CN109621488A - A method of using ion chelating resin purification copper electrolyte - Google Patents
A method of using ion chelating resin purification copper electrolyte Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/014—Ion-exchange processes in general; Apparatus therefor in which the adsorbent properties of the ion-exchanger are involved, e.g. recovery of proteins or other high-molecular compounds
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Abstract
The present invention provides a kind of methods using ion chelating resin purification copper electrolyte, comprising: S1) by ion chelating ion exchange resin conversion be H+Type；The ion chelating resin is the sequestering ion exchange resin of phosphoramidic acid base using polystyrene as skeleton, maximal absorptive capacity >=20g/L of the ion chelating resin to antimony and bismuth；S2) the ion chelating resin by copper electrolyte after transition carries out impurity absorption, obtains removing impurities electrolyte；S3 it) is desorbed using ion chelating resin of the eluant, eluent hydrochloric acid to adsorbing contaminant, obtains desorption resin.In the present invention, the ion chelating resin is to maximal absorptive capacity >=20g/L of antimony and bismuth, and directional separation antimony bismuth rate is high and very stable, and the removal efficiency of antimony is up to 98%, the removal efficiency of bismuth does not influence the other compositions in electrolyte by selectivity desorption up to 97%.Entire operation process simple and effective of the present invention, continuous compact, adaptivity is strong, resin long service life used.
Description
Technical field
The invention belongs to copper electrolyzing refining technical fields more particularly to a kind of using ion chelating resin purification electrolyte
Method.
Background technique
In electrolytic refining course of copper, the electrolyte used is mainly the copper-bath containing free sulfuric acid, but is electrolysed
The chemical potentials of the impurity such as arsenic (As), antimony (Sb) and bismuth (Bi) in liquid and copper are very close to therefore influencing very the quality of electrolytic copper
Greatly, the open circuit of arsenic, antimony and bismuth becomes inevitable.Mainly there are revulsion directional separation antimony, bismuth at present, but this method power consumption is high, equipment
Investment is big, workshop land occupation is big, and production process generates toxic and harmful gas, and the miscellaneous black copper slag of height of generation has enough to meet the need in systems, handles
It is expensive.
For the method for some other purifying copper electrolyte also in attempting research, such as extraction usually uses organic extraction
It takes agent to separate and recover arsenic from copper electrolyte, but there are problems that subsequent organic phase processor is big, organic phase enters asking for electrolyte
Topic.Other continuous purification methods such as electrodeposition and eddy flow electrodeposition, are all the improvement of its revulsion, in itself the shortcomings that do not change
Become.
In recent years, the experimental study that arsenic in copper electrolyte, antimony, bismuth are adsorbed and removed using ion exchange resin is had been reported that.Shen
Please publication No. be 103539283 A of CN Chinese patent literature disclose it is a kind of removal copper electrolyte in antimony bismuth impurity synthesis
Processing method, this method sequentially includes the following steps: step 1, by the copper electrolyte discharged in tough cathode production process 40~65
Continuous ultrafiltration under conditions of DEG C, trapped fluid sedimentation, filters pressing, must remove the copper electrolyte of antimony bismuth solid phase；Setting at least two sets from
Sub- switch has the concatenated ion exchange column equipped with chelating resin of two columns in every set ion interchange unit, clear with acid water
Ion exchange column is washed until the pH value < 3 of its water outlet；Step 2: the copper electrolyte that antimony bismuth solid impurity is removed in step 1 is sent into
First set ion interchange unit after being cleaned with acid water consolidates removal antimony bismuth when the impurity ion content of its water outlet is exceeded
The copper electrolyte of body impurity enters second set of ion interchange unit by same flow velocity, continues with removal antimony bismuth solid impurity
Copper electrolyte；Step 3, by cleaning chelating resin, desorption or regeneration chelating resin, desorption or regeneration after clean chelating resin it is suitable
Sequence handles the ion interchange unit；The pH value for the solution that the waste water containing EDTA of step 4, adjusting waste regeneration liquid and concentration is formed,
EDTA regeneration becomes EDETATE SODIUM salt.
The above method includes the experimental procedure of ion exchange, good separating effect, but ion exchange resin and eluant, eluent used
Have an impact to electrolyte into system, is unfavorable for industrial application.
