CN100378233C - Process for cleaning decopper nickel electrolytic solution - Google Patents
Process for cleaning decopper nickel electrolytic solution Download PDFInfo
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- CN100378233C CN100378233C CNB2004100568942A CN200410056894A CN100378233C CN 100378233 C CN100378233 C CN 100378233C CN B2004100568942 A CNB2004100568942 A CN B2004100568942A CN 200410056894 A CN200410056894 A CN 200410056894A CN 100378233 C CN100378233 C CN 100378233C
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- thiosulfate
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Abstract
The present invention relates to a method for removing copper from a nickel electrolyte, which relates to a method for carrying out purifying impurity removal to an electrolyte in the process of producing metal nickel by hydrometallurgy technology, particularly to a method for carrying out purifying copper removal to the nickel electrolyte. The present invention is characterized in that nickel thiosulfate is added to the nickel electrolyte as a copper removing agent. In the technological processes, the nickel thiosulfate is added to the nickel electrolyte according to a proportion of (4.4 to 7): 1 of S2O3<2-> and Cu<2+>, and the pH value is regulated to be from 0.5 to 2 by adding acid at a temperature of 65 to 70 DEG C; the time of stirring reactions is from 30 to 40 min, generated CuS precipitates are separated, and purified liquid after the copper removal is obtained. The thiosulfate copper removing agent of the present invention is easy to dissolve in water; even if the copper removing agent is excessively added in the copper removal, the increase of the nickel content of copper slag can not be caused, which is different from the copper removal of nickel powder, nickel concentrates and nickel sulfide; therefore, the nickel content of the slag is low. The quantity of the copper slag is decreased to one fourth of the present quantity of the copper slag by the use of the nickel thiosulfate copper removing agent, the technological intensity is reduced, and man power and energy consumption are saved.
Description
Technical field
A kind of nickel electrolyte copper-removing method relates to a kind of purifying and impurity-removing method, the particularly method of nickel electrolyte purification copper removal that adopts electrolytic solution in the process that hydrometallurgical processes produces metallic nickel.
Background technology
During the wet method nickel electrowinning, solution composition is generally after the deironing: Ni:65～75g/L, Cu:0.3～0.6g/L, Fe＜0.001g/L, SO
4 2-: 100～120g/L, Cl
-: 80～90g/L.In order to guarantee the quality of electrolytic nickel, constantly take nickel ore concentrate to add anode sludge method copper removal, this method copper removal is effective, and speed of response is fast, can satisfy production requirement substantially.But because the nickel ore concentrate poor activity causes the nickel ore concentrate displacement not exclusively, make except that the nickeliferous height of copper ashes, average nickeliferous up to 40%, cupric only is 20%, and the quantity of slag is big, and directly direct yield is produced in influence.
In recent years, in order to improve the direct yield of nickel, people have adopted the full soaking technology of copper ashes chlorine, institute is produced copper ashes all leach, and the workshop direct yield has been had increase substantially.But, in leaching copper ashes in the nickel, copper is also entered in the solution system by leaching in the slag, this just causes the vicious cycle of copper in the solution system undoubtedly, though this part solution at first will pass through the liquid making decopper(ing), but circulation accumulation limited in one's ability, that this just causes copper in the solution inevitably brings many difficulties to production.People are seeking a kind of more efficiently copper-removing method.
At present, the method of soaking purification copper removal in the method metallurgy at the nickel cobalt is a lot, the method of only vulcanizing just has nearly ten kinds, except that the present nickel ore concentrate that adopts adds anode sludge copper removal method, also have Sulfothiorine, hydrogen sulfide, sodium sulphite, active nickel sulfide, nickel powder, nickel rondelle, sulfurous gas to add copper-removing methods such as sulphur.Wherein, the Sulfothiorine copper removal is effective, and the reaction times is short, labor condition, but owing to bring a large amount of sodium ions into to solution system, it is unfavorable that system balancing is brought.
