CN102730746A - Process of removing tin from high-purity plating-stage copper sulfate - Google Patents
Process of removing tin from high-purity plating-stage copper sulfate Download PDFInfo
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- CN102730746A CN102730746A CN2012102353723A CN201210235372A CN102730746A CN 102730746 A CN102730746 A CN 102730746A CN 2012102353723 A CN2012102353723 A CN 2012102353723A CN 201210235372 A CN201210235372 A CN 201210235372A CN 102730746 A CN102730746 A CN 102730746A
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Abstract
The main content of the invention is to take the etching waste liquor containing copper as raw material to remove impurity tin in the etching waste liquor with copper by adopting the process of purifying and removing tin so as to ensure that the tin content in the finally produced plating-stage copper sulfate is not greater than 5 ppm and meet the requirements of products at the excellent national grade. 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; (3) neutralizing acidity and alkali to produce copper-salt sediment; (4) washing and purifying the copper-salt sediment; (5) acidizing the concentrated sulfuric acid; and (6) cooling and crystallizing to form copper sulfate crystallization. The process has the advantages of low production cost, simple technology, high purity of produced copper sulfate and high tin removing rate.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of high-purity plating grade bluestone deleading technique.
Background technology
Copper sulfate is most important a kind of mantoquita in the copper compound, and is of many uses.In the industry, being the compound that raw material can prepare copper and a series of copper with copper sulfate, is important chemical material; On the agricultural, copper sulfate is important inorganic pesticide raw material, or important trace mineral supplement in the animal-feed; Copper sulfate can also be as the mordant of fabric, wood preservative, coating etc.Electroplating grade bluestone has important use in electroplating industry, along with developing rapidly of China's non-metal electroplating, decorative electroplating and printed circuit board industry, the demand of electroplating grade bluestone is increased sharply.Electroplate grade bluestone and require the purity of copper sulfate high, foreign matter content is low, metallic impurity such as Fe, Ni, Zn, Ca, Pb particularly, and the Pb content that GB requires to electroplate the grade bluestone premium grads is not more than 5ppm.
In recent years along with electronic industry the developing rapidly of China, also develop rapidly as the printed substrate (being called for short PCB) of electron device and electronic devices and components supporter, output increases year by year, the environmental problem of thereupon bringing is also serious day by day.The PCB industry can produce a large amount of copper-containing etching waste solutions, because the copper content in the etching waste liquor up to 150 ~ 200g/L, is arbitrarily discharged, can cause serious harm to environment, is not only a kind of source of pollution, especially a kind of waste of resource.Realize the recycling of copper in the etching waste liquor, can cut the waste, reduce harm simultaneously environment.The recycling mode of existing etching waste liquor is more, and wherein a kind of recoverying and utilizing method is produced copper sulfate with etching waste liquor exactly.Electroplating grade bluestone has higher economic benefit than technical grade copper sulfate, utilizes copper-containing etching waste solution directly to prepare high-purity plating grade bluestone and has bigger profit margin, and product has more the market competitiveness.But outside copper removal in the etching waste liquor; The metallic impurity that also contain other; Like Fe, Ni, Zn, Ca, Pb etc., require the content of metallic impurity very low and electroplate grade bluestone, so how to realize that the purification and impurity removal in the copper-containing etching waste solution is the urgent and challenging work of tool.
Plumbous (Pb); Be a kind of beavy metal impurity in the copper-containing etching waste solution, well-known, all solubility lead salts are virose; Be dissolved in the water body; When concentration surpasses 0.1mg/L, all can produce harm, when the plumbous amount of picked-up every day surpasses 0.3 ~ 1.0mg, just can in human body, accumulate, cause anaemia, neuritis, cancer etc. human body, fishery and agricultural irrigation.And lead can't be degraded in environment, still keeps its characteristic in case enter environment for a long time." integrated wastewater discharge standard " classified lead as first kind pollutent, and the emission standard of clearly stipulating lead waste water in the GB emission standard is plumbous total content≤1mg/L.Stipulated the material and the technological standards of electronic product among the RoHS, content plumbous in the electronic product has been made strict qualification.Electroplate the important source material of grade bluestone as electroplating industry, its impurity Pb can enrichment in wiring board, and the discharging of lead waste water can cause that serious environmental pollutes, so will introduce deleading technique utilizing the etching waste liquor preparation to electroplate in the technology of grade bluestone.
Summary of the invention
Purpose: the present invention is exactly to the leaded high problem of copper sulfate lead content that generates of causing of above-mentioned copper-containing etching waste solution; Provide a kind of copper-containing etching waste solution to purify the technology of deleading; Purification deleading through to copper-containing etching waste solution is handled, and makes the lead content in the plating grade bluestone of finally preparing drop to 5ppm and following, reaches the standard that GB quality product level is electroplated grade bluestone; Advantages such as it is low to have production cost, and technology is simple.