Summary of the invention
In view of this, the application provides a kind of method using ion chelating resin purification copper electrolyte, the application method
Impurity in electrolyte can effectively be removed, and remove front and back electrolyte effective component will not significant change, after being conducive to
Continuous system production.
The present invention provides a kind of method using ion chelating resin purification copper electrolyte, comprising the following steps:
It S1 is) H by ion chelating ion exchange resin conversion+Type；
The ion chelating resin is the sequestering ion exchange resin of phosphoramidic acid base using polystyrene as skeleton, described
Maximal absorptive capacity >=20g/L of the ion chelating resin to antimony and bismuth；
S2) the ion chelating resin by copper electrolyte after transition carries out impurity absorption, obtains removing impurities electrolyte；
S3 it) is desorbed using ion chelating resin of the eluant, eluent hydrochloric acid to adsorbing contaminant, obtains desorption resin.
Preferably, step S1) specifically: ion chelating resin is first rinsed with water, then rinses sulfuric acid and is transformed into H+Type.
Preferably, step S1) in, by ion chelating resin according to resin volume ratio 3~5Bv flushing water, then rinse 2~
20% sulfuric acid of 4Bv is transformed into H+Type.
Preferably, step S2) in, ion chelating resin after the transition to copper electrolyte according to not less than 2Bv/h into
Row impurity absorption.
Preferably, step S2) in, impurity absorption terminates, Sb < 10mg/L in gained removing impurities electrolyte, and Bi < 15mg/
L。
Preferably, step S3) in, the eluant, eluent is the hydrochloric acid of 1~5mol/L.
Preferably, step S3) in, it is desorbed using eluant, eluent according to 2~5Bv/h, respectively obtains desorption resin and wash
Liquid is taken off, antimony and bi content are all larger than 20g/L in the eluent.
Preferably, step S3) after further include: S4) by the desorption resin dechlorination, loop cycle uses.
Preferably, step S4) specifically: the desorption resin is first rinsed with water, then rinses sulfuric acid and carries out dechlorination, period
It is recycled.
Compared with prior art, the present invention uses the sequestering amberlite of phosphoramidic acid base using polystyrene as skeleton
Rouge, orientation carries out absorption exchange to the high-valency metal in copper electrolyte after transition, obtains removing impurities electrolyte；It is subsequent to reach saturation
When, antimony can be desorbed by concentrated hydrochloric acid, and be stabilized antimony in eluent, to antimony successfully is desorbed, weight
The ion chelating resin is utilized again.In the present invention, the coordination combining form of the ion chelating resin and heavy metal ion is
With the coordinate bond that the O atom on N atom and phosphoric acid hydroxyl forms, to maximal absorptive capacity >=20g/L of antimony and bismuth, directional separation antimony
Bismuth rate is high and very stable, and the removal efficiency of antimony is up to 98%, and the removal efficiency of bismuth is up to 97%, by selectivity desorption to electrolyte
In other compositions do not influence.Entire operation process simple and effective of the present invention, continuous compact, adaptivity is strong, resin used
The problem of long service life to the directional separation of antimony bismuth and elute, and antimony bismuth impurity difficulty separates in very good solution electrolyte.
Detailed description of the invention
Fig. 1 is the process flow diagram of purifying copper electrolyte provided in an embodiment of the present invention.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of methods using ion chelating resin purification copper electrolyte, comprising the following steps:
It S1 is) H by ion chelating ion exchange resin conversion+Type；
The ion chelating resin is the sequestering ion exchange resin of phosphoramidic acid base using polystyrene as skeleton, described
Maximal absorptive capacity >=20g/L of the ion chelating resin to antimony and bismuth；
S2) the ion chelating resin by copper electrolyte after transition carries out impurity absorption, obtains removing impurities electrolyte；
S3 it) is desorbed using ion chelating resin of the eluant, eluent hydrochloric acid to adsorbing contaminant, obtains desorption resin.
Method provided by the present application can effectively remove the impurity in electrolyte, and it is effective to remove front and back electrolyte
Ingredient will not significant change, be conducive to follow-up system produce.