Summary of the invention
The present invention seeks in order to overcome the deficiency that above-mentioned prior art exists, provide a kind of can degree of depth copper removal, effectively reduce slag nickeliferous, reduce the quantity of slag, improve direct yield, and loose, the maneuverable nickel electrolyte purification copper-removing method of technical qualification.
The objective of the invention is to be achieved through the following technical solutions.
A kind of nickel electrolyte purification copper-removing method is characterized in that adding nickel thiosulfate and carries out the copper removal purification as decoppering agent in nickel electrolyte, its technological process is: press S in nickel electrolyte
2O
3 2-/ Cu
2+Mol ratio=4.4～7: 1 ratio adds nickel thiosulfate, and under 65 ℃～70 ℃ temperature, adding acid adjustment pH value is 0.5-2; Stirring reaction 30-40min, the CuS post precipitation that filters to isolate generation obtain liquid behind the copper removal.
Adopt copper-removing method of the present invention, the liquid cupric is less than 0.001g/l behind the copper removal, and copper ashes is nickeliferous extremely low, and copper nickel ratio reaches more than 100: 1.Existing production copper removal equipment is not done big change and just be can be used for producing, and can satisfy and produce the requirement of electric nickel copper removal.
Decoppering agent copper removal method of the present invention is applicable to the clean liquid copper removal of nickel electrowinning, and its technical qualification are loose, and the workman operates easily.Copper nickel ratio behind the copper removal in the copper ashes is far longer than 20: 1, and slag is nickeliferous less than 1%, can be used as copper ore concentrates fully and enters the copper system, forms the open circuit of copper, does not cause the circulation of copper at nickel electrowinning, and improves the rate of recovery and the direct yield of nickel.This method can not brought other harmful ion into to solution system, and unreacted is S completely
2O
3 2-Ion stability is relatively poor, when the road removes the cobalt operation under entering, is easy to be become sulfate ion by chlorine oxidation, and therefore, the road electrowinning process brought detrimentally affect under this method can not be given.
Method of the present invention, the liquid nickel thiosulfate of employing is made decoppering agent, and raw materials for production are the solution and the part solid sulphuric acid nickel of new liquid of nickel electrowinning system or sulfur acid nickel, S powder and SO
2Also can originate from the byproduct of nickel production process, its raw material sources are convenient.By the nickel thiosulfate decoppering agent that the new liquid of electrolysis is produced, wherein nickel only as the carrier of thiosulfate anion, is got back to the nickel electrowinning system again during copper removal in whole process, can not cause damage, and can improve Ni in the electrolytic solution
2+2～4 percentage points of concentration.
The thiosulphate of the decoppering agent of the inventive method and to contain sulfide complex soluble in water, even add the excessive nickeliferous rising of copper ashes that also can not cause during copper removal, this is different from nickel powder, nickel ore concentrate, the nickelous sulfide copper removal is so slag is nickeliferous low.And make the copper ashes amount reduce to present 1/4, reduced technology intensity, saved manpower and energy consumption.With the thiosulphate of soluble nickel and contain the sulfide complex copper removal, also avoided embodying and brought sodium ion into to solution, it is nickeliferous to reduce slag again.The liquid cupric reaches below the 0.001g/L behind the copper removal, and copper nickel ratio reaches more than 20: 1 in the copper ashes, on average reaches 136: 1.
The nickel thiosulfate of the decoppering agent of the inventive method is used for reference the prior synthesizing method of thiosulphate in preparation: promptly in the sulfurous acid nickel solution, add an amount of sulphur powder and boil altogether, under the effect of catalyzer, obtain nickel thiosulfate.The concrete operations step is: take by weighing an amount of nickelous carbonate and place sulfurous acid solution, make it at first be converted into sulfurous acid nickel, add the excess of sulfur powder then.Under catalyst action, the reflux certain hour is cooled to room temperature, removes by filter residue, collects filtrate.Proof contains certain density thiosulfate ion in the filtrate after testing.Repeated experiments, when its fluctuation of concentration between 0.5～1.8moL, be 50%～75% in the nickel direct yield.Along with the prolongation of storage period, find that the concentration of thiosulfate ion is descending gradually.Its density loss about 65% after 24 hours.Separating out of simultaneous elemental sulfur.As adding an amount of oxidation inhibitor, situation can greatly be taken on a new look.
