CN102643990A - Method for removing trace Cu in high-purity Ni by chelate resin - Google Patents
Method for removing trace Cu in high-purity Ni by chelate resin Download PDFInfo
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- CN102643990A CN102643990A CN2012101578895A CN201210157889A CN102643990A CN 102643990 A CN102643990 A CN 102643990A CN 2012101578895 A CN2012101578895 A CN 2012101578895A CN 201210157889 A CN201210157889 A CN 201210157889A CN 102643990 A CN102643990 A CN 102643990A
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- copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for removing trace Cu in high-purity Ni by chelate resin. The method comprises the steps of: pretreating anolyte obtained by electrolyzing nickel sulfide to remove impurities including Fe, Co, Zn, Pb and the like so as to obtain 3N Ni electrolyte containing trace impurity Cu; pumping the 3N Ni electrolyte into an adsorption tower filled with the chelate resin so as to obtain a Ni solution with the purity higher than 5N and 4N; and after the adsorption tower reaches a leakage point, stopping water supply, and carrying out regeneration treatment by a regenerant, wherein the regeneration rate approximately equals to 100%.The method can be used for removing trace Cu in high-purity Ni, thus the purity of Ni is increased by more than one order of magnitude in high efficiency and low consumption, and other impurities are not introduced, and secondary pollution is not caused. The method disclosed by the invention has remarkable economic benefit and wide application prospect.
Description
Technical field
The 3N nickel electrolyte that the present invention relates to contain trace impurity copper is removed the method for trace copper, is specifically related to the method that a kind of resin is removed trace copper in the high purity nickel.
Background technology
High purity nickel has extremely strong erosion resistance and physical strength, and plasticity is good and can form alloy with multiple metal; What is more important; The polishing performance of high purity nickel is fabulous; Can be used for also can be used as high-temperature structural material and being used for rocketry in large-scale integrated circuit and wiring material, magnetic membrane material and the modern high technologies such as special package material, radar and nuclear industry and Long-distance Control.Therefore, high purity nickel is the grand strategy resource of science and techniques of defence.
High purity nickel is very strict to the content requirement of other heavy metal elements, particularly copper.How from the nickel of high density, to remove trace copper, become the key link that promotes the high purity nickel quality.Copper removal has several methods such as the precipitator method, solvent extration, electrochemical process and ion-exchange-resin process in the high purity nickel at present.Have copper ashes after the precipitator method are handled and produce, although copper ashes can be used as the copper ore concentrates copper smelting, copper nickel mass ratio wherein requires very high (Cu/Ni >=15), therefore handles cumbersome.Solvent extration, electrochemical process and ion-exchange-resin process all can address this problem, and realize no scorification.But solvability is limited in the extraction agent water of solvent extration, so there is emulsion often in extraction, can organic substance be brought in the solution, need add that operation behind the organism place to go could guarantee the purity of output high purity nickel, has increased processing cost.And electrochemical process generally is applicable to content of copper ion condition with higher in the solution, can't accomplish degree of depth copper removal, has limited the high purity nickel purity that makes.Advantages such as ion-exchange-resin process has overcome above shortcoming, has the clearance height, and regeneration back is reusable and receiving much concern.This wherein, resin is stronger because of the binding ability of itself and metal, selectivity is better and in the high purity nickel preparation, have a extensive future.
China's application number is that the patent document of CN200910242127.3 discloses a kind of method that adopts the chelating resin associated treatment to remove heavy metal ion; File is mentioned the chelating resin selectivity copper removal/nickel divalent-metal ion that can adopt after the chemically modified; But its effect is collaborative two kinds of metals (nickel and copper) ion of removing; Can't accomplish selective removal trace copper in high concentration of nickel solution, be not suitable for being used in the high purity nickel preparation.Simultaneously also there is same problem in one Chinese patent application number for the patent of CN00812095.1; Removal effect to metallic cation in the liquid is fine; But the selective difference (like nickel and copper) for metallic cation can not well embody, and therefore is not suitable for from high purity nickel, removing trace copper equally.
