waste tank is simultaneously protruded into Zinc electrolysis waste liquid.Thus, it is possible to further increase to the defluorination effect of liquid after Zinc electrolysis and
Fluorine removing rate, and then it is back to the introduction volume that fluorine ion can be further reduced when middle leaching processing and acidleach processing.
According to a particular embodiment of the invention, when into Zinc electrolysis waste liquid, addition aluminium skimmings are impregnated, the partial size of aluminium skimmings can
To be not more than 1cm, the volume ratio of aluminium skimmings and Zinc electrolysis waste liquid can be 0.4~0.6, for example, 0.4,0.45,0.5,0.55 or
0.6.Inventors have found that when aluminium skimmings partial size is excessive or with the volume ratio of Zinc electrolysis waste liquid it is too small when, aluminium skimmings and Zinc electrolysis waste liquid
Contact is not enough, and influences the reaction rate of aluminium skimmings Yu Zinc electrolysis waste liquid, so influence to the fluorine removing rate of Zinc electrolysis waste liquid and
Defluorination effect.1cm is not more than by the partial size of control aluminium skimmings as a result, the volume ratio of aluminium skimmings and Zinc electrolysis waste liquid is 0.4~0.6
When, it can be further improved the fluorine removing rate and defluorination effect to electrodeposition waste liquid.A specific example according to the present invention, aluminium skimmings
Partial size can be not more than 0.8cm, the volume ratio of aluminium skimmings and Zinc electrolysis waste liquid can be 0.5, thus, it is possible to Zinc electrolysis waste liquid
Reach more excellent fluorine removing rate and defluorination effect.
Another specific embodiment according to the present invention, time for being impregnated of aluminium skimmings is added into Zinc electrolysis waste liquid can be with
For 4~6h, such as 4h, 4.5h, 5h, 5.5h or 6h.Thus, it is possible to further increase on the basis of ensuring fluorine removing rate to zinc
The defluorination effect of electrodeposition waste liquid, to make liquid after impregnating that there is lower fluorinion concentration.Further, soaking temperature can be
30-40 DEG C, thus, it is possible to further increase the fluorine removing rate and defluorination effect to Zinc electrolysis waste liquid.One according to the present invention
Specific example, it can be 5h that the time that aluminium skimmings are impregnated is added into Zinc electrolysis waste liquid, and soaking temperature can be 30-40 DEG C,
Thus, it is possible to further increase production efficiency while reaching significant defluorination effect.
Another specific embodiment according to the present invention, when aluminium sheet being arranged in liquid waste tank, aluminium sheet immerses liquid after immersion
In surface area and immersion after the volume ratio of liquid can be not less than 30cm2/ L, such as 32cm2/L、35cm2/L、37cm2/L、
40cm2/ L etc..Thus, it is possible to further increase the defluorination effect and fluorine removing rate to liquid after immersion.It specifically, can in the present invention
To protrude into the length after impregnating in liquid by the number and aluminium sheet of control setting aluminium sheet, the table after making aluminium sheet immerse immersion in liquid
The volume ratio of liquid is not less than 30cm after area and immersion2/L。
Another specific embodiment according to the present invention, the time that Zinc electrolysis waste liquid is contacted with aluminium sheet can be 7~9h, example
Such as 7.5h, 8h, 8.5h or 9h.Thus, it is possible to be removed being significantly improved on the basis of ensuring production efficiency to Zinc electrolysis waste liquid
Fluorine effect, and further increase the removal efficiency of fluorine.Further, the reaction temperature that Zinc electrolysis waste liquid is contacted with aluminium sheet can be
20-28 DEG C, thus, it is possible to further increase the fluorine removing rate and defluorination effect to Zinc electrolysis waste liquid.One according to the present invention
Specific embodiment, the time that Zinc electrolysis waste liquid is contacted with aluminium sheet can be 8h, the reaction temperature that Zinc electrolysis waste liquid is contacted with aluminium sheet
It can be 25-28 DEG C, thus, it is possible to further increase production efficiency while reaching significant defluorination effect.
Another specific embodiment according to the present invention, can by aluminium sheet is hung and is immersed impregnate after realize in liquid and soak
Contact of the liquid with aluminium sheet after bubble specifically can make aluminium sheet hang on the top of liquid waste tank and protrude into after immersion in liquid.By
This, can not only make being immersed in be in contact in waste liquid pool with aluminium sheet and reacting for fluoride ion, and then achieve the purpose that fluorine removal, and
And by hanging on aluminium sheet in waste liquid pool, the aluminium sheet of suspension can also can effectively be avoided with long duration of action due to often more
Aluminium sheet is changed to cause cumbersome and then influence production efficiency and wasting manpower and material resources' resource.