Referring to Fig. 1, Fig. 1 is the process flow diagram of purifying copper electrolyte provided in an embodiment of the present invention.The present invention is real
Electrolyte directional separation antimony and bismuth technique disclosed in example are applied, resin used is polystyrene-based ion chelating resin.Also, institute
Stating ion chelating resin is the sequestering ion exchange resin of phosphoramidic acid base by particular polymeric, is inhaled to antimony and the maximum of bismuth
Attached amount >=20g/L has significant removing effect to antimony, the bismuth in electrolyte.
In a specific embodiment of the present invention, the ion chelating resin can be commercial resins, may also pass through special conjunction
It is obtained at processing；For such resin component based on amino phosphorous acid, skeleton is polystyrene.The ion chelating resin
It is reacted by primary amine ball, formaldehyde, phosphorous acid and hydrochloric acid；In synthesis process, the amount of hydrochloric acid is increased, when hydrochloric acid is more, primary amine
Ball is shunk, and carboxylation reaction can occur to avoid the primary amine ball in synthesis and formaldehyde.If hydrochloric acid content is few, primary amine ball and formaldehyde hold
Side reaction easily occurs, causes the hydrogen on skeleton styrene to be refined by the side reaction of formaldehyde, the resolving hydrochloric acid finally used in resin
In the process, the alcohol-OH of the side reaction can be replaced by the Cl of hydrochloric acid, and chlorine is caused to remain on resin.When resin adsorption electrolyte,
Chlorine can be substituted out by certain anion therein, this reaction occurs again when resolving hydrochloric acid, and the chlorine in final electrolyte is continuous
Rise, destroys whole system.
The embodiment of the present invention, which passes through to handle above in the resin of synthesis, avoids the generation of some side reactions, and then after avoiding
The problem of continuous resolving hydrochloric acid, occurs.Ion chelating resin of the present invention has stronger adsorption capacity, the parsing to hydrochloric acid
It is adaptable.Specifically, the granularity of the ion chelating resin is 520 μm~620 μm, and density can be 1.2g/L；Weight in wet base
For 730~770g/L.
The ion chelating resin is generally Na+Type；The ion exchange resin conversion is first H with transition agent by the embodiment of the present invention+
Type.The transition agent is usually water and the sulfuric acid greater than 10%, such as 15~20% (mass concentration)；Specifically: column will be filled
Ion chelating resin is first rinsed with water, then is rinsed sulfuric acid and be transformed into H+Type.The ion exchange resin conversion is resin pre-processing, this hair
Resin pre-processing described in bright embodiment is needed according to resin volume ratio 3~5Bv flushing water, then rinses 20% sulphur of 2~4Bv
Acid is transformed into H+Type.
Copper electrolyte is carried out resin and orients removing impurities, that is, the ion by electrolyte after transition by the embodiment of the present invention
Chelating resin carries out impurity absorption, obtains removing impurities electrolyte.
The present invention does not have particular/special requirement to the sour dense, copper content and other impurities content of the copper electrolyte, especially right
The content of Sb, Bi do not have particular/special requirement.The method of the present invention adaptivity is strong, for the electrolyte directional separation of different impurities concentration
Antimony bismuth can effectively realize purification purpose by controlling relevant parameter.In an embodiment of the present invention, after the transition
When resin carries out impurity absorption to copper electrolyte, N and O atom in resin can form coordinate bond with Sb, Bi, actually should be
To SbO2+、SbO+、BiO2+、BiO+The coordinate bond of equal formation, and to Cu2+Do not play suction-operated.
Specifically, the ion chelating resin after the transition is according to the content of antimony bismuth impurity in copper electrolyte according to being not less than
2Bv/h carries out adsorption operation, and the removing impurities electrolyte after absorption can return to electrolysis system.The embodiment of the present invention is arrived when resin adsorption
It can stop operation when 25Bv or more；Impurity absorption terminates, gained removing impurities electrolyte impurity content Sb < 10mg/L, and Bi < 15mg/
L。
The embodiment of the present invention elutes resin using eluant, eluent hydrochloric acid, and impurity is desorbed, and obtains desorption resin.Wherein,
The eluant, eluent is preferably the hydrochloric acid of 1~5mol/L.The embodiment of the present invention after absorption, be rinsed with water resin to neutrality,
1~5mol/L the hydrochloric acid prepared can carry out elution operation according to 2~5Bv/h.According to conventional art, resin of the invention is at
In elution operation after reason, the efficiency of lower eluant strength and higher elution impurity can adapt to.Wherein, due to from
The parsing of 1Bv to 5Bv has sequencing, and as major part impurity early period is eluted, the antimony bi concns of eluent are gradually lowered,
Therefore the hydrochloric acid of parsing needs classification to handle, and realizes reuse, and eluent antimony and bi concns are greater than at the direct outlet of 20g/L in the process
Reason, the circulator that the eluent less than 20g/L enters continues next round elution and uses, when antimony and bismuth contain in obtained elution end liquid
When amount is respectively less than 1g/L, elution is completed.