Summary of the invention
1. the present invention's technical problem that will solve
Deficiency to copper-removing method in the above-mentioned high purity nickel; Especially resin is removed the defective workmanship of copper; Be problems such as selectivity is not good; The invention provides a kind of resin and remove the method for trace copper in the high purity nickel; Particularly, be meant and utilize highly selective resin
to remove trace copper in the nickel electrolyte, thereby obtain the very low high purity nickel solution of foreign matter content.
2. technical scheme
Inventive principle: resin choice property can use selectivity coefficient
to represent, concrete calculation formula is following:
Wherein, C
eThe equilibrium concentration of expression metals ion in solution, Q
eThe equilibrium concentration of expression metals ion in resin.
value is big more, and resin is just good more to the selectivity of metals ion 1.Usually it is very good to the selectivity of metals ion 1 that
value surpasses 1000 explanation resins.
Technical scheme of the present invention is following:
A kind of resin is removed the method for trace copper in the high purity nickel, the steps include:
(1) purity that contains trace impurity copper that obtains behind the impurity such as iron, cobalt, zinc and lead being removed in the electrolytic anolyte pre-treatment of nickelous sulfide is the adsorption tower that 3N (99.9%) nickel electrolyte pumps into the filling resin; Regulate control adsorption temp and absorption flow velocity, collecting and obtaining purity is the nickel solution that 5N (99.999%) is above and 4N (99.99%) is above;
(2) after adsorption tower reaches leakage point, stop into water, with regenerator the resin in the step (1) is carried out manipulation of regeneration, the resin after the regeneration is washed till neutrality with clear water, reuses again.
The D403 resin that the Amberlite IRC-748 that resin described in the step (1) is the Amberlite IRC-747 that produces of U.S. Rohm&Haas company, U.S. Rohm&Haas company produces, the Purolite S950 that Britain Purolite company produces, Purolite S910 resin that Britain Purolite company produces or Shanghai Hua Shen resin processing plant produce, its preferably in high concentration of nickel solution to very the Amberlite IRC-748 or the Amberlite IRC-747 resin of highly selective
are arranged.
In the step (1), adsorption temp is 5-50 ℃, and the absorption flow velocity is 5-30 BV/h.
In the step (1), through the water outlet in 200-3500 BV (BV the is the resin bed volume) scope before collecting, obtaining purity is the above nickel solution of 5N (99.999%); The water outlet in the 1100-4600 BV scope is collected in the back, and obtaining purity is the above nickel solution of 4N (99.99%).
In the step (2), used regenerator is weight percentage and is the HCl solution of 5-25%, and regeneration temperature is 5-50 ℃, and regeneration velocity is 5-30 BV/h.
3. beneficial effect
The invention discloses a kind of resin and remove the method for trace copper in the high purity nickel; The resin
to copper very highly selective need not to regulate the nickel electrolyte original ph in the high concentration of nickel solution through being chosen in; After containing the nickel electrolyte of trace copper through present method art breading simultaneously, but efficient low-consume obtain purity be 4N (99.99%) above with other high purity nickel solution of 5N (99.999%) higher level, and handle the no copper ashes generation in back; Realize degree of depth copper removal; Simultaneously do not bring other impurity into, do not produce secondary pollution, remarkable in economical benefits; Environmental friendliness has broad application prospects.
Embodiment
Below further specify the present invention through embodiment.
Embodiment 1
Take by weighing 5 kinds of resins of 0.5 g (Amberlite IRC-747, Amberlite IRC-748, Purolite S950, Purolite S910 and D403) respectively in 1.0 L Erlenmeyer flasks; Add 0.5 L mixing solutions, Cu in the mixing solutions (II) and Ni (II) starting point concentration are respectively 0.04 mmol/L and 5 mmol/L.Place constant temperature oscillator, make absorption reach balance, calculate 5 kinds of resin choice property coefficients with speed oscillation 24 h of 120 r/min.