Another specific embodiment according to the present invention, aluminium sheet can scrap cathode plate for what is generated during Zinc electrolysis,
Aluminium skimmings can scrap the clast that cathode plate or aluminum material generate for cutting and polishing, can not only make Zinc electrolysis mistake as a result,
The aluminum cathode plate that journey is scrapped is fully used, and fluorine removal cost can also be further decreased.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
Fluorine removal processing is carried out to acid zinc sulfate leaching liquid using aluminium sheet
Acid zinc sulfate leaching liquid is flowed through into concentration basin and carries out fluorine removal processing, during processing leaches acid zinc sulfate
Liquid is contacted with aluminium sheet, to generate fluorination aluminum precipitation.Wherein, chloride ion content is 1051.5mg/ in acid zinc sulfate leaching liquid
L, content of fluoride ion 126.3mg/L, sulfuric acid content 20g/L.Aluminium sheet immerses the surface area and sulphur in acid zinc sulfate leaching liquid
The volume ratio of sour zinc lixiviating solution is 10cm2/ L, the time that acid zinc sulfate leaching liquid is contacted with aluminium sheet are 17.5h, reaction temperature
It is 65 DEG C, the fluorinion concentration in concentrate is 108mg/L, carries out the fluorine removal of fluorine removal to acid zinc sulfate leaching liquid using aluminium sheet
Rate is 14.3%.
Embodiment 2
Fluorine removal processing is carried out to Zinc electrolysis waste liquid using aluminium skimmings and aluminium sheet.
The Zinc electrolysis waste liquid generated during Zinc electrolysis is passed through in liquid waste tank, into Zinc electrolysis waste liquid be added aluminium skimmings into
Row impregnates, while in liquid waste tank upper suspension aluminium sheet and immersing in Zinc electrolysis waste liquid and contact the generation that reacts with waste liquid and be fluorinated
Aluminum precipitation finally obtains fluorine removal waste liquid；Wherein, Cl in waste liquid-Content is 1200-1600mg/L, sulfuric acid content 150-180g/
L, the partial sizes of aluminium skimmings are 1cm, and the volume ratio of aluminium skimmings and electrodeposition waste liquid is 0.5, and the time of immersion is 5h, and soaking temperature is 35 DEG C；
The volume ratio of liquid is not less than 30cm after surface area and immersion after aluminium sheet immersion is impregnated in liquid2/ L, liquid is contacted with aluminium sheet after immersion
Time be 8h, reaction temperature be 25 DEG C.Table 1 be count 10 times using aluminium skimmings to Zinc electrolysis waste liquid progress fluorine removal before and after fluorine from
Sub- concentration results.
The concentration variation of fluorine ion before and after 1 Zinc electrolysis waste liquid fluorine removal of table
As can be seen from the table, fluorine removal processing, fluoride removing rate are carried out to Zinc electrolysis waste liquid by using aluminium skimmings and aluminium sheet
It can reach 39.8%；Content of fluoride ion is higher in Zinc electrolysis waste liquid, and the fluoride removing rate of fluorine removal processing is higher.
Embodiment 3
Fluorine removal processing is carried out to acidic zinc sulphate solution using aluminium sheet.
Fluorine-containing 224.1mg/L is taken, the acid zinc sulfate leaching liquid of chlorine 926.45mg/L, zinc 70.58g/L carry out at fluorine removal
Reason.It takes zinc sulfate leaching liquid 5L and is warming up to 40 DEG C, a certain amount of aluminium scrap plate, the surface area and sulphur of aluminium scrap plate are put into solution
The volume ratio of sour zinc lixiviating solution is 50cm2/ L, it is static to put 24 hours, make fluorine ion existing for the chloride ion under the conditions of with aluminium sheet
It sufficiently reacts, generates precipitating；It is filtered by vacuum filtration machine, filtrate volume 4.995L, fluorine-containing 80.67mg/L,
Zinc 70.49g/L, fluoride removing rate 64.04%, the loss late 0.23% of zinc.
The experimental results showed that carrying out fluorine removal processing not only without adding other medicaments to zinc sulfate leaching liquid using aluminium scrap plate
And auxiliary material, it only can be realized by contacting zinc sulfate leaching liquid with aluminium sheet, and defluorination effect is good, zinc almost free of losses.
Embodiment 4
Fluorine-containing 224.1mg/L is taken, the acid zinc sulfate leaching liquid of chlorine 926.45mg/L, zinc 70.58g/L carry out at fluorine removal
Reason.It takes zinc sulfate leaching liquid 5L and is warming up to 50 DEG C, a certain amount of aluminium scrap plate, the surface area and sulphur of aluminium scrap plate are put into solution
The volume ratio of sour zinc lixiviating solution is 50cm2/ L, it is static to put 24 hours, make fluorine ion existing for the chloride ion under the conditions of with aluminium sheet
It sufficiently reacts, generates precipitating；It is filtered by vacuum filtration machine, filtrate volume 4.990L, fluorine-containing 75.65mg/L,
Zinc 70.67g/L, fluoride removing rate 66.31%, the loss late 0% of zinc.