The application uses hydrochloric acid as eluant, eluent, can be good at that the impurity for introducing sodium is avoided to cause electrolyte component by shadow
It rings.Desorbed solution in the application after described resolving hydrochloric acid, can be recycled, parse the higher antimony of content in electrolyte
20g/L or more is enriched in liquid, subsequent desorbed solution is replaced using iron powder is enriched with valuable metal, and the processing of hydrochloric acid outlet is
It can.
Resin after the elution can be rinsed dechlorination using antichlor by the present invention, carry out next round absorption, recycling.
Wherein, the antichlor is usually water and the sulfuric acid greater than 10%, such as 15~20% (mass concentration)；Specifically: it will be described
Desorption resin is first rinsed with water, then is rinsed sulfuric acid and carried out dechlorination, and loop cycle uses.Desorption resin described in the embodiment of the present invention
3~5Bv water is rinsed, 20% sulfuric acid for rinsing 2~4Bv carries out dechlorination, so completes one cycle operation.Institute of the embodiment of the present invention
The above each step operation stated does not specially require temperature, and environment and liquid temperature are lower than 80 DEG C.
Present invention elution thoroughly, by the particular polymeric and antichlor of resin avoids the chlorine of hydrochloric acid elution to electrolyte
Interference.In addition, obtained eluent is able to carry out valuable metal recovery.For example, eluent alkali neutralization to PH=1~2,
After diluting 10Bv by iron replacement or water, valuable metal antimony and bismuth etc. are recycled.
The present invention takes full advantage of the low cost, high efficiency and reusing of ion chelating resin, carries out electrolyte
Directional separation antimony bismuth, electrolyte impurity-removing rate is high, and the removal efficiency of antimony is up to 98%, and the removal efficiency of bismuth is up to 97%.The present invention is adaptive
Ying Xingqiang, resin life used up to 2 years, recycling 600 times or more.Resin stability used herein is good, when long
Between there is no larger change to its removing impurities performance after use, the new resin of a part is replaced after being crushed to be continued to use.In addition, should
The complete equipment occupied area that resin uses is small, and equipment investment is small, is easy to implement, at low cost.
The present invention uses antichlor for the first time, is effectively taken off in such a way that competitive advantage combines to elution resin
Chlorine processing solves the problems, such as the chlorine evil of resin removing impurities.Present invention process increases small investment, and labor intensity is small, environmentally friendly, institute
The eluent obtained can distill hydrochloric acid recycling, be discharged into wastewater treatment after can also recycling valuable metal, and environmental pollution is small, increase
Add added benefit.Whole process simple process of the present invention easily realizes industrialization.
For a further understanding of the application, ion chelating resin purification is used to provided by the present application below with reference to embodiment
The method of copper electrolyte is specifically described.
In following embodiment, elemental composition detection is carried out according to conventional method in that art.The ion chelating resin by
Primary amine ball, formaldehyde, phosphorous acid and hydrochloric acid react；In synthesis process, the amount of hydrochloric acid is increased, primary amine ball: hydrochloric acid: phosphorous
Acid: 90 DEG C of reaction temperature, primary amine ball, phosphorous acid solution, hydrochloric acid is added in formaldehyde=1:2:2:2 (molar ratio) in the reaction vessel,
Formalin is added dropwise after heating, reacts 8 hours, after completion of the reaction plus alkali removes extra phosphorous acid, and gained resin is protected after filtering
It deposits stand-by；The granularity of the resin is 520 μm~620 μm, density 1.2g/L, and weight in wet base is 730~770g/L, most to antimony and bismuth
Big adsorbance is 20g/L.
