CN101240429B - Technique for smelting high-purity metal nickel electrodeposition and electrolysis bath thereof - Google Patents
Technique for smelting high-purity metal nickel electrodeposition and electrolysis bath thereof Download PDFInfo
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- CN101240429B CN101240429B CN 200810070698 CN200810070698A CN101240429B CN 101240429 B CN101240429 B CN 101240429B CN 200810070698 CN200810070698 CN 200810070698 CN 200810070698 A CN200810070698 A CN 200810070698A CN 101240429 B CN101240429 B CN 101240429B
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Abstract
The invention discloses a smelting process for high-pure metal nickel electrowinning and the electrobath thereof. An anode plate covered with an anode diaphragm bag and a cathode plate are equipped in the electrobath body, electrolyte flows into the eletrobath by a liquid inlet pipe, electrochemical reacts in the electrobath and permeates the anode diaphragm bag, the electrolyzed anode liquid flows from the bottom of the anode diaphragm bag into the underflow pipe by a connecting pipe and flows out from the underflow outlet pipe, thus the electrowinning is finished. The anode plate is a titanium-iridium anode plate. Since nickel electrolysis is carried out with new electrobath and new titanium-iridium anode, the invention has the following advantages: 1.the cathode space solution has stable the pH value, stable compositions insusceptible to great change caused by leakage of diaphragm bag; 2. the current efficiency is high; and 3. the economical efficiency is obvious. The electrowinning nickel meets the national standard of special nickel.
Description
Technical field
The present invention relates to the smelting technology of metallic nickel, especially relate to a kind of smelting technology and electrolyzer thereof of high-purity metal nickel electrodeposition.
Background technology
Flourish along with domestic coloured industry, the output of coloured product is soaring year by year, the particularly develop rapidly of Chinese stainless steel industry and production domesticization, and the consumption and the output of domestic nickel sheet metal improve year by year, especially high-purity four or nine metallic nickel electrodeposition sheet materials, but be becoming tight nickel resources day.As nickel electrodeposition, in sulfate system, generally adopt alloy lead anode, this anode forms one deck plumbous oxide (PbO on the surface in electrolytic process
2) anonite membrane.This film is not very fine and close, is dashed by the oxygen of separating out at anode in the electrolytic process easily.Be suspended in the PbO in the electrolytic solution
2Particulate also very easily is attached to the electro deposited nickel surface, is wrapped in electrolytic process in the cathode nickel plate, increases the lead tolerance of metallic nickel, reduces the electro deposited nickel quality.For this reason, nickel electrodeposition technology all adopts membranous form that anode and cathode is separated.Disclosed technology all adopts cathode diaphragm bag, with diaphragm bag negative electrode is wrapped exactly.Large-scale nickel smeltery, each electrolyzer has more than 60 of cathode diaphragm bags, and each diaphragm bag all need be settled a controlled liquid-inlet pipe, to regulate the feed liquor amount of each diaphragm bag.The total liquid-inlet pipe quantity in full workshop is nearly thousands of.So not only increase the operation number, and will realize the control of the flow equalization between each bag in the groove, operation easier is also very big.Therefore, how to solve above-mentioned these problems, reach the special utmost point (nickeliferous 99.96%-99.99%) of metallic nickel quality, cost is minimum, and production efficiency is higher, is to be badly in need of the further problem of discussion.
Summary of the invention
First purpose of the present invention is to provide a kind of smelting technology of high-purity metal nickel electrodeposition, it is coated with the iridium anode by adopting novel electrolytic bath and Novel Titanium, in sulfuric acid system, carry out the electrodeposition of metallic nickel, thereby obtain under standard conditions, the cathodic area pH value of solution value stabilization of electrolyzer, current efficiency higher (greater than more than 96%), the electro deposited nickel quality can reach the national standard of nickeliferous 99.96%-99.99% spy's nickel.
Second purpose of the present invention is to provide a kind of electrolyzer of smelting high-purity metal nickel electrodeposition.