The experimental results showed that carrying out fluorine removal to zinc sulfate leaching liquid using aluminium scrap plate handles the free of losses of base metal zinc, rise
High-temperature can accelerate aluminium sheet to react, and promote defluorination effect.
Embodiment 5
Fluorine removal processing is carried out to acidic zinc sulphate solution using aluminium sheet.
Fluorine-containing 224.1mg/L is taken, the acid zinc sulfate leaching liquid of chlorine 1250.4mg/L, zinc 70.58g/L carry out at fluorine removal
Reason.It takes zinc sulfate leaching liquid 5L and is warming up to 50 DEG C, a certain amount of aluminium scrap plate, the surface area and sulphur of aluminium scrap plate are put into solution
The volume ratio of sour zinc lixiviating solution is 50cm2/ L, it is static to put 24 hours, make fluorine ion existing for the chloride ion under the conditions of with aluminium sheet
It sufficiently reacts, generates precipitating；It is filtered by vacuum filtration machine, filtrate volume 4.990L, fluorine-containing 67.8mg/L, zinc
70.67g/L, fluoride removing rate 69.74%, the loss late 0% of zinc.
The experimental results showed that carrying out fluorine removal to zinc sulfate leaching liquid using aluminium scrap plate handles the free of losses of base metal zinc, chlorine
Ion concentration raising is able to ascend defluorination effect.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (7)
1. a kind of method of fluorine removal in Zinc Hydrometallurgy Process characterized by comprising
It contacts the perchloric acid solution of zinc sulfate with aluminium sheet or aluminium skimmings to chemically react, so that the aluminum fluoride of generation sinks
Shallow lake is removed from solution, to reduce the content of fluoride ion in the perchloric acid solution of zinc sulfate.
2. the method according to claim 1, wherein chloride ion content is not in the perchloric acid solution of zinc sulfate
Lower than 900mg/L, content of fluoride ion is not less than 70mg/L.
3. the method according to claim 1, wherein chloride ion content is not in the perchloric acid solution of zinc sulfate
Lower than 1200mg/L, content of fluoride ion is not less than 70mg/L.
4. the method according to claim 1, wherein the perchloric acid solution of zinc sulfate is Zinc Hydrometallurgy Process
The acid zinc sulfate leaching liquid and/or Zinc electrolysis waste liquid of middle generation.
5. the method according to claim 1, wherein the aluminium sheet scraps cathode for what is generated during Zinc electrolysis
Plate, the aluminium skimmings are that the clast that cathode plate or aluminum material generate is scrapped described in cutting and polishing.
6. the method according to claim 1, wherein liquid storage of the chemical reaction in Zinc Hydrometallurgy Process
It deposits in equipment and carries out.
7. being refined the method according to claim 1, wherein the fluorination aluminum precipitation is removed from solution by wet process
Sedimentation and filter progress during zinc are completed.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453097A (en) * | 2019-09-17 | 2019-11-15 | 广东先导稀材股份有限公司 | A method of germanium is extracted in distillation from fluorine-containing germanium concentrate |
| CN110669933A (en) * | 2019-10-21 | 2020-01-10 | 金驰能源材料有限公司 | Method for removing fluorine in nickel-cobalt-manganese solution |
| CN114058871A (en) * | 2021-11-16 | 2022-02-18 | 安徽铜冠有色金属（池州）有限责任公司 | Method for removing F in zinc hydrometallurgy system by using spray iron deposition process-、Al3+Method (2) |
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|---|---|---|---|---|
| CN1966407A (en) * | 2005-11-17 | 2007-05-23 | 祥云县飞龙实业有限责任公司 | Fluorine-removing process for zinc sulphate solution |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966407A (en) * | 2005-11-17 | 2007-05-23 | 祥云县飞龙实业有限责任公司 | Fluorine-removing process for zinc sulphate solution |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453097A (en) * | 2019-09-17 | 2019-11-15 | 广东先导稀材股份有限公司 | A method of germanium is extracted in distillation from fluorine-containing germanium concentrate |
| CN110453097B (en) * | 2019-09-17 | 2021-12-17 | 广东先导稀材股份有限公司 | Method for distilling and extracting germanium from fluorine-containing germanium concentrate |
| CN110669933A (en) * | 2019-10-21 | 2020-01-10 | 金驰能源材料有限公司 | Method for removing fluorine in nickel-cobalt-manganese solution |
| CN114058871A (en) * | 2021-11-16 | 2022-02-18 | 安徽铜冠有色金属（池州）有限责任公司 | Method for removing F in zinc hydrometallurgy system by using spray iron deposition process-、Al3+Method (2) |
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