Embodiment 1
Firstly, 150L ion chelating resin to be carried out to the dress column of early period, according to resin volume ratio 3~5Bv flushing water, then rush
20% sulfuric acid for washing 2Bv is transformed into H+Type.Then, the resin by electrolyte after transition carries out resin orientation point with 4Bv/h
From antimony bismuth, gained removing impurities electrolyte 1 returns electrolysis system.It stops operation when resin adsorption is to 33Bv, is rinsed with water resin in
Property, elution operation is carried out according to 2~5Bv with the hydrochloric acid of 2N, since the parsing from 1Bv to 5Bv has sequencing, as early period is big
Partial impurities are eluted, and the antimony bi concns of eluent are gradually lowered, therefore the hydrochloric acid parsed needs classification to handle, and realizes back
With eluent antimony and bi concns are greater than the direct outlet processing of 20g/L in the process, and the eluent less than 20g/L enters circulator
Continue next round elution to use, when antimony and bi content are respectively less than 1g/L in obtained elution end liquid, elution is completed, and is made even at this time
Equal sample is eluent 1.Resin after elution rinses 3~5Bv water, and 20% sulfuric acid for rinsing 2~4Bv carries out dechlorination, then carries out down
One wheel absorption.
Third round absorb-elute is completed according to above step.It can carry out more frequently adsorbing to parse in the above manner inhaling again
It is attached to parse again, realize the sharpest edges in absorption and the time eluted, cost.
Directional separation antimony bismuth situation see the table below:
3 wheel circulation directional separation antimony bismuth situation in 1 embodiment 1 of table
Result above can be seen that, respectively reach 95.87% and 89.03%, removing effect to the removal efficiency highest of low miscellaneous low copper
Rate is high.
Subsequent outlet eluent is added iron powder and restores to antimony bismuth according to 1.2 times of antimony bismuth theoretical amount, obtains thick
Antimony can effectively recycle valuable metal.
Embodiment 2
Firstly, 160L ion chelating resin to be carried out to the dress column of early period, according to resin volume ratio 3~5Bv flushing water, then rush
20% sulfuric acid for washing 2Bv is transformed into H+Type.Then, the resin by electrolyte after transition carries out resin orientation point with 2Bv/h
From antimony bismuth, gained removing impurities electrolyte 1 returns electrolysis system, stops operation when resin adsorption is to 31Bv, is rinsed with water resin in
Property, elution operation is carried out according to 2~5Bv with the hydrochloric acid of 2.5N, since the parsing from 1Bv to 5Bv has sequencing, with early period
Most of impurity is eluted, and the antimony bi concns of eluent are gradually lowered, therefore the hydrochloric acid parsed needs classification to handle, and realizes back
With eluent antimony and bi concns are greater than the direct outlet processing of 20g/L in the process, and the eluent less than 20g/L enters circulator
Continue next round elution to use, when antimony and bi content are respectively less than 1g/L in obtained elution end liquid, elution is completed, and is made even at this time
Equal sample is eluent 1.Resin after elution rinses 3~5Bv water, and 20% sulfuric acid for rinsing 2~4Bv carries out dechlorination, then carries out down
One wheel absorption.
Next round elution antimony bismuth is consistent with the first round, and only the eluent epicycle of the first round non-outlet continues according to successively suitable
Sequence continues to use, and the hydrochloric acid of 2N is supplemented on the basis of subsequent, and eluent impurity early period is greater than the outlet of 20g/L, is less than 20g/L
Eluent enter circulator continue next round elution use, when antimony and bi content are respectively less than 1g/L in obtained elution end liquid
When, elution is completed, and taking average sample at this time is eluent 2.Resin after elution rinses 3~5Bv water, rinses 20% sulphur of 2~4Bv
Acid carries out dechlorination, then carries out next round absorption.
Third round absorb-elute is completed according to above step.It can carry out more frequently adsorbing to parse in the above manner inhaling again
It is attached to parse again, realize the sharpest edges in absorption and the time eluted, cost.