Table 1 Choice of Resin property coefficient
Embodiment 2
The copper bearing nickel electrolyte of 3N (99.9%) that will contain trace copper under the absorption flow velocity of 30 BV/h through the glass adsorption column (adsorption tower) of 1 mLAmberlite IRC-748 resin is housed; Adsorption temp is controlled at 20 ℃; Through the water outlet in the 200-3500BV scope before collecting, obtaining purity is the above nickel solution of 5N (99.999%); The water outlet in the 1100-4600 BV scope is collected in the back, and obtaining purity is the above nickel solution of 4N (99.99%).Using weight percent is that 15% the HCl solution Amberlite IRC-748 after to absorption regenerates, and regeneration temperature is 20 ℃, and regeneration velocity is 10 BV/h.Resin after the regeneration is washed till neutrality with clear water, and is reusable.
Embodiment 3
Adsorption temp is controlled at 5 ℃, and the absorption flow velocity is 10 BV/h, and regeneration temperature is 50 ℃, and other parameters are with embodiment 2.
Embodiment 4
The absorption flow velocity is 5 BV/h, and adsorption temp is controlled at 20 ℃, and regeneration temperature is 20 ℃, and other parameters are with embodiment 2.
Embodiment 5
Adsorption temp is controlled at 50 ℃, be weight percentage 25% HCl solution of regenerated liquid, and regeneration velocity is that 5 BV/h regeneration temperatures are 5 ℃.Other parameters are with embodiment 4.
Embodiment 6
Be weight percentage 5% HCl solution of regenerated liquid, regeneration velocity is 30 BV/h.Other parameters are with embodiment 4.
Embodiment 7
Adopt Amberlite IRC-747 resin.Other parameters are with embodiment 4.
Embodiment 8
Adopt homemade D403 resin.Other parameters are with embodiment 4.
Embodiment 9
Adopt Purolite S950 resin, other parameters are with embodiment 4.
Embodiment 10
Adopt Purolite S910 resin, other parameters are with embodiment 4.
In embodiment 2-10, it is as shown in table 2 that each embodiment high purity nickel prepares the result.
Table 2 high purity nickel prepares the result
Claims (7)
1. a resin is removed the method for trace copper in the high purity nickel, and its step comprises:
(1) purity that contains impurity copper that obtains behind iron, cobalt, zinc and the plumbous impurity pumps into the filling resin for the 3N nickel electrolyte adsorption tower is removed in the electrolytic anolyte pre-treatment of nickelous sulfide; Regulate control adsorption temp and absorption flow velocity; Collecting and obtaining purity is 5N and the above nickel solution of 4N, and described resin is Amberlite IRC-747, Amberlite IRC-748, Purolite S950, Purolite S910 or D403 resin;
(2) after adsorption tower reaches leakage point, stop into water, with regenerator the resin in the step 1 is carried out manipulation of regeneration, the resin after the regeneration is washed till neutrality with clear water, reuses again.
2. resin according to claim 1 is removed the method for trace copper in the high purity nickel, it is characterized in that the resin described in the step 1 is Amberlite IRC-747 or Amberlite IRC-748 resin.
3. resin according to claim 1 is removed the method for trace copper in the high purity nickel, it is characterized in that in the step 1 that said adsorption temp is 5-50 ℃, and the absorption flow velocity is 5-30 BV/h.
4. resin according to claim 1 is removed the method for trace copper in the high purity nickel, it is characterized in that in the step 1, and through the water outlet of 200-3500BV before collecting, obtaining purity is the above nickel solution of 5N; The water outlet in the 1100-4600 BV scope is collected in the back, and obtaining purity is the above nickel solution of 4N.
5. resin according to claim 1 is removed the method for trace copper in the high purity nickel, it is characterized in that in the step 2 that said regenerator is weight percentage and is the HCl solution of 5-25%, and regeneration temperature is 5-50 ℃, and regeneration velocity is 5-30 BV/h.
6. resin according to claim 3 is removed the method for trace copper in the high purity nickel, it is characterized in that in the said step (1), said adsorption temp is 20 ℃, and the absorption flow velocity is 5 BV/h.