First purpose of the present invention is achieved in that titanium is housed is coated with iridium positive plate and negative plate in the cell body of electrolyzer, outside being coated with the iridium positive plate, titanium is with the anode diaphragm bag, electrolytic solution flows in the cell body by liquid-inlet pipe, in cell body, carry out electrochemical reaction, electrolytic solution infiltrates in the anode diaphragm bag again, anolyte after electrolysis is intact flows into the underflow pipe by pipe connecting from the bottom of anode diaphragm bag, from the underflow outlet pipe, flow out again, finish electrodeposition, wherein in the electrolytic solution of being prepared: 80g/l＜nickel≤90g/l, 20g/l≤sodium＜40g/l, 15g/l≤boric acid＜50g/l, pH=2--5 (pH test paper mensuration); Electrolytic condition is: current density: 200-350A/m
2, electrolyte temperature 50--70 ℃, homopolarity width between centers L is 100-180mm, bath voltage 2.5--4.0v, and negative electrode week: 4--8 days, anode and cathode liquid level difference H was 5-14mm.
The acidity of effusive anolyte is 0.5--1.5N from the underflow outlet pipe, nickeliferous＞60g/l, use the own phosphorus 2-of 2-ethyl (ethyl hexyl) ester (P507) in 2-7 level extraction tank, to strip again and can make qualified nickel sulfate solution, further extract through purifying extraction tank, after the oil removing, recirculation enters by liquid-inlet pipe carries out electrolysis once more in the cell body.
After the metallic nickel negative plate grooving behind the electrodeposition, with the temperature of boronic acid containing concentration 10--40g/l more than 50 ℃ pure water or tap water carry out soup and wash.
Second purpose of the present invention is achieved in that a kind of electrolyzer, feature is the top that the opening of bringing the liquid-inlet pipe of liquid valve into is located at cell body, the titanium that is distributed in distance is housed in cell body is coated with iridium positive plate and negative plate, the underflow pipe of sealing is installed in the intravital bottom of groove, outside being coated with the iridium positive plate, titanium is with the anode diaphragm bag, the upper end of pipe connecting is installed in the bottom of anode diaphragm bag, the lower end connects the underflow pipe of left end sealing, and the right-hand member of underflow pipe stretches out cell body and connects liquid-outlet valve and underflow outlet pipe outward successively; On the bottom of cell body, bottom plug is installed.
The anode diaphragm bag is formed by terylene and cotton synthetic fibre blending.
The present invention is coated with the iridium anode by adopting novel electrolytic bath and Novel Titanium, carries out the electrolysis of nickel in sulfuric acid system, has the following advantages:
1, the cathodic area pH value of solution value stabilization of electrolyzer, solution composition is more stable, makes the cathodic area solution composition not be subject to the diaphragm bag seepage and causes the change significantly of solution composition.
2, current efficiency height.The applicant observes in electrolytic process: when catholyte pH value was lower than 2.5, the bubble hydrogen that negative plate produces was along with the continuation reduction of pH value and increase rapidly.Therefore, the cathodic area pH value stabilization of electrolyzer is the higher principal element of current efficiency.
3, remarkable in economical benefits.By 1,2 described condition controls, not only total system is stable, simple to operate, labour intensity reduces, and has improved working efficiency, and the current efficiency height, guarantees constant product quality, and the electro deposited nickel quality can satisfy the national standard of spy's nickel.
4, the present invention also is applicable to the smelting of high pure metal cobalt electrodeposition.
Description of drawings
Fig. 1 is the structural representation of electrolyzer of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1:
Titanium is housed in the cell body 3 of electrolyzer is coated with iridium positive plate 5 and negative plate 7, outside being coated with iridium positive plate 5, titanium is with anode diaphragm bag 4, electrolytic solution flows in the cell body 3 by liquid-inlet pipe 1, in cell body 3, carry out electrochemical reaction, electrolytic solution infiltrates in the anode diaphragm bag 4 again, anolyte after electrolysis is intact flows into the underflow pipe 8 by pipe connecting 6 from the bottom of anode diaphragm bag 4, from underflow outlet pipe 11, flow out again, finish electrodeposition, wherein in the electrolytic solution of being prepared: bath composition: nickel 85g/l, sodium 20g/l, boric acid 15g/l, pH=3.0 (pH test paper mensuration), plumbous 0.0005g/l, cobalt 0.0008g/l, copper 0.0003g/l, manganese 0.0007g/l, zinc 0.0005g/l, iron 0.0004g/l, the residual impurity element all＜0.0005g/l, electrolytic condition is: electrolytic current density 220A/m
2, 60 ℃ of electrolyte temperatures, homopolarity width between centers L is 120mm, bath voltage 3.2v, negative electrode week: 7 days, anode and cathode liquid level difference H was 10mm, cathode efficiency 97.25%.After testing, in the product electro deposited nickel, contain Co7.6 μ g/g, Si44 μ g/g, P1.0 μ g/g, Fe80 μ g/g, Cu62 μ g/g, Zn16 μ g/g, As 2.0 μ g/g, Cd0.1 μ g/g, Sn0.1 μ g/g, Sb0.4 μ g/g, Pb1.6 μ g/g, Bi 0.6 μ g/g, Al 2.0 μ g/g, Mn0.6 μ g/g, Mg6.0 μ g/g, S0.0023%, C0.005%, Ni 99.97%.