In order to improve the quality product of nickel thiosulfate, prepare stable nickel thiosulfate, more reasonably prepare route so just found out.Mechanism is as follows:
RS
2O
3+BaCl
2＝BaS
2O
3↓+2RCl
BaS
2O
3+NiSO
4＝BaSO
4↓+NiS
2O
3
Because BaSO
4Ksp=1.1 * 10
-10And BaS
2O
3Ksp=8.0 * 10
-7So above-mentioned reaction is feasible.Promptly directly in the aqueous solution of single nickel salt, introduce thiosulfate ion, itself and nickel ion are reacted, reacted solution is therefrom isolated nickel thiosulfate after separating slagging-off (precipitation), concentrate the thiosulfuric acid nickel solution and the solid crystal product that can obtain any concentration through dewatering.Experimental results show that total yield is not less than 90%.Take special measure for the liquid or solid product, the activity of can remaining valid for a long time.
A kind of nickel electrolyte purification copper-removing method is characterized in that the preparation process of the nickel thiosulfate decoppering agent that adds is: press BaS in nickel electrolyte
2O
3And NiSO
4The mole proportioning be 1: 0.94 ratio, 35 ℃-40 ℃ of temperature of reaction, reaction times 85-110min makes liquid nickel thiosulfate decoppering agent.
A kind of nickel electrolyte purification copper-removing method, it is characterized in that in the preparation process of the nickel thiosulfate decoppering agent that in nickel electrowinning solution, adds, liquid nickel thiosulfate decoppering agent by volume 1 in preparation: the proportioning of 2.5-4.5 adds enriching agent ethanol, reaction times 24h, preparation solid nickel thiosulfate decoppering agent.
A kind of nickel electrolyte purification copper-removing method is characterized in that when preparation solid nickel thiosulfate decoppering agent being is to add the enriching agent alcoholic acid in the 80-160g/L liquid nickel thiosulfate to concentration.
Experimental results show that: the concentration of the purity of solid nickel thiosulfate decoppering agent and liquid nickel thiosulfate decoppering agent has certain relation.Illustrate that enriching agent has certain influence to the stability of the higher liquid nickel thiosulfate decoppering agent of concentration.
The ion-product constant of barium sulfate and barium thiosulfate barium hyposulflte is respectively: 1.1 * 10
-10, 8.0 * 10
-7Utilize the difference of ionic product, at first the solubility thiosulphate is converted into barium thiosulfate barium hyposulflte, then by control NiSO
4Concentration and serial reaction condition, twice transformation is preparation NiS after separate
2O
3Solution, this solution and then make solid NiS under the effect of enriching agent
2O
3.xH
2O, i.e. nickel thiosulfate decoppering agent.Identify that by analysis confirm the nickel thiosulfate decoppering agent of preparation, main body is NiS
2O
3.6H
2O, the light green styloid, its purity is between 94%-96%.
By different detection meanss, confirm that having prepared solid nickel thiosulfate decoppering agent main body is NiS
2O
3.6H
2O, the light green styloid.Its purity is between 94%～96%.During in temperature≤10 ℃, decomposition reaction can not take place in its better heat stability.But lose crystal water to some extent.
Embodiment
A kind of nickel electrolyte purification copper-removing method adds nickel thiosulfate at nickel electrolyte and carries out as decoppering agent that copper removal purifies, and its technological process is: press S in nickel electrolyte
2O
3 2-/ Cu
2+Mol ratio=4.4～7: 1 ratio adds nickel thiosulfate, and under 65 ℃～70 ℃ temperature, adding acid adjustment pH value: PH is 0.5-2; Stirring reaction time: 30-40min separates generating the CuS precipitation, liquid behind the copper removal after must purifying.The preparation process of nickel thiosulfate decoppering agent is: press BaS
2O
3And NiSO
4The mole proportioning be that 1: 0.94 ratio cooperates, 35 ℃-40 ℃ of temperature of reaction, reaction times 90min generates liquid nickel thiosulfate decoppering agent.