Directional separation antimony bismuth situation see the table below:
3 wheel circulation directional separation antimony bismuth situation in 2 embodiment 2 of table
Result above can be seen that, respectively reach 97.08% and 95.79%, removal efficiency to the rate highest of removing of high miscellaneous low copper
It is still higher.
Subsequent outlet eluent is added iron powder and restores to antimony bismuth according to 1.2 times of antimony bismuth theoretical amount, obtains thick
Antimony can effectively recycle valuable metal.
Embodiment 3
Firstly, 200L ion chelating resin to be carried out to the dress column of early period, according to resin volume ratio 3~5Bv flushing water, then rush
20% sulfuric acid for washing 2~4Bv is transformed into H+Type.Then, it is fixed to carry out resin with 2Bv/h for the resin by electrolyte after transition
To separation antimony bismuth, gained removing impurities electrolyte 1 returns electrolysis system.It stops operation when resin adsorption is to 25Bv, is rinsed with water resin
To neutrality, elution operation is carried out according to 2~5Bv with the hydrochloric acid of 3N, since the parsing from 1Bv to 5Bv has sequencing, with preceding
Phase major part impurity is eluted, and the antimony bi concns of eluent are gradually lowered, therefore the hydrochloric acid parsed needs classification to handle, and is realized
Reuse, eluent antimony and bi concns are greater than the direct outlet processing of 20g/L in the process, and the eluent less than 20g/L enters circulation dress
It sets and continues next round elution use, when antimony and bi content are respectively less than 1g/L in obtained elution end liquid, elution is completed, and is taken at this time
Average sample is eluent 1.Resin after elution rinses 3~5Bv water, and 20% sulfuric acid for rinsing 2~4Bv carries out dechlorination, then carries out
Next round absorption.
Next round elution antimony bismuth is consistent with the first round, and only the eluent epicycle of the first round non-outlet continues according to successively suitable
Sequence continues to use, and the hydrochloric acid of 2N is supplemented on the basis of subsequent, and eluent impurity early period is greater than the outlet of 20g/L, is less than 20g/L
Eluent enter circulator continue next round elution use, when antimony and bi content are respectively less than 1g/L in obtained elution end liquid
When, elution is completed, and taking average sample at this time is eluent 2.Resin after elution rinses 3~5Bv water, rinses 20% sulphur of 2~4Bv
Acid carries out dechlorination, then carries out next round absorption.
Third round absorb-elute is completed according to above step.It can carry out more frequently adsorbing to parse in the above manner inhaling again
It is attached to parse again, realize the sharpest edges in absorption and the time eluted, cost.
Directional separation antimony bismuth situation see the table below:
3 wheel circulation directional separation antimony bismuth situation in 3 embodiment 3 of table
Result above can be seen that, respectively reach 98.24% and 97.09%, removing effect to the removal efficiency highest of high miscellaneous high-copper
Rate is higher.
Subsequent eluent is added iron powder and restores to antimony bismuth, obtain needle antimony, energy according to 1.2 times of antimony bismuth theoretical amount
It is enough that valuable metal is effectively recycled.
Above embodiments have all done the repeated experiment up to half a year, and number of repetition is more than 600 times, experiment effect and implementation
Example is consistent, being capable of stable operation.
Comparative example
In order to more preferably verify the effect after resin specially treated, by untreated phosphoramidic acid base chelating resin (by primary
Amine ball, formaldehyde, phosphorous acid and hydrochloric acid react；In synthesis process, primary amine ball: hydrochloric acid: phosphorous acid: formaldehyde=1:1:2:2 (rubs
That ratio), 90 DEG C of reaction temperature, primary amine ball, phosphorous acid solution, hydrochloric acid are added in the reaction vessel, formalin is added dropwise after heating,
Reaction 8 hours, after completion of the reaction plus alkali removes extra phosphorous acid, and gained resin saves stand-by after filtering) comparative test.The tree
Fat granule degree is 340 μm~1560 μm, and coefficient of uniformity is poor, density 1.4g/L, and the maximal absorptive capacity to antimony and bismuth is 7g/L.