7. resin according to claim 5 is removed the method for trace copper in the high purity nickel, it is characterized in that in the step 2, and be weight percentage 15% HCl solution of said regenerator, regeneration velocity is 10 BV/h.
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| CN201210157889.5A CN102643990B (en) | 2012-05-18 | 2012-05-18 | Method for removing trace Cu in high-purity Ni by chelate resin |
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|---|---|---|---|
| CN201210157889.5A CN102643990B (en) | 2012-05-18 | 2012-05-18 | Method for removing trace Cu in high-purity Ni by chelate resin |
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| CN102643990A true CN102643990A (en) | 2012-08-22 |
| CN102643990B CN102643990B (en) | 2014-03-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820809A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Copper removal method |
| CN106283108A (en) * | 2016-08-31 | 2017-01-04 | 中南大学 | A kind of spent ion exchange resin is the method for deep copper removal from nickle electrolysis anode solution |
| CN106702427A (en) * | 2016-11-29 | 2017-05-24 | 河南科技大学 | Method for deeply removing trace iron in cobalt solution through electrodeposition |
| CN108559844A (en) * | 2018-05-21 | 2018-09-21 | 金川集团股份有限公司 | A kind of method of nickel solution deep purifying copper removal |
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| CN1587441A (en) * | 2004-07-28 | 2005-03-02 | 金川集团有限公司 | Process for preparing high purity nickel |
| CN101024163A (en) * | 2007-01-10 | 2007-08-29 | 南京大学 | Method for leading in surface functional to intensify adsorbing resin regeneration characteristics |
| CN101680053A (en) * | 2007-05-14 | 2010-03-24 | Bhp比利通Ssm开发有限公司 | Reclaim nickel in the laterite by high ferrous content |
| CN101811030A (en) * | 2009-12-08 | 2010-08-25 | 北京欧凯纳斯科技有限公司 | Method for removing heavy metal ion by adopting chelate resin cooperative processing |
| CN102268691A (en) * | 2011-08-04 | 2011-12-07 | 苏州晶纯新材料有限公司 | Method for producing high-purity nickel |
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2012
- 2012-05-18 CN CN201210157889.5A patent/CN102643990B/en active Active
Patent Citations (5)
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| CN1587441A (en) * | 2004-07-28 | 2005-03-02 | 金川集团有限公司 | Process for preparing high purity nickel |
| CN101024163A (en) * | 2007-01-10 | 2007-08-29 | 南京大学 | Method for leading in surface functional to intensify adsorbing resin regeneration characteristics |
| CN101680053A (en) * | 2007-05-14 | 2010-03-24 | Bhp比利通Ssm开发有限公司 | Reclaim nickel in the laterite by high ferrous content |
| CN101811030A (en) * | 2009-12-08 | 2010-08-25 | 北京欧凯纳斯科技有限公司 | Method for removing heavy metal ion by adopting chelate resin cooperative processing |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820809A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Copper removal method |
| CN103820809B (en) * | 2014-02-28 | 2017-03-01 | 金川集团股份有限公司 | A kind of copper-removing method |
| CN106283108A (en) * | 2016-08-31 | 2017-01-04 | 中南大学 | A kind of spent ion exchange resin is the method for deep copper removal from nickle electrolysis anode solution |
| CN106283108B (en) * | 2016-08-31 | 2018-04-03 | 中南大学 | A kind of method of spent ion exchange resin deep copper removal from nickle electrolysis anode solution |
| CN106702427A (en) * | 2016-11-29 | 2017-05-24 | 河南科技大学 | Method for deeply removing trace iron in cobalt solution through electrodeposition |
| CN106702427B (en) * | 2016-11-29 | 2019-04-02 | 河南科技大学 | A kind of method that depth removes Trace Iron in electrodeposition cobalt liquor |
| CN108559844A (en) * | 2018-05-21 | 2018-09-21 | 金川集团股份有限公司 | A kind of method of nickel solution deep purifying copper removal |
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| CN102643990B (en) | 2014-03-12 |
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