Embodiment 1
The preparation method one of nickel thiosulfate
Take by weighing an amount of NiCO
3Place sulfurous acid solution, make it at first be converted into sulfurous acid nickel, add the excess of sulfur powder then.Under catalyst action, the reflux certain hour is cooled to room temperature, removes by filter residue, collects filtrate.Proof contains certain density thiosulfate ion in the filtrate after testing.Repeated experiments, when its fluctuation of concentration between 0.5～1.8moL, be 50%～75% in the nickel direct yield.
Embodiment 2
The preparation method two of nickel thiosulfate
(1) preparation of barium thiosulfate barium hyposulflte
Adopt orthogonal experiment method to seek BaS
2O
3Optimum preparating condition
Table one level of factor table
| A | B | C | |
| Proportioning (mol/mol) | Temperature ℃ | Time min | |
| 1 | 0.98∶1 | 20 | 5 |
| 2 | 1∶1 | 30 | 10 |
| 3 | 1∶0.98 | 40 | 15 |
Annotate: proportioning refers to Na
2S
2O
3.5H
2O and BaCl
2.2H
2The mol ratio of O
Know scheme C by analysis
2A
2B
1Be the best.That is:
1. proportioning is 1: 1
2. 20 ℃ of temperature (near room temperature)
3. churning time 10min
In order to make comparatively purified BaS
2O
3, with BaS
2O
3With the hot water injection of about 60 ℃ of T ≈ 2～3 times.
(2) preparation of liquid nickel thiosulfate decoppering agent
Adopt orthogonal experiment to seek the optimum preparating condition of preparation liquid nickel thiosulfate decoppering agent
Table two level of factor table
| A | B | C | |
| Proportioning (mol/mol) | Reaction times min | Temperature ℃ | |
| 1 | 1∶0.94 | 30 | 20 |
| 2 | 1∶1 | 60 | 30 |
| 3 | 0.94∶1 | 90 | 35 |
Annotate: proportioning refers to BaS
2O
3And NiSO
4Mol ratio
Know scheme C by analysis
3A
1B
3Be the best.That is:
1. proportioning is 1: 0.94
2. 35 ℃ of temperature (near room temperature)
3. reaction times 90min
C is for the preparation of solid nickel thiosulfate decoppering agent
Adopt orthogonal experiment to seek the optimum preparating condition of preparation liquid nickel thiosulfate decoppering agent
Table three level of factor table
| A | B | C | |
| Proportioning (ml/ml) | Time h | Liquid nickel thiosulfate decoppering agent concentration (is S 2O 3 2-Content) g/L | |
| 1 | 1∶2.5 | 16 | 80 |
| 2 | 1∶3.5 | 24 | 120 |
| 3 | 1∶4.5 | 32 | 160 |
Annotate: proportioning refers to the volume ratio of liquid nickel thiosulfate decoppering agent and enriching agent, and the reaction times refers to the crystalline time of repose
Annotate: be investigation rate of recovery problem, and with oxidized partially recycled in the crystallization, thereby influenced its purity to a certain extent.
Know scheme C by analysis
1A
3B
2Be the best.That is:
1. proportioning is 1: 4.5
2. crystallization time 24h
3. liquid nickel thiosulfate decoppering agent concentration (is S
2O
3 2-Content) 80g/L
In serial crystallization concentration process, the height that we find liquid sample concentration with make solid phase prod purity certain relation arranged.It is low more to be specially liquid nickel thiosulfate decoppering agent concentration, and it is high more to make solid purity.
Embodiment 3
At first with sulfuric acid with iron after the liquid value be transferred to preset value, measure this solution, be contained in the beaker, place in the electron temperature-control water-bath.And temperature regulation controller is preset to preset temperature, and slowly stir, heat up simultaneously.After solution temperature reaches preset value, add in right amount, and pick up counting, reaction after finishing is filtered solution, analyzes filtrate and slag composition.
