CN102730745B - Process for removing nickel from high-purity plating-stage copper sulfate - Google Patents
Process for removing nickel from high-purity plating-stage copper sulfate Download PDFInfo
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- CN102730745B CN102730745B CN201210235287.7A CN201210235287A CN102730745B CN 102730745 B CN102730745 B CN 102730745B CN 201210235287 A CN201210235287 A CN 201210235287A CN 102730745 B CN102730745 B CN 102730745B
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Abstract
The invention discloses a process for removing nickel from high-purity plating-stage copper sulfate, which takes the etching waste liquor containing copper as raw material to remove impurity nickel by adopting the process of purifying and removing impurities so as to ensure that the nickel ion content in the finally produced plating-stage copper sulfate is not greater than 10 ppm. The preparation method comprises the following steps: (1) filtering the etching waste liquor containing copper to remove the mechanical impurities; (2) purifying to remove tin and arsenic; (3) adjusting the pH value to remove ferrum; (4) removing the calcium and the magnesium; (5) neutralizing acidity and alkali to produce copper-salt sediment; (6) washing and purifying the copper-salt sediment; (7) acidizing the concentrated sulfuric acid; and (8) cooling and crystallizing. The process has the advantages of low production cost, simple technology, high purity of produced copper sulfate and low nickel content.
Description
Technical field
The present invention relates to belong to chemical field, be specifically related to a kind of high-purity cupric sulfate purified except nickel technique.
Background technology
Copper sulfate is most important a kind of mantoquita in copper compound, of many uses.Industrial, the copper sulfate of take can be prepared the compound of copper and a series of copper as raw material, is important industrial chemicals; In agricultural, copper sulfate is important inorganic pesticide raw material, or important trace mineral supplement in animal-feed; Copper sulfate can also be as the mordant of fabric, wood preservative, coating etc.Cupric sulfate purified has important application in electroplating industry, along with developing rapidly of China's non-metal electroplating, decorative electroplating and printed circuit board industry, the demand of cupric sulfate purified is increased sharply.Cupric sulfate purified requires the purity of copper sulfate high, and foreign matter content is low, particularly the metallic impurity such as Fe, Zn, Pb, Ca, Mg, Ni.
PCB(printed circuit board) developing rapidly of industry produces a large amount of etching waste liquors, realizes the recycling of copper in etching waste liquor and has important economic worth and environmental benefit.But owing to also containing a lot of metallic impurity in copper-containing etching waste solution simultaneously, as Fe, Zn, Pb, Ca, Mg, Ni etc., what first the copper in recycling copper-containing etching waste solution needed in for the process of high-purity cupric sulfate purified to consider is the removal problem of impurity.
Summary of the invention
Object: the present invention is directed in copper-containing etching waste solution nickel content high, cause take copper-containing etching waste solution problem of nickel too high levels in copper sulfate when raw material is prepared cupric sulfate purified, the invention provides a kind of high-purity cupric sulfate purified except nickel technique, nickel content in the cupric sulfate purified that makes finally to prepare is not more than 10ppm, and it is low to have production cost, the advantage such as technique is simple.
Technical scheme: for solving the problems of the technologies described above, the technical solution used in the present invention is: 1. high-purity cupric sulfate purified, except nickel technique, is characterized in that this technique comprises the following steps:
(1) by acidic etching waste liquid and alkaline etching waste liquid for producing press filtration respectively, remove mechanical impurity;
(2) respectively acid and alkaline etching waste liquid for producing are carried out to deleading arsenic technique;
(3) under stirring, with the pH of basic solution adjustment of acidity etching waste liquor;
(4) acidic etching waste liquid is carried out to deliming, magnesium technique;
(5) alkaline etching waste liquid for producing is carried out to deliming, magnesium technique;
(6) reaction is completed to acidic etching waste liquid and alkaline etching waste liquid for producing sedimentation afterwards, filter;
(7) in, generate intermediate with acidic etching waste liquid and alkaline etching waste liquid for producing, except nickel;
(8) stir ageing, filter;
(9) washing;
(10) acidifying;
(11) crystallisation by cooling.
In described step (2), adopt magnesium chloride arsenic removal, with sodium sulfate and bariumchloride deleading.
Described step (3) neutral and alkali solution is Na
2cO
3or NaOH solution, the pH of adjustment of acidity etching waste liquor is 2.0～3.0.
In described step (6), add Polyferric Sulfate to play the effect of Flocculation Filter; Filter and adopt filter press, the specification of filter cloth filter cloth is 600～1000 orders.
In described step (7), neutralization acid and alkaline etching waste liquid for producing needs buffered soln, adds in advance NH in reactor
4cl solution or mother liquor are made buffered soln.
In described step (7), the neutralization of acidic etching waste liquid and alkaline etching waste liquid for producing adopts the mode of cocurrent adding material, and temperature of reaction is controlled 60～75 ℃, and process pH value is controlled at 3.5～4.3.
In described step (8), stirring digestion time is 10 minutes～1 hour; Filter and adopt Plate Filtration, filtrate collection is made buffered soln and is used.
In described step (9), washing adopts the mode of making beating washing, and washing water adopt pure water; Washing times is no less than 2 times.
In described step (10), adopt vitriol oil acidifying.
Beneficial effect: high-purity cupric sulfate purified of the present invention is except nickel technique, and purification, except nickel rate is high, reaches the removal effect to nickel by forming intermediate, makes the nickel content in the final cupric sulfate purified generating be not more than 10ppm; And it is low that technique of the present invention has production cost, and technique is simple, the copper sulfate purity advantages of higher of producing.