Firstly, the untreated phosphoramidic acid base resin of 200L to be carried out to the dress column of early period, according to resin volume ratio 3~
5Bv flushing water, then rinse 20% sulfuric acid of 2Bv and be transformed into H+Type.Then, the resin by electrolyte after transition, with 2Bv/h
Resin directional separation antimony bismuth is carried out, gained removing impurities electrolyte 1 returns electrolysis system.It stops operation, uses when resin adsorption is to 25Bv
Water rinse resin carries out elution operation with 2~5Bv of hydrochloric acid of 3N to neutrality, and when hydrochloric acid uses 5Bv, elution is completed.After elution
Resin rinse 3~5Bv water, 20% sulfuric acid for rinsing 2~4Bv carries out dechlorination, then carries out next round absorption, is so repeated 2 times.
It when being eluted after the second wheel absorption, is parsed, is operated and above consistent using the hydrochloric acid of 6N.
Third round repeats the second wheel test.
Directional separation antimony bismuth situation see the table below:
3 wheel circulation directional separation antimony bismuth situation in 4 comparative example of table
Result above can be seen that untreated resin impurity removal effect is poor, the removing highest 49.85% of Sb, Cl-
Reach 2962.63mg/L.If guaranteeing removal efficiency, increase the adsorbance of single, parsing and the regeneration frequency increase, removal efficiency
It reduces obvious.In addition, being increased obviously by the chloride ion that the subsequent electrolyte of resolving hydrochloric acid is handled, system balancing is destroyed.
By comparative test, comparative resin need high concentration of hydrochloric acid could elution effect to impurity it is preferable, Cai Nengrang
Subsequent repetition absorption goes on.
If handled with EDTA, agent and piece alkali somewhat expensive are parsed, because adsorption capacity is poor, repeatedly parsing, regeneration, are produced
Raw wastewater flow rate is big, also, all can have the residual of EDTA to be mixed into waste water and in electrolyte, and waste water is difficult, and system is impacted.
As seen from the above embodiment, the present invention effectively removes the impurity in electrolyte, and directional separation antimony bismuth rate is high
And very stable, up to 98%, the removal efficiency of bismuth is desorbed by selectivity in electrolyte the removal efficiency of antimony up to 97%
Other compositions do not influence.Entire operation process simple and effective of the present invention, continuous compact, adaptivity is strong, and resin used uses
Service life is long, environmentally friendly.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (9)
1. a kind of method using ion chelating resin purification copper electrolyte, comprising the following steps:
It S1 is) H by ion chelating ion exchange resin conversion+Type；
The ion chelating resin is the sequestering ion exchange resin of phosphoramidic acid base using polystyrene as skeleton, the ion
Maximal absorptive capacity >=20g/L of the chelating resin to antimony and bismuth；
S2) the ion chelating resin by copper electrolyte after transition carries out impurity absorption, obtains removing impurities electrolyte；
S3 it) is desorbed using ion chelating resin of the eluant, eluent hydrochloric acid to adsorbing contaminant, obtains desorption resin.
2. the method according to claim 1, wherein step S1) specifically: ion chelating resin is first rushed with water
It washes, then rinses sulfuric acid and be transformed into H+Type.
3. according to the method described in claim 2, it is characterized in that, step S1) in, by ion chelating resin according to resin volume
Than 3~5Bv flushing water, then rinses 20% sulfuric acid of 2~4Bv and be transformed into H+Type.
4. the method according to claim 1, wherein step S2) in, the ion chelating resin pair after the transition
Copper electrolyte carries out impurity absorption according to not less than 2Bv/h.
5. according to the method described in claim 4, it is characterized in that, step S2) in, impurity absorption terminates, the electrolysis of gained removing impurities
Sb < 10mg/L in liquid, and Bi < 15mg/L.
6. the method according to claim 1, wherein step S3) in, the eluant, eluent is the salt of 1~5mol/L
Acid.
7. according to the method described in claim 6, it is characterized in that, step S3) in, it is carried out using eluant, eluent according to 2~5Bv/h
Desorption respectively obtains desorption resin and eluent, and antimony and bi content are all larger than 20g/L in the eluent.
8. method according to any one of claims 1 to 7, which is characterized in that step S3) after further include: S4) by institute
Desorption resin dechlorination is stated, loop cycle uses.
9. according to the method described in claim 8, it is characterized in that, step S4) specifically: the desorption resin is first rushed with water
It washes, then rinses sulfuric acid and carry out dechlorination, loop cycle uses.
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