The investigative test of nickel thiosulfate decoppering agent copper removal, its copper removal condition is: 60 ℃ of temperature of reaction, reaction times 15min, solution PH are controlled between 3.5～4.0, and the long-pending 600ml of liquid after the deironing adds liquid nickel thiosulfate decoppering agent 38ml, (contains S
2O
3 2-120g/l), [S wherein
2O
3 2-]: [Cu
2+] (MR)=7: 1,
Now experimental result is listed as follows:
Table four experimental result table
| Composition | Ni(g/l) | SO 4 2-(g/l) | S 2O 3 2-(g/l) - | Cu(g/l) | PH |
| Liquid before the copper removal | 71.8 | 111.52 | 0.60 | 3.8 | |
| Liquid behind the copper removal | 72.75 | 120.02 | 7.68 | 0.54 | 4.0 |
Condition test
By above-mentioned experimental result as can be known, the copper removal effect under this condition is very undesirable, solution cupric only descend 0.06g/l and the S in the solution
2O
3 2-Total amount is with the S that is added
2O
3 2-It is very little to compare variation, that is to say under this reaction conditions, and the decoppering agent of adding is not almost participated in reaction, also is not decomposed.Therefore, if do not change reaction conditions, just be difficult to the copper removal effect that reaches predetermined, change corresponding copper removal condition, situation is as follows:
A. temperature is to the influence experiment of copper removal effect
The liquid composition is before the copper removal: Ni:77.44g/l, Cu:0.60g/l, Co:0.28g/l, SO
4 2-: 111.89g/l, other condition and test-results such as following table:
Table five temperature is to the influence of copper removal effect
| Temperature of reaction (℃) | Time (min) | PH | Liquid composition (g/l) behind the copper | |||
| Before the copper removal | Behind the copper removal | Cu | SO 4 2- | S 2O 3 2- | ||
| 70 | 30 | 3.6 | 3.0 | 0.26 | 120 | 6.45 |
| 80 | 30 | 3.7 | 2.8 | 0.15 | 121 | 6.23 |
| 86 | 30 | 3.7 | 2.6 | 0.11 | 120.2 | 6.22 |
| 90 | 30 | 3.6 | 2.5 | 0.010 | 4.76 | |
| 96 | 30 | 3.6 | 2.4 | 0.0004 | 4.15 | |
By last watch test result as can be seen temperature of reaction the copper removal degree of depth is had a significant impact, as can be seen, under the same conditions, along with the rising of temperature of reaction, the solution cupric descends gradually, this illustrates elevated temperature, helps the carrying out of copper-stripping reaction.Temperature is fairly obvious to the influence of the copper removal degree of depth, and temperature of reaction is a very The key factor.
B. the solution pH value is to the influence of copper removal effect
Test finds, when liquid pH value before the copper removal greater than 2.0 the time, even the nickel thiosulfate decoppering agent added to mol ratio 7: 1, the copper removal degree of depth also is difficult to reach below the 0.002g/l.Other condition and test-results such as following table:
Table six solution pH value is to the influence of copper removal effect
| Temperature (℃) | PH value | Add-on (MR) | Time (min) | Liquid (Cu behind the copper removal 2+g/l) |
| 70 | 1.2 | 7∶1 | 15 | 0.0005 |
| 70 | 1.5 | 7∶1 | 15 | 0.002 |
| 70 | 2.0 | 7∶1 | 15 | 0.033 |
| 70 | 2.5 | 7∶1 | 15 | 0.22 |
As can be seen, under the same conditions, solution PH is to the obvious effect of copper removal effect, and the solution pH value is low more, the copper removal effect is good more, and when pH value greater than 2 the time, influence degree is strong more, i.e. the copper removal weak effect, and when pH value less than 2 the time, along with the reduction of pH value, the copper removal effect is good more, and it is a stagnation point to copper removal under this condition that this explanation pH value equals 2.
