CN102963921A - Preparation method of electroplating-grade copper sulfate - Google Patents
Preparation method of electroplating-grade copper sulfate Download PDFInfo
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- CN102963921A CN102963921A CN2012105531718A CN201210553171A CN102963921A CN 102963921 A CN102963921 A CN 102963921A CN 2012105531718 A CN2012105531718 A CN 2012105531718A CN 201210553171 A CN201210553171 A CN 201210553171A CN 102963921 A CN102963921 A CN 102963921A
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Abstract
The invention relates to a preparation method of electroplating-grade copper sulfate. The preparation method comprises the following steps: step I: mixing water with industrial-grade copper oxide according to the weight ratio of 3.4-3.7: 1 and beating to form mixed slurry; step II: adding acid liquor into the mixed slurry for acidification; regulating the pH of the mixed slurry to 1-2, and stirring and reacting for 1.5-3h to form a mixed system; step III: adding the acid liquor to regulate the pH of the mixed system to below 1, and cooling and crystallizing the mixed system; and step IV: performing solid-liquid separation on the mixed system to get a copper sulfate crystal. The preparation method disclosed by the invention has the advantages of simplicity and easiness in operation and low treatment cost; and produced electroplating-grade copper sulfate is very low content of impurities, is completely in line with a national standard, can be suitable for market demands and further has higher economic benefits.
Description
Technical field
The present invention relates to the mantoquita production technique, the novel process that especially a kind of cupric sulfate purified is produced.
Background technology
In China, the production method of copper sulfate is a lot, and it is also more extensive to originate, but great majority produce still with by-product recovery, or utilizes the copper scrap acidification and get.Therefore, for now, the production of copper sulfate product is still in the roughing mode as main, main production agricultural grade and technical grade copper sulfate.
At present, copper sulfate is produced raw material and is mainly contained waste electrolyte, waste product copper, printed circuit board etching waste solution, Copper Ores, copper metallurgy cigarette ash and the waste residue that copper electrolyzing refining produces.The roughly method of copper sulfate production mainly contains ammonia leaching process, catalytic oxidation, acid-base neutralisation method and extraction process.
(1) ammonia leaching process
Ammonia leaching process mainly is to utilize Cu and NH
3H
2O reaction under the condition of heating generates cupric ammine complex, and cupric ammine complex is processed through ammonia steaming system ammonia still process and generated ventilation breather, and then ventilation breather can produce copper sulfate with the dilute sulphuric acid acidification.Mention such as patent CN97115802.9 and to make in this way, the CN97115802.9 patent characteristic is with the solution that ammonia and bicarbonate of ammonia are made welding wire to be soaked moltenly, and ammonia concentration is 1.5 ~ 10mol/L in the solution, and material molar ratio is Cu:NH
3: NH
4HCO
3=1:2 ~ 4:1 ~ 2, the filtering and heating crystallization gets ventilation breather; Use again its oxygenerating copper or copper sulfate.
The characteristics one of present method are that the waste material utilization is drawn materials conveniently, and Recycling Mother Solution is used, and is with low cost; The 2nd, product purity is high, environmental contamination reduction; The 3rd, using value is high.Shortcoming is exactly to need to consume a large amount of ammoniacal liquor and perishable to equipment.
(2) catalytic oxidation
Catalytic oxidation mainly refers under the medium of dilute sulphuric acid, utilizes airborne dioxygen oxidation metallic copper to generate cupric oxide, and then cupric oxide generates copper sulfate under the effect of dilute sulphuric acid.Catalytic oxidation comprises room-temperature catalytic oxidation method and high-temperature catalytic oxidation style, patent CN89104857.X mentions and making in this way, mention the existing copper sulfate production technique of present the method and have two kinds, a kind of is with air the copper oxidation to be generated copper sulfate in the dilute sulphuric acid of heating, another kind is to produce copper sulfate with the cupric chloride method, the former energy consumption is large, and equipment is perishable; The latter is that raw materials cost is high.This patent is to have under the existence of copper sulfate, makees catalyzer with hydrochloric acid, at normal temperatures copper sulfate is produced in the copper oxidation, overcomes above-mentioned shortcoming, less investment, and simple to operate, economical efficiency and social benefit are remarkable.Shortcoming uses hydrochloric acid to make catalyzer exactly, will introduce a large amount of chlorions during production, affects the quality of copper sulfate product.
(3) extraction process
Extraction process mainly is thick cupric sulphate crystal or copper alloy dissolving, it is carried out solvent extraction process, and makes copper-bath carry out recrystallization, thereby produces copper sulfate product high-quality, purity.CN200480023147.7 has mentioned the method such as patent, and the copper sulfate quality that this method is produced is high, but needs to use thick copper sulfate as raw materials for production, and its production cost is larger.