Accompanying drawing explanation
Fig. 1 is production process flow process figure of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
example 1:high-purity cupric sulfate purified, except nickel technique, comprises the following steps:
(1) by acidic etching waste liquid and alkaline etching waste liquid for producing press filtration respectively, remove mechanical impurity;
(2) respectively acid and alkaline etching waste liquid for producing are carried out to deleading arsenic technique;
(3) under stirring, with the pH of basic solution adjustment of acidity etching waste liquor, be 2.0～3.0;
(4) acidic etching waste liquid is carried out to deliming, magnesium technique;
(5) alkaline etching waste liquid for producing is carried out to deliming, magnesium technique;
(6) reaction is completed to acidic etching waste liquid and alkaline etching waste liquid for producing sedimentation afterwards, filter;
(7) in reactor, add in advance NH4Cl solution to make buffered soln, in and acidic etching waste liquid and alkaline etching waste liquid for producing generate intermediate, neutralization adopts the mode of cocurrent adding material, temperature of reaction is controlled 60 ℃, process pH value is controlled at 3.5, except nickel;
(8) stir ageing 10 minutes～1 hour, adopt Plate Filtration;
(9) with pure water washing 2 times;
(10) adopt vitriol oil acidifying;
(11) crystallisation by cooling.
With this high-purity cupric sulfate purified, be not more than 10ppm except the nickel ion content in the cupric sulfate purified of the final generation of nickel technique, qualified.
example 2-embodiment 6:
Use the technique deleading identical with embodiment 1, and carry out testing experiment.Difference is the difference of using respectively neutralization reaction temperature listed in table 1, neutralization reaction pH value, stirring digestion time, washing times; The test experiments result of prepared cupric sulfate purified is also shown in Table 1.
Table 1
| ? | Neutralization reaction temperature (℃) | Neutralization reaction pH value | Stirring digestion time (minute) | Washing times (inferior) | Calcium-magnesium content |
| Embodiment 1 | 60 | 3.5 | 10 | 2 | Qualified |
| Embodiment 2 | 65 | 3.7 | 20 | 5 | Qualified |
| Embodiment 3 | 70 | 4.0 | 30 | 3 | Qualified |
| Embodiment 4 | 75 | 4.3 | 40 | 6 | Qualified |
| Embodiment 5 | 65 | 4.0 | 50 | 2 | Qualified |
| Embodiment 6 | 60 | 3.5 | 60 | 2 | Qualified |
From the test result shown in table 1, can find out, with this high-purity cupric sulfate purified, all be not more than 10ppm except the nickel ion content in the cupric sulfate purified of the final generation of nickel technique, qualified.
Although above invention has been done to detailed explanation in conjunction with the embodiments,, person of ordinary skill in the field can understand, and not departing under the prerequisite of aim of the present invention, in claim protection domain, can also change or change etc. above-described embodiment.
Claims (5)
1. high-purity cupric sulfate purified, except nickel technique, is characterized in that this technique comprises the following steps:
(1) by acidic etching waste liquid and alkaline etching waste liquid for producing press filtration respectively, remove mechanical impurity;
(2) respectively acid and alkaline etching waste liquid for producing are carried out to deleading arsenic technique, wherein adopt magnesium chloride arsenic removal, with sodium sulfate and bariumchloride deleading;
(3) under stirring, with pH to 2.0～3.0 of basic solution adjustment of acidity etching waste liquor; Described basic solution is Na
2cO
3or NaOH solution;
(4) acidic etching waste liquid is carried out to deliming, magnesium technique;
(5) alkaline etching waste liquid for producing is carried out to deliming, magnesium technique;
(6) reaction is completed to acidic etching waste liquid and alkaline etching waste liquid for producing sedimentation afterwards, filter;
(7) in reactor, add in advance NH
4cl solution or mother liquor are made buffered soln, in and acidic etching waste liquid and alkaline etching waste liquid for producing pH value be controlled at 3.5～4.3, adopt the mode of cocurrent adding material, temperature of reaction is controlled 60～75 ℃, generates intermediate, removes nickel;
(8) stir ageing, filter;
(9) washing;
(10) acidifying;
(11) crystallisation by cooling.
2. high-purity cupric sulfate purified according to claim 1, except nickel technique, is characterized in that: in described step (6), add Polyferric Sulfate to play the effect of Flocculation Filter; Filter and adopt filter press, the specification of filter cloth is 600～1000 orders.
3. high-purity cupric sulfate purified according to claim 1, except nickel technique, is characterized in that: in described step (8), stirring digestion time is 10 minutes～1 hour; Filter and adopt Plate Filtration, filtrate collection is made buffered soln and is used.
4. high-purity cupric sulfate purified according to claim 1, except nickel technique, is characterized in that: in described step (9), washing adopts the mode of making beating washing, and washing water adopt pure water; Washing times is no less than 2 times.
5. high-purity cupric sulfate purified according to claim 1, except nickel technique, is characterized in that: in described step (10), adopt vitriol oil acidifying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210235287.7A CN102730745B (en) | 2012-07-09 | 2012-07-09 | Process for removing nickel from high-purity plating-stage copper sulfate |
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| CN201210235287.7A CN102730745B (en) | 2012-07-09 | 2012-07-09 | Process for removing nickel from high-purity plating-stage copper sulfate |
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| CN102730745B true CN102730745B (en) | 2014-01-22 |
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| CN105129838A (en) * | 2015-07-02 | 2015-12-09 | 清远市新绿环境技术有限公司 | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant |
| CN110228814B (en) * | 2019-07-23 | 2021-08-17 | 深圳市海文环保技术有限公司 | Impurity removal method and impurity removal equipment applied to copper sulfate preparation process |
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