C. reagent dosage is to the influence of the copper removal degree of depth
What of nickel thiosulfate decoppering agent add-on also have certain influence to the copper removal degree of depth, shown in the table specific as follows:
Table seven reagent dosage is to the influence of copper removal
| Temperature (℃) | Add-on (MR) | PH value | Time (min) | Liquid (Cu behind the copper removal 2+g/l) |
| 70 | 15 | 2.0 | 30 | 0.14 |
| 70 | 20 | 2.0 | 30 | 0.001 |
| 70 | 25 | 2.0 | 30 | 0.0005 |
| 70 | 30 | 2.0 | 30 | 0.0004 |
As seen from the above table, under the same conditions, reagent dosage is big more, and the copper removal effect is good more, and the liquid cupric is low more behind the copper removal.Simultaneously, we also find by test, in other condition one regularly, improve temperature of reaction, can reduce the reagent usage quantity, when temperature of reaction reduces, can reach the identical copper removal degree of depth by increasing amount of reagent.
D. the time is to the influence of copper removal
In general, the reaction times is long more, reacts complete more.This test has also proved this point.By the following table data as can be seen under the same conditions, along with the prolongation of time, the liquid cupric descends gradually behind the copper removal, but its influence degree is not too big.
Table eight time is to the influence of copper removal
| Temperature (℃) | Time (min) | Add-on (MR) | PH value | Liquid (Cu behind the copper removal 2+g/l) |
| 70 | 15 | 20 | 2.0 | 0.063 |
| 70 | 20 | 20 | 2.0 | 0.012 |
| 70 | 30 | 20 | 2.0 | 0.001 |
Embodiment 4
Replication experiment
According to above-mentioned four kinds of conditions that influence the copper removal effect, selected to have made replication experiment with the immediate condition of existing production.
Actual conditions is as follows: temperature: 65 ℃～70 ℃; Reaction 30min; Solution pH value: PH≤2; Nickel thiosulfate decoppering agent consumption: S
2O
3 2-/ Cu
2+(MR)＞4.4; Stirring velocity: 200～250r/min
As can be known: test under these conditions, it is very satisfied that the copper removal effect is made us, and the liquid cupric is almost all less than 0.001g/l behind the copper removal, and copper ashes is nickeliferous extremely low, and copper nickel ratio reaches more than 100: 1.Be the top condition that adapts under the present production technique, existing production copper removal equipment is not done big change and just be can be used for producing, and can satisfy and produce the requirement of an electric nickel copper removal.
Nickel thiosulfate decoppering agent copper removal is used for the clean liquid copper removal of nickel electrowinning, and its technical qualification are loose, and the workman operates easily.Copper nickel ratio behind the copper removal in the copper ashes is far longer than 20: 1, slag is nickeliferous less than 1%, can be used as copper ore concentrates fully and enter the copper system, form the open circuit of copper, do not cause the circulation of copper at nickel electrowinning, and improve the rate of recovery and the direct yield of nickel, this method can not brought other harmful ion into to solution system, and unreacted is S completely
2O
3 2-Ion stability is relatively poor, when the road removes the cobalt operation under entering, is easy to be become sulfate ion by chlorine oxidation, and therefore, the road electrowinning process brought detrimentally affect under this method can not be given.The nickel thiosulfate decoppering agent that this method adopts, raw materials for production are new liquid of nickel electrowinning system or sulfur acid nickel solution, part solid sulphuric acid nickel, S powder and SO
2Be the byproduct of nickel cobalt metal, its raw material sources are convenient.By the nickel thiosulfate decoppering agent that the new liquid of electrolysis is produced, wherein nickel only as the carrier of nickel thiosulfate, is got back to the nickel electrowinning system again, and is improved its Ni in whole process during copper removal
2+2～4 percentage points of concentration can not lost.
Thiosulphate decoppering agent of the present invention is soluble in water, even add the excessive nickeliferous rising of copper ashes that also can not cause during copper removal, this is different from nickel powder, nickel ore concentrate, and the nickelous sulfide copper removal is so slag is nickeliferous low.The use of nickel thiosulfate decoppering agent makes the copper ashes amount reduce to present 1/4, has reduced technology intensity, has saved manpower and energy consumption.