(4) acid-base neutralisation method
The acid-base neutralisation method refers to that mainly sour the neutralization with alkali produces a large amount of copper sludges, and copper sludge generates the copper sulfate product through sulfuric acid acidation processing, crystallization reaction.Less investment of the present invention, instant effect, simple to operate, non-secondary pollution fully and completely disposes waste liquid, and is conducive to environment protection.But it is higher to produce the copper sulfate foreign matter content that obtains, and directly affects the quality of product.
Summary of the invention
, complex process not high in view of the copper sulfate product purity of present technology output, high in cost of production defective, the production method of therefore developing a kind of high-quality cupric sulfate purified product is very necessary.
The invention provides a kind of preparation method of cupric sulfate purified, comprise the steps:
Step I: be that 3.4 ~ 3.7:1 mix making beating with the technical grade cupric oxide according to mass ratio with water, form mixed slurry;
Step II: add acid solution in the mixed slurry and carry out acidifying; And the pH that regulates mixed slurry is 1 ~ 2, and stirring reaction 1.5 ~ 3h forms mixed system;
Step III: add acid solution and regulate described mixed system pH less than 1, and make described mixed system crystallisation by cooling in cooling recirculation system;
Step IV: described mixed system is carried out obtaining copper sulfate mother liquor and copper sulfate crystal after the solid-liquid separation, obtain cupric sulfate purified (CuSO after the oven dry
45H
2O) product.
Preferably, in order to obtain preferably acidizing effect, the pH that further controls mixed slurry in the described step II is 1.4 ~ 1.8.
Preferably, also comprise the tail gas absorption step in the described step II, absorb the acidic substance that volatilize by tail gas absorbing system.Because the vitriol oil and cupric oxide, water hybrid reaction can produce a large amount of heat, even the solution local boiling be can allow, a large amount of acid mists or acid vapors produced.
Preferably, described acid solution is the technical grade vitriol oil, and run-of-the-mill per-cent is 98%.
Preferably, in order to obtain better crystallization effect, effectively save sour consumption, control cost, the pH value 0.3 ~ 0.5 of control mixed system in the described step III.
Preferably, treat that the mixed system temperature of described step III is down to below 40 ℃, carry out again solid-liquid separation.
Preferably, described step IV also comprises washs described copper sulfate crystal, and obtains washings.
Preferably, the copper sulfate mother liquor is circulated in the step II together with described washings and replaces the part acid solution that described mixed slurry is carried out acidifying in the described step IV.
Beneficial effect: the preparation method of cupric sulfate purified of the present invention is simple, processing cost is low, mother liquor can reclaim use, the cupric sulfate purified product foreign matter content of producing is very low, be up to state standards fully, greatly improve copper sulfate product salt quality and meeting the market requirement, have higher economic benefit.
Description of drawings
Fig. 1 is the making schematic flow sheet of the embodiment of the invention 1.
Embodiment
Below in conjunction with specific embodiment the present invention is described in more details, protection scope of the present invention includes but not limited to following examples.
Embodiment 1
The technical grade cupric oxide of present embodiment is from certain environmental protection company, mainly is that the form with solid powdery exists.Wherein, the copper content of technical grade cupric oxide is 58%, cl content is 0.11%, moisture content is 22%.
Adopting above-mentioned technical grade cupric oxide to prepare technical grade, to electroplate the step of copper sulfate as follows, as shown in Figure 1:
Step I: with 3.5m
3Tap water is added in the souring tank, opens whipping appts, adds simultaneously 1t technical grade cupric oxide mixing making beating, and reaction 10min obtains mixed slurry.With tap water industrial cupric oxide is diluted making beating, help to clean the lip-deep chlorion of cupric oxide and other impurity, and further so that more complete during acidification reaction.
Step II: at first, open the souring tank tail gas absorbing system.Because the vitriol oil and cupric oxide, water hybrid reaction can produce a large amount of heat, even can allow the solution local boiling, produce a large amount of acid mists or acid vapors, therefore need to cooperate tail gas absorbing system to collect and processing.Then, add 98% the technical grade vitriol oil in the mixed slurry that forms to the step I and carry out acidifying, the pH that regulates mixed slurry is 1.5.Add the beginning timing from the vitriol oil, stirring reaction 2h forms mixed system to reacting complete.Wherein, the main component of mixed system is copper sulfate.