Technological principle:
Ba
2?++?Pb
2+?+?2SO
4 2-=?BaPb(SO
4)
2?
According to Solubility-Product Principle, the Ba in solution
2+With SO
4 2-Concentration is greater than BaSO
4During solubility product, permanent white just generates with precipitation forms, meanwhile, and the Pb in the solution
2+With SO
4 2-Form lead sulfate with the permanent white coprecipitation, thereby the lead in the solution is removed.
Technical scheme: for solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of high-purity plating grade bluestone deleading technique is characterized in that this technology may further comprise the steps:
(1) with acidic etching waste liquid and alkaline etching waste liquid for producing press filtration respectively, removes mechanical impurity;
(2) take by weighing the Na of certain mass
2SO
4And the soluble barium salt, be dissolved in wiring solution-forming in the water respectively;
(3) under agitation with barium salt solution and Na
2SO
4Solution adds in acidic etching waste liquid and the alkaline etching waste liquid for producing, continues stirring reaction for some time after adding;
(4) will react completion acidic etching waste liquid and alkaline etching waste liquid for producing sedimentation afterwards, filter;
(5) in acidic etching waste liquid and alkaline etching waste liquid for producing;
(6) ageing is filtered;
(7) washing;
(8) acidifying;
(9) crystallisation by cooling.
As of the present invention preferred, in the present invention, the concentration of acidic etching waste liquid and alkaline etching waste liquid for producing is 1～10% in the said step (1), and described acidic etching waste liquid is one or more in cupric chloride, cupric nitrate or the copper sulfate etching waste liquor; Filter press is adopted in press filtration in the said step (1), and the specification of filter cloth is 600～1000 orders.
As of the present invention preferred, in the present invention, Na in the said step (2)
2SO
4Consumption be 2～3 kilograms/10 tons acidic etching waste liquids or alkaline etching waste liquid for producing, concrete add-on is calculated with measuring according to acidic etching waste liquid and alkaline etching waste liquid for producing; The soluble barium salt is BaCl in the said step (2)
2Or Ba (NO
3)
2, soluble barium salt's quality is according to stoichiometric ratio and Na
2SO
4Consumption corresponding.
As of the present invention preferred, in the present invention, barium salt solution and Na in the said step (3)
2SO
4Being incorporated as simultaneously of solution adds, and the adding completion continued stirring reaction time is not less than 30 minutes.
As of the present invention preferred, in the present invention, filter press is adopted in the press filtration in the said step (4) after acidic etching waste liquid and the alkaline etching waste liquid for producing deleading, and the specification of filter cloth filter cloth is 600～1000 orders.
As of the present invention preferred, in the present invention, the pH value is 4.7～5.2 after the neutralization of middle acidic etching waste liquid of said step (5) and alkaline etching waste liquid for producing.
As of the present invention preferred, in the present invention, the mode of making beating washing is adopted in washing in the said step (7), and pure water is adopted in washing, and washing times is no less than 2 times.
As of the present invention preferred, in the present invention, adopt vitriol oil acidifying in the said step (8).
Beneficial effect: high-purity plating grade bluestone deleading technique of the present invention, it is high to purify the deleading rate, makes the lead content in the plating grade bluestone of final generation be not more than 5ppm, reaches the requirement of GB premium grads; And technology of the present invention has that production cost is low, and technology is simple, and the copper sulfate purity of producing is high, deleading rate advantages of higher.
Description of drawings
Fig. 1 is production process flow process figure of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Instance 1:
High-purity plating grade bluestone deleading technique comprises the steps: that (1) adopt filter press respectively with acidic etching waste liquid and alkaline etching waste liquid for producing, removes mechanical impurity;
(2) be 2 kilograms of Na according to per 10 tons of etching waste liquor consumptions
2SO
4, take by weighing the Na of equimolar amount
2SO
4And BaCl
2, be dissolved in wiring solution-forming in the water respectively;
(3) under agitation with BaCl
2Solution and Na
2SO
4Solution adds in acidic etching waste liquid etching waste liquor and the alkaline etching waste liquid for producing simultaneously, continues stirring reaction 1 hour after adding;
(4) will react completion acidic etching waste liquid and alkaline etching waste liquid for producing sedimentation afterwards, adopt filter press;
(5) make pH value to 4.7～5.2 with acidic etching waste liquid and alkaline etching waste liquid for producing in;
(6) ageing is filtered;
(7) with pure water making beating washing 2 times;
(8) use vitriol oil acidifying;
(9) crystallisation by cooling.
Lead content with in the plating grade bluestone of the final generation of this high-purity plating grade bluestone deleading technique is not more than 5ppm, reaches the requirement of GB premium grads.
Instance 2-embodiment 6:
Use the technology deleading identical, and carry out testing experiment with embodiment 1.Difference is respectively listed different soluble barium salts, stirring reaction time in the use table 1, washing times.The test experiments result of prepared plating grade bluestone also is shown in Table 1.