The acidity of effusive anolyte is 0.5--1.5N from underflow outlet pipe 11, nickeliferous＞60g/l, use the own phosphorus 2-of 2-ethyl (ethyl hexyl) ester (P507) in 2-7 level extraction tank, to strip again and can make qualified nickel sulfate solution, further extract through purifying extraction tank, after the oil removing, recirculation enters by liquid-inlet pipe 1 carries out electrolysis once more in the cell body 3.
After metallic nickel negative plate 7 groovings behind the electrodeposition, with the temperature of boronic acid containing concentration 10--40g/l more than 50 ℃ pure water or tap water carry out soup and wash.
A kind of electrolyzer, the opening of bringing the liquid-inlet pipe 1 of liquid valve 2 into is located at the top of cell body 3, the titanium that is distributed in distance is housed in cell body 3 is coated with iridium positive plate 5 and negative plate 7, bottom in cell body 3 is equipped with the underflow pipe 8 of left end sealing, outside being coated with iridium positive plate 5, titanium is with anode diaphragm bag 4, the upper end of pipe connecting 6 is installed in the bottom of anode diaphragm bag 4, and the lower end connects underflow pipe 8, and the right-hand member of underflow pipe 8 stretches out cell body 3 outer liquid-outlet valve 10 and the underflow outlet pipes 11 of connecing successively; Bottom plug 9 is installed on the bottom of cell body 3.
Anode diaphragm bag 4 is formed by terylene and cotton synthetic fibre blending.
Embodiment 2:
The technology of embodiment 2 and the structure of electrolyzer are substantially the same manner as Example 1, difference in:
Bath composition: nickel 90g/l, sodium 25g/l, boric acid 15g/l, pH=3.5 (pH test paper mensuration), plumbous 0.0004g/l, cobalt 0.0009g/l, copper 0.0004g/l, manganese 0.0008g/l, zinc 0.0004g/l, iron 0.0004g/l, the residual impurity element all＜0.0005g/l, electrolytic condition: current density 215A/m
2, 55 ℃ of electrolyte temperatures, homopolarity width between centers L is 120mm, bath voltage 3.0v, negative electrode week: 6 days, anode and cathode liquid level difference H was 10mm, cathode efficiency 97.70%.After testing, in the product electro deposited nickel, contain Co7.6 μ g/g, Si10 μ g/g, P3.5 μ g/g, Fe20 μ g/g, Cu3.0 μ g/g, Zn1.8 μ g/g, As8.0 μ g/g, Cd0.56 μ g/g, Sn0.5 μ g/g, Sb0.2 μ g/g, Pb1.6 μ g/g, Bi0.6 μ g/g, Al3.9 μ g/g, Mn0.6 μ g/g, Mg2.1 μ g/g, S0.001%, C0.005%, Ni99.99%.
Claims (5)
1. the smelting technology of a high-purity metal nickel electrodeposition, it is characterized in that: titanium is housed in the cell body (3) of electrolyzer is coated with iridium positive plate (5) and negative plate (7), outside being coated with iridium positive plate (5), titanium is with anode diaphragm bag (4), electrolytic solution flows in the cell body (3) by liquid-inlet pipe (1), in cell body (3), carry out electrochemical reaction, electrolytic solution infiltrates in the anode diaphragm bag (4) again, anolyte after electrolysis is intact flows into the underflow pipe (8) by pipe connecting (6) from the bottom of anode diaphragm bag (4), from underflow outlet pipe (11), flow out again, finish electrodeposition, wherein in the electrolytic solution of being prepared: 80g/l＜nickel≤90g/l, 20g/l≤sodium＜40g/l, 15g/l≤boric acid＜50g/l, pH=2-5;
The content of impurity element is in the above-mentioned electrolytic solution:
(A) lead: 0.0005g/l, cobalt: 0.0008g/l, copper: 0.0003g/l, manganese: 0.0007g/l, zinc: 0.0005g/l, iron: 0.0004g/l, residual impurity element all＜0.0005g/l;
Perhaps (B) lead: 0.0004g/l, cobalt: 0.0009g/l, copper: 0.0004g/l, manganese: 0.0008g/l, zinc: 0.0004g/l, iron: 0.0004g/l, residual impurity element all＜0.0005g/l;
Electrolytic condition is: current density: 200-350A/m
2, electrolyte temperature 50--70 ℃, homopolarity width between centers L is 100-180mm, bath voltage 2.5--4.0v, and negative electrode week: 4--8 days, anode and cathode liquid level difference H was 5-14mm.