The reaction principle of this step is: can emit a large amount of heat when the cupric oxide after making beating is processed and strong sulfuric acid response, the temperature of solution sharply rises, major cause is because the vitriol oil has strong oxidizing property, cupric oxide after the making beating mixes with water along with being stirred in rotation, the vitriol oil is met water and is emitted a large amount of heat, the heat that the vitriol oil is emitted helps cupric oxide and sulfuric acid system reaction rate accelerates, its reaction process was divided into for two steps, the first step is that the cupric oxide reaction generates copper hydroxide, second step is the continuation adding along with the vitriol oil, and temperature rises to 98 ℃ of copper hydroxides reactions and generates the copper sulfate hot solution.Concrete reaction equation is as follows:
2CuO+H
2SO
4(dense) → Cu (OH)
2+ CuSO
4
Cu (OH)
2+ H
2SO
4(dense) → 2H
2O+CuSO
4
The step III: the mixed system that the step II is formed is transferred to and carries out crystallisation by cooling in the crystallizer.In the process, adopt water as refrigerant, open cooling recirculation system and make the mixed system crystallisation by cooling.Add simultaneously 98% the technical grade vitriol oil and mend acid treatment, regulating described mixed system pH is 0.3.In the process of mending acid, along with the drop in temperature copper sulfate crystal has begun crystallization, get the 100mL mixed system every 1h and place beaker this moment, with thermometer mixed system carried out temperature detection, the fractional crystallization of preparing when measuring temperature near 40 ℃ to be checked.
The effect of mending acid have following some:
1. generate because cupric oxide and the vitriol oil have the hydroxide copper sludge in the souring tank reaction process, have copper sludge to adhere in crystallisation process for fear of the copper sulfate hydrothermal solution, affect the copper sulfate quality product, need be mended acid treatment to the copper sulfate hydrothermal solution.
2. mend the pH ﹤ 1 that the copper sulfate hot solution is regulated in acid, improve the free acid content in the copper sulfate hot solution, a ketone-sulphoxylate yield is improved, crystal is large.
3. mend the vitriol oil in the crystallisation process, copper sulfate hot solution temperature is raise again, thereby the crystal of separating out is dissolved again, the copper sulfate crystal that helps again to separate out is grown slightly, helps to improve output.
The step IV: treat that described mixed system temperature is down to below 40 ℃, contain a large amount of solid-state copper sulfate crystal and mother liquors this moment in the mixed system, shifts the solid-liquid separation that mixed system carries out mother liquor and sulfuric acid crystal to the vacuum filtration device.Temperature is below 40 ℃, crystallization and the crystal that separates out can get more and more in the mother liquor, help to improve the amount of separating out of copper sulfate crystal and improve whole output, but temperature should not too low (can not be lower than 38 ℃), temperature is lower than 38 ℃, and then can produce a large amount of white fineves affects quality product.Temperature is higher than 40 ℃ and then contains a large amount of crystal in the mother liquor and do not separate out, and affects output.Therefore mixing system being carried out the preferred temperature that suction filtration reaches solid-liquid separation is controlled between 38 ℃ to 40 ℃.
Water washs the copper sulfate crystal that suction filtration obtains, and washings is kept in through thrust-augmenting nozzle overflow to copper sulfate mother liquor tank together with the mother liquor that suction filtration obtains.Since copper sulfate mother liquor acidity very high (pH is less than 1), and copper content is also higher, directly falls both to increase cost as liquid waste disposal, causes again waste.Therefore the copper sulfate mother liquor is circulated in the souring tank as acid regulator solution reuse together with washing liq.And copper sulfate crystal carries out the centrifugal drying water treatment, copper sulfate crystal is dried after getting rid of the water droplet that copper sulfate crystal shows absorption through whizzer is centrifugal, and packing is cupric sulfate purified (CuSO after the oven dry
45H
2O) product.
Carry out respectively five parallel tests according to above-mentioned preparation method, the cupric sulfate purified quality product of acquisition
Detect as follows:
Table 1 cupric sulfate purified product detects index
As can be seen from the above data, it is all lower that the cupric sulfate purified that uses the technical grade cupric oxide to produce respectively detects index, and the As of 5 copper sulfate samples, Ni, Pb, Ca, Fe, Co, Zn, III IV water-insoluble all reach the cupric sulfate purified quality standard.
Embodiment 2
The technical grade cupric oxide main ingredient content (massfraction) of present embodiment is: copper content 58.38%, cl content are 0.09%, moisture content is 24.37%.
In the present embodiment, be successively to add tap water 3.7m in the step I with embodiment 1 difference
3, 1t technical grade cupric oxide, forming tap water and technical grade cupric oxide mass ratio is 3.7:1.
The technical grade vitriol oil of adding 98% carries out acidifying in the step II, regulates the pH to 1.4 of mixed slurry, and keeping the stirring reaction time is that 2.5h forms mixed system.
Mixed system pH regulator in the step III after the benefit acid treatment is 0.5.
All the other step reference examples 1 are described.
It is as follows that product after the test respectively detects index:
Table 2 cupric sulfate purified product detects index
Can be learnt that by test-results the product of the cupric sulfate purified products production that present embodiment obtains reaches the premium grads standard of national cupric sulfate purified product.
