CN101445952B - Purifying treatment method for waste silver electrolyte - Google Patents
Purifying treatment method for waste silver electrolyte Download PDFInfo
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- CN101445952B CN101445952B CN 200810143885 CN200810143885A CN101445952B CN 101445952 B CN101445952 B CN 101445952B CN 200810143885 CN200810143885 CN 200810143885 CN 200810143885 A CN200810143885 A CN 200810143885A CN 101445952 B CN101445952 B CN 101445952B
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Abstract
The invention discloses a purifying treatment method for waste silver electrolyte. The method aims to hydrolyze and precipitate impurity ions of copper and bismuth in the waste silver electrolyte through ammonia water neutralization and precipitation and separation, so as to purify silver electrolyte and improve quality and reclaiming ratio of silver powder. The method comprises the following method: A, ammonia water neutralization, namely, injecting the waste silver electrolyte containing silver, copper and bismuth ions into a neutralizing tank for mechanically stirring, adding ammonia waterduring stirring to neutralize, controlling pH value of the waste electrolyte to be 5 to 6, and hydrolyzing and precipitating the copper ions and the bismuth ions in the waste electrolyte; and B, precipitation and separation, namely, firstly stopping stirring, keeping the hydrolyzed waste electrolyte standing for at least 24 hours in the neutralizing tank or a precipitation tank to carry out precipitation and separation, returning the precipitated solution to be used as electrolyte, and conveying precipitated dregs after being washed and filtered to a converter for smelting. The method is mainly used for removing the impurity ions of copper and bismuth in the waste silver electrolyte.
Description
Technical field
The present invention relates to a kind of cleaning method of waste silver electrolyte.More particularly, relate to a kind of method that copper, bismuth foreign ion are removed in hydrolysis from waste silver electrolyte.
Background technology
The processing of waste silver electrolyte is that silver is smelted an important step in producing, and directly the quality of silver powder is separated out in impact.On the one hand electrolytic solution is by after certain production time in silver-colored electrolysis production, and impurity wherein is such as Cu
2+(bivalent cupric ion), Bi
3+Impurity such as (trivalent bismuth ions) is accumulation constantly, and the quality of silver powder is separated out in impact, must regularly process; Silver-colored electrolysis contains the method processing that the processing of the impurity such as Cu, Bi in the nitric acid waste electrolyte all is the employing thermolysis all the time on the other hand, the method adopts the straight fire of gas heating concentrated, nitric acid is decomposed efflux a large amount of oxynitride obnoxious flavour of generation, though through the nitric acid tail gas treatment system, but poor effect causes the severe contamination to environment.And need to expend a large amount of water and coal gas, steam, the treatment time is longer, processes the time that once electrolytic liquid approximately needs a week.
Summary of the invention
The object of the present invention is to provide a kind of cleaning method of waste silver electrolyte, the method is by adding ammoniacal liquor in waste silver electrolyte under room temperature and mechanical stirring, control the pH value of waste liquid, making the Cu in this waste liquid
2+And Bi
3+Hydrolytic precipitation gets off and is removed, and Ag
+Then stay behind the hydrolytic precipitation in the liquid and return silver-colored electrolyzer, remove the purpose that impurity improves quality of cathode silver and the rate of recovery thereby reach.
For achieving the above object, technical solution of the present invention is: will contain Ag
+, Cu
2+, Bi
3+Deng waste silver electrolyte inject in the neutralizing well, under room temperature and churned mechanically condition, add ammonia neutralization, the pH value of control waste liquid, hydrolysis removes Bi in the scope of 3.5-4.5
3+, in the scope of 5.0-6.0, remove Cu
2+, the rear liquid of hydrolysis leaves standstill and carried out precipitate and separate at least in 24 hours, and liquid returns and does the silver electrolyte use after the precipitation, and precipitation slag then send the converter melting after washing, filtration.
Although also can add the pH value that NaOH (caustic alkali) adjusts solution in waste silver electrolyte, the NaOH adition process namely generates bolarious silver suboxide precipitation, causes a large amount of losses of noble silver, and its chemical equation is as follows:
2AgNO
3+2NaOH＝2NaNO
3+Ag
2O↓+H
2O
Owing to adding NaOH neutralization reaction speed, its add-on is difficult control, although the impurity hydrolytic precipitation is more complete in the rear liquid of neutralization, and Ag in the solution
+(silver ions) also is hydrolyzed thereupon and precipitates, Ag in the liquid after the neutralization
+Loss is larger.So, should not select NaOH to adjust the pH value of solution.