Table 1
Can find out from the test result shown in the table 1, all be not less than 5ppm, reach the requirement of GB premium grads with the lead content in the plating grade bluestone of the final generation of this high-purity plating grade bluestone deleading technique.
Below disclose the present invention with preferred embodiment, so it is not in order to restriction the present invention, and all employings are equal to replacement or the technical scheme that obtained of equivalent transformation mode, all drop within protection scope of the present invention.
Claims (8)
1. high-purity plating grade bluestone deleading technique is characterized in that this technology may further comprise the steps:
(1) with acidic etching waste liquid and alkaline etching waste liquid for producing press filtration respectively, removes mechanical impurity;
(2) take by weighing the Na of certain mass
2SO
4And the soluble barium salt, be dissolved in wiring solution-forming in the water respectively;
(3) under agitation with barium salt solution and Na
2SO
4Solution adds in acidic etching waste liquid and the alkaline etching waste liquid for producing, continues stirring reaction for some time after adding;
(4) will react completion acidic etching waste liquid and alkaline etching waste liquid for producing sedimentation afterwards, filter;
(5) in acidic etching waste liquid and alkaline etching waste liquid for producing;
(6) ageing is filtered;
(7) washing;
(8) acidifying;
(9) crystallisation by cooling.
2. high-purity plating grade bluestone deleading technique according to claim 1; It is characterized in that: the concentration of acidic etching waste liquid and alkaline etching waste liquid for producing is 1～10% in the said step (1), and described acidic etching waste liquid is one or more in cupric chloride, cupric nitrate or the copper sulfate etching waste liquor; Filter press is adopted in press filtration in the said step (1), and the specification of filter cloth is 600～1000 orders.
3. high-purity plating grade bluestone deleading technique according to claim 1 is characterized in that: Na in the said step (2)
2SO
4Consumption be 2～3 kilograms/10 tons acidic etching waste liquids or alkaline etching waste liquid for producing, concrete add-on is calculated with measuring according to acidic etching waste liquid and alkaline etching waste liquid for producing; The soluble barium salt is BaCl in the said step (2)
2Or Ba (NO
3)
2, soluble barium salt's quality is according to stoichiometric ratio and Na
2SO
4Consumption corresponding.
4. high-purity plating grade bluestone deleading technique according to claim 1 is characterized in that: barium salt solution and Na in the said step (3)
2SO
4Being incorporated as simultaneously of solution adds, and the adding completion continued stirring reaction time is not less than 30 minutes.
5. high-purity plating grade bluestone deleading technique according to claim 1 is characterized in that: filter press is adopted in the press filtration in the said step (4) after acidic etching waste liquid and the alkaline etching waste liquid for producing deleading, and the specification of filter cloth filter cloth is 600～1000 orders.
6. high-purity plating grade bluestone deleading technique according to claim 1 is characterized in that: the pH value is 4.7～5.2 after the neutralization of middle acidic etching waste liquid of said step (5) and alkaline etching waste liquid for producing.
7. high-purity plating grade bluestone deleading technique according to claim 1 is characterized in that: the mode of making beating washing is adopted in washing in the said step (7), and pure water is adopted in washing, and washing times is no less than 2 times.
8. high-purity plating grade bluestone deleading technique according to claim 1 is characterized in that: adopt vitriol oil acidifying in the said step (8).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102353723A CN102730746A (en) | 2012-07-09 | 2012-07-09 | Process of removing tin from high-purity plating-stage copper sulfate |
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|---|---|---|---|
| CN2012102353723A CN102730746A (en) | 2012-07-09 | 2012-07-09 | Process of removing tin from high-purity plating-stage copper sulfate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630826A (en) * | 2015-01-29 | 2015-05-20 | 中南大学 | Technique for recovering tin from tin anode sludge |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372431A (en) * | 2010-08-09 | 2012-03-14 | 深圳市格林美高新技术股份有限公司 | Method for treating waste and old lead-containing glass |
-
2012
- 2012-07-09 CN CN2012102353723A patent/CN102730746A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372431A (en) * | 2010-08-09 | 2012-03-14 | 深圳市格林美高新技术股份有限公司 | Method for treating waste and old lead-containing glass |
Non-Patent Citations (2)
| Title |
|---|
| 李国斌等: "从含铜蚀刻废液中回收硫酸铜", 《无机盐工业》, vol. 37, no. 2, 28 February 2005 (2005-02-28) * |
| 杨晓娇: "硫酸钡共沉淀法从镍电积阳极液中除铅的研究", 《中国稀土学报》, vol. 28, 30 April 2010 (2010-04-30) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630826A (en) * | 2015-01-29 | 2015-05-20 | 中南大学 | Technique for recovering tin from tin anode sludge |
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Application publication date: 20121017 |