2. the smelting technology of high-purity metal nickel electrodeposition as claimed in claim 1, it is characterized in that: the acidity of effusive anolyte is 0.5--1.5N from underflow outlet pipe (11), nickeliferous＞60g/l, strip in 2-7 level extraction tank with the own phosphorus of 2-ethyl-2-(ethyl hexyl) ester again and can make qualified nickel sulfate solution, further extract through purifying extraction tank, after the oil removing, recirculation enters in the cell body (3) by liquid-inlet pipe (1) carries out electrolysis once more.
3. the smelting technology of high-purity metal nickel electrodeposition as claimed in claim 1 is characterized in that: after metallic nickel negative plate (7) grooving behind the electrodeposition, with the temperature of boronic acid containing concentration 10--40g/l more than 50 ℃ pure water or tap water carry out soup and wash.
4. the electrolyzer that is used for high-purity metal nickel electrodeposition smelting technology as claimed in claim 1, it is characterized in that: the opening of bringing the liquid-inlet pipe (1) of liquid valve (2) into is located at the top of cell body (3), the titanium that is distributed in distance is housed in cell body (3) is coated with iridium positive plate (5) and negative plate (7), bottom in cell body (3) is equipped with the underflow pipe (8) of left end sealing, outside being coated with iridium positive plate (5), titanium is with anode diaphragm bag (4), the upper end of pipe connecting (6) is installed in the bottom of anode diaphragm bag (4), the lower end connects underflow pipe (8), and the right-hand member of underflow pipe (8) stretches out outer liquid-outlet valve (10) and the underflow outlet pipe (11) of connecing successively of cell body (3); Bottom plug (9) is installed on the bottom of cell body (3).
5. electrolyzer as claimed in claim 4 is characterized in that: anode diaphragm bag (4) is formed by terylene and cotton synthetic fibre blending.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200810070698 CN101240429B (en) | 2008-02-29 | 2008-02-29 | Technique for smelting high-purity metal nickel electrodeposition and electrolysis bath thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200810070698 CN101240429B (en) | 2008-02-29 | 2008-02-29 | Technique for smelting high-purity metal nickel electrodeposition and electrolysis bath thereof |
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| Publication Number | Publication Date |
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| CN101240429A CN101240429A (en) | 2008-08-13 |
| CN101240429B true CN101240429B (en) | 2010-06-23 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103046076B (en) * | 2012-12-26 | 2016-06-08 | 浙江华友钴业股份有限公司 | A kind of preparation method of electro deposited nickel |
| CN103409771B (en) * | 2013-08-13 | 2017-07-21 | 四川省尼科国润新材料有限公司 | A kind of environment-friendly type electrolytic nickel continuous and stable production technique |
| CN103436913B (en) * | 2013-08-13 | 2016-03-09 | 四川省尼科国润新材料有限公司 | The device of a kind of electro deposited nickel or electrodeposited cobalt |
| CN105274563A (en) * | 2014-05-28 | 2016-01-27 | 北京有色金属研究总院 | High-purity cobalt preparation method |
| CN104532293B (en) * | 2014-12-22 | 2017-06-09 | 无锡市瑞思科环保科技有限公司 | The method of purifying nickel and nickel purifying plant in chemical nickel plating waste solution |
| CN104928476B (en) * | 2015-02-05 | 2017-08-04 | 青岛科技大学 | A kind of processing method of cobalt-copper alloy Water Quenching Slag |
| CN105349780A (en) * | 2015-11-20 | 2016-02-24 | 兰州金川新材料科技股份有限公司 | Purification method for nickel electric accumulated liquid for manufacturing high-purity nickel plate |
| CN111663153B (en) * | 2020-05-20 | 2022-03-15 | 金川集团股份有限公司 | Method for inhibiting impurities of lead and zinc from being separated out at cathode in nickel electrolysis process |
| CN112695344A (en) * | 2020-12-30 | 2021-04-23 | 金川集团股份有限公司 | Method for producing electrodeposited nickel |
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