Cupric sulfate purified making method of the present invention, the production technique simple possible has satisfied the demand of client for quality product, the requirement of realistic production application and market development.
Claims (8)
1. the preparation method of a cupric sulfate purified is characterized in that, comprises the steps:
Step I: be that 3.4 ~ 3.7:1 mix making beating with the technical grade cupric oxide according to mass ratio with water, form mixed slurry;
Step II: add acid solution in the mixed slurry and carry out acidifying; And the pH that regulates mixed slurry is 1 ~ 2, and stirring reaction 1.5 ~ 3h forms mixed system;
Step III: add acid solution and regulate described mixed system pH less than 1, and make described mixed system crystallisation by cooling in cooling recirculation system;
Step IV: described mixed system is carried out obtaining copper sulfate mother liquor and copper sulfate crystal after the solid-liquid separation the dry rear cupric sulfate purified product that obtains.
2. described preparation method according to claim 1 is characterized in that, the pH of control mixed slurry is 1.4 ~ 1.8 in the described step II.
3. described preparation method according to claim 1 and 2 is characterized in that, also comprises the tail gas absorption step in the described step II, absorbs the acidic substance that volatilize by tail gas absorbing system.
4. described preparation method according to claim 1 is characterized in that described acid solution is the technical grade vitriol oil.
5. described preparation method according to claim 1 is characterized in that, the pH value 0.3 ~ 0.5 of control mixed system in the described step III.
6. described preparation method according to claim 1 is characterized in that the mixed system temperature is down to below 40 ℃ in the described step III.
7. according to claim 1 or 6 described preparation methods, it is characterized in that described step IV also comprises washs described copper sulfate crystal, and obtain washings.
8. described preparation method according to claim 6 is characterized in that, the copper sulfate mother liquor is circulated to together with described washings and replaces the part acid solution that described mixed slurry is carried out acidifying in the step II in the described step IV.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693673A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Producing method for producing electroplating grade copper sulfate with acid copper-bearing waste etching liquid |
| CN103739000A (en) * | 2013-12-25 | 2014-04-23 | 广州科城环保科技有限公司 | Production method of high-purity electroplating grade copper oxide |
| CN104108740A (en) * | 2014-08-05 | 2014-10-22 | 浙江科菲科技股份有限公司 | Novel method for selectively producing high-quality copper sulfate from copper-containing wastes |
| CN104611572A (en) * | 2015-01-13 | 2015-05-13 | 武汉工程大学 | Method for preparing copper sulfate through wet oxidation of copper concentrate |
| CN113213525A (en) * | 2021-05-25 | 2021-08-06 | 广东致卓环保科技有限公司 | Preparation process of copper sulfate pentahydrate with spherical crystal form |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275753A (en) * | 2022-01-21 | 2022-04-05 | 上海太洋科技有限公司 | Preparation method of high-purity copper metaphosphate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693673A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Producing method for producing electroplating grade copper sulfate with acid copper-bearing waste etching liquid |
| CN103739000A (en) * | 2013-12-25 | 2014-04-23 | 广州科城环保科技有限公司 | Production method of high-purity electroplating grade copper oxide |
| CN103739000B (en) * | 2013-12-25 | 2015-11-18 | 广州科城环保科技有限公司 | A kind of production method of high-purity plating-grade copper oxide |
| CN103693673B (en) * | 2013-12-25 | 2016-08-31 | 广州科城环保科技有限公司 | A kind of production method utilizing acid copper-containing etching waste solution to produce cupric sulfate purified |
| CN104108740A (en) * | 2014-08-05 | 2014-10-22 | 浙江科菲科技股份有限公司 | Novel method for selectively producing high-quality copper sulfate from copper-containing wastes |
| CN104108740B (en) * | 2014-08-05 | 2015-09-30 | 浙江科菲科技股份有限公司 | A kind of novel method of selectivity production high-quality copper sulfate from copper-bearing waste material |
| CN104611572A (en) * | 2015-01-13 | 2015-05-13 | 武汉工程大学 | Method for preparing copper sulfate through wet oxidation of copper concentrate |
| CN113213525A (en) * | 2021-05-25 | 2021-08-06 | 广东致卓环保科技有限公司 | Preparation process of copper sulfate pentahydrate with spherical crystal form |
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Effective date of registration: 20161019 Address after: 518104, Guangdong, Shenzhen, Baoan District manhole Street neighborhood Republican office building 8, two floor Patentee after: Shenzhen Baoan Dongjiang Environmental Protection Technology Co., Ltd. Address before: 518057 Guangdong province Shenzhen city Nanshan District high tech park, North Long Road No. 9 building, 10 floor, Dongjiang environmental Patentee before: Dongjiang Environmental Co., Ltd. |