Ammonia neutralization is to utilize the degree of stability of material in the aqueous solution to depend primarily on the pH value of solution, this basic theory of the activity alpha of current potential E and reaction, difference according to the activity of pH value, current potential and the reaction of each impurity in the electrolytic solution, regulate the pH value of electrolytic solution, make impurity in electrolytic solution hydrolytic precipitation and being removed in its corresponding pH value scope.Relevant Me-H
2O is E
0-pH
0Numerical value sees Table 1.
The relevant Me-H of table 1
2O is E
0-pH
0Numerical value
As can be known from Table 1, select the pH value in the 4.6-6.32 scope, can make BiO in the solution
+, Cu
2+Ion converts Cu (OH) to
2, Bi
2O
3Precipitate and isolate etc. solid-state goods and materials, and Ag
+Still stay in the solution, reduce BiO in the solution thereby reach
+, Cu
2+The purpose of ionic concn plays the effect of cleaning waste electrolyte.
Because silver ammino ion and ammoniacal copper complex ion are similar with weak electrolyte in the aqueous solution, there are complex ion and form its central ion, the dissociation equilibrium between the ligand:
The stability constant of the common complex ion of table 2
As known from Table 2: silver ammino ion Ag (NH
3)
2 +Stability constant 1.6 * 10
7Than ammoniacal copper complex ion Cu (NH
3)
2 +Stability constant 7.4 * 10
10Little, Cu (NH is described
3)
2 +Than Ag (NH
3)
2 +More stable.According to the while equilibrium principle, when pH value in solution is 4.6-6.32, Cu (NH
3)
2 +In can not the situation of stable existence, Ag (NH
3)
2 +Also can not stable existence.Explanation adopts the technique of ammonia treatment waste silver electrolyte can not have Ag (NH again
3)
2 +Negative impact.And pH value in solution can not the stable existence ammoniacal copper complex ion in the scope of 4.6-6.32, and copper will be with CuO, Cu
2The form of O exists.When explanation added ammoniacal liquor in silver salt solution, the copper in the waste silver electrolyte can be cleaned away.
The invention is characterized in following steps:
A, ammonia neutralization are that the waste silver electrolyte with argentiferous, copper, bismuth ion injects in the churned mechanically neutralizing well, add while stirring ammoniacal liquor and neutralize, and the pH value of controlling above-mentioned waste liquid is 5-6, makes cupric ion and bismuth ion hydrolytic precipitation in the waste liquid;
B, precipitate and separate are to stop first stirring, again with the waste liquid after the said hydrolyzed in neutralizing well or settling bath, leave standstill and carried out precipitate and separate at least in 24 hours, liquid returns and is used as silver electrolyte after the precipitation, precipitation slag is then through washing, be sent to the converter melting after filtering.
Described mechanical stirring speed is 20-22 rev/min.
The invention has the beneficial effects as follows: 1, waste silver electrolyte is processed and is given off a large amount of nitric acid tail gas when adopting original thermolysis process, pollution to environment is very serious, can not adapt to the requirement of environmental protection, now adopt ammonia liquor neutralization process Processing Ag electrolysis waste solution, there has not been the discharging of nitric acid tail gas, the execute-in-place environment is greatly improved, and has eliminated the pollution to atmosphere.2, process per month once electrolytic waste liquid 12M before the improvement
3Need about 10 days consuming time, expend coal gas approximately: 120000 cubes, the electrolysis waste solution that improves the same quantity of aftertreatment only needed about 3-4 days, needed ammoniacal liquor 600-700 liter, did not need to consume coal gas.Do not adopt thermolysis process, reduce per month nitric acid and consume approximately 1 ton.
Year is saved gas consumption: 12 * 120000m
3* 0.4 yuan/m
3=59.25 (ten thousand yuan)
Year save nitric acid consumption: 12t * 2480 yuan/t=2.9 (ten thousand yuan)
Year increases ammoniacal liquor consumption: 12 * 700 liters * 1.77 yuan/liter=14868 yuan
Year economic benefit is approximately: 59.25+2.9-1.4868 ≈ 60.6 (ten thousand yuan)
Description of drawings
Accompanying drawing is process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention and embodiment thereof are described in further detail.
Referring to accompanying drawing, the invention is characterized in following steps:
A, ammonia neutralization are that the waste silver electrolyte with argentiferous, copper, bismuth ion injects in the churned mechanically neutralizing well, add while stirring ammoniacal liquor and neutralize, and the pH value of controlling above-mentioned waste liquid is 5-6, makes cupric ion and bismuth ion hydrolytic precipitation in the waste liquid;
B, precipitate and separate are to stop first stirring, again with the waste liquid after the said hydrolyzed in neutralizing well or settling bath, leave standstill and carried out precipitate and separate at least in 24 hours, liquid returns and is used as silver electrolyte after the precipitation, precipitation slag is then through washing, be sent to the converter melting after filtering.
Described mechanical stirring speed is 20-22 rev/min.
Below tabulation provides each embodiment:
Waste silver electrolyte neutralization precipitation industrial implementation example data
The technological process of each embodiment is all identical, and example 2 is to adopt NaoH to make neutralizing agent, therefore Ag
+Loss larger, containing Ag in the precipitation slag is 35%, should not adopt.The pH value is to use artificial controlled in the scope of 5-6 by precision test paper, uncontrollable exact value, and stirring velocity also is to use artificial controlled in 20-22 rev/min scope by step-down gear.
Ammoniacal liquor adopts " starry sky board " 2500ml/ bottled, molecular formula: NH
3, molecular weight: 17.03, content 25.0-28.0%, the place of production: Zhuzhou Inst. of Chemical Industry, Hunan Prov. produces.
Precision test paper adopts " trying three boards ", two kinds of pH value 3.8-5.4 and 5.4-7.0, and the place of production: Chinese Shanghai three likes to think reagent company limited (former Shanghai reagent three factories).
Claims (2)
1. the cleaning method of a waste silver electrolyte is characterized in that following steps:
A, ammonia neutralization are that the waste silver electrolyte with argentiferous, copper, bismuth ion injects in the churned mechanically neutralizing well, add while stirring ammoniacal liquor and neutralize, and the pH value of controlling above-mentioned waste liquid is 5-6, makes cupric ion and bismuth ion hydrolytic precipitation in the waste liquid;
B, precipitate and separate are to stop first stirring, again with the waste liquid after the said hydrolyzed in neutralizing well or settling bath, leave standstill and carried out precipitate and separate at least in 24 hours, liquid returns and is used as silver electrolyte after the precipitation, precipitation slag is then through washing, be sent to the converter melting after filtering.
2. by cleaning method claimed in claim 1, it is characterized in that described mechanical stirring speed is 20-22 rev/min.
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|---|---|---|---|
| CN 200810143885 CN101445952B (en) | 2008-12-10 | 2008-12-10 | Purifying treatment method for waste silver electrolyte |
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|---|---|---|---|
| CN 200810143885 CN101445952B (en) | 2008-12-10 | 2008-12-10 | Purifying treatment method for waste silver electrolyte |
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| CN101445952B true CN101445952B (en) | 2013-04-24 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844842A (en) * | 2010-05-21 | 2010-09-29 | 安徽宏宇玻璃有限公司 | Waste silver treatment device for silver mirror production line |
| CN102983340B (en) * | 2012-11-21 | 2015-04-29 | 中国科学院金属研究所 | Method for removing copper ions from copper-containing vanadium liquid |
| CN108480647B (en) * | 2018-01-23 | 2022-01-18 | 珠海纳金科技有限公司 | Recycling method of nano-silver particle waste liquid |
| CN111099652B (en) * | 2020-01-06 | 2022-05-31 | 金隆铜业有限公司 | Method for separating silver and copper in silver electrolysis waste liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043529A (en) * | 1988-12-13 | 1990-07-04 | 山东焦家金矿 | Ammonia process separates the gold and silver in the gold mud |
| CN1339619A (en) * | 2000-08-23 | 2002-03-13 | 内蒙古乾坤金银精炼股份有限公司 | Method for removing bismuth and antiomny from silver electrolyte |
| CN1884623A (en) * | 2006-05-21 | 2006-12-27 | 郴州市金贵有色金属有限公司 | Purifying method for silver electrolytic solution |
| CN101109089A (en) * | 2007-05-21 | 2008-01-23 | 江西铜业集团公司 | Self-purification process for silver electrolytic solution |
| CN101113526A (en) * | 2006-07-28 | 2008-01-30 | 上海银城佘山白银开发有限公司 | Method for purifying silver electrolytic solution during high-purity silver production process |
-
2008
- 2008-12-10 CN CN 200810143885 patent/CN101445952B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043529A (en) * | 1988-12-13 | 1990-07-04 | 山东焦家金矿 | Ammonia process separates the gold and silver in the gold mud |
| CN1339619A (en) * | 2000-08-23 | 2002-03-13 | 内蒙古乾坤金银精炼股份有限公司 | Method for removing bismuth and antiomny from silver electrolyte |
| CN1884623A (en) * | 2006-05-21 | 2006-12-27 | 郴州市金贵有色金属有限公司 | Purifying method for silver electrolytic solution |
| CN101113526A (en) * | 2006-07-28 | 2008-01-30 | 上海银城佘山白银开发有限公司 | Method for purifying silver electrolytic solution during high-purity silver production process |
| CN101109089A (en) * | 2007-05-21