Claims (4)
1. a nickel electrolyte purification copper-removing method is characterized in that adding nickel thiosulfate and carries out the copper removal purification as decoppering agent in nickel electrolyte, and its technological process is: press S in nickel electrolyte
2O
3 2-/ Cu
2+Mol ratio=4.4～7: 1 ratio adds nickel thiosulfate, and under 65 ℃～70 ℃ temperature, adding acid adjustment pH value is 0.5-2; Stirring reaction 30-40min, the CuS post precipitation that filters to isolate generation obtain liquid behind the copper removal.
2. a kind of nickel electrolyte purification copper-removing method according to claim 1 is characterized in that the preparation process of the nickel thiosulfate decoppering agent that adds is: press BaS in nickel electrolyte
2O
3And NiSO
4The mole proportioning be 1: 0.94 ratio, 35 ℃-40 ℃ of temperature of reaction, reaction times 85-110min makes liquid nickel thiosulfate decoppering agent.
3. a kind of nickel electrolyte purification copper-removing method according to claim 2, it is characterized in that in the preparation process of the nickel thiosulfate decoppering agent that in nickel electrowinning solution, adds, liquid nickel thiosulfate decoppering agent in preparation is 1 by volume: the proportioning of 2.5-4.5 adds enriching agent ethanol, reaction times 24h, preparation solid nickel thiosulfate decoppering agent.
4. a kind of nickel electrolyte purification copper-removing method according to claim 3 is characterized in that when preparation solid nickel thiosulfate decoppering agent being is to add the enriching agent alcoholic acid in the 80-160g/L liquid nickel thiosulfate to concentration.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101063210B (en) * | 2006-04-25 | 2010-05-26 | 襄樊化通化工有限责任公司 | Technique for producing high activity nickel cake with regeneration of waste material containing nickle as raw material |
| CN103320811B (en) * | 2013-06-05 | 2015-08-12 | 中南大学 | A kind of method removing impurity from nickle electrolysis anode solution |
| CN103320622A (en) * | 2013-07-18 | 2013-09-25 | 海南金亿新材料股份有限公司 | Technological process for preparing electronic-grade nickel methylsulfonate by utilization of nickel waste material |
| CN103820809B (en) * | 2014-02-28 | 2017-03-01 | 金川集团股份有限公司 | A kind of copper-removing method |
| CN106834740B (en) * | 2016-12-30 | 2019-02-12 | 四川师范大学 | The method for decoppering of nickel solution |
| CN115650319B (en) * | 2022-10-22 | 2024-02-20 | 兰州大学 | Method for synchronously and efficiently removing copper and cobalt ions from nickel sulfate solution |
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| WO1999060179A1 (en) * | 1998-05-14 | 1999-11-25 | Falconbridge Limited | Recovery of nickel from copper refinery tankhouse electrolyte |
-
2004
- 2004-08-30 CN CNB2004100568942A patent/CN100378233C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1827393C (en) * | 1991-04-17 | 1993-07-15 | Химико-металлургический институт АН КазССР | Method of copper precipitation from copper-nickel sulfate electrolyte |
| CN1088266A (en) * | 1993-12-27 | 1994-06-22 | 杨春青 | The method and apparatus of leaching and recoverying copper, silver, gold, lead, iron, sulphur from sulphuretted copper ore |
| CN1100153A (en) * | 1994-06-29 | 1995-03-15 | 北京有色冶金设计研究总院 | Method for removal of copper from electrolytic nickel anodic liquid |
| WO1999060179A1 (en) * | 1998-05-14 | 1999-11-25 | Falconbridge Limited | Recovery of nickel from copper refinery tankhouse electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| 室温下用氨性硫代硫酸盐从含铜金矿中浸出金. 周国华等.矿产综合利用，第5期. 1999 * |
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| CN1598012A (en) | 2005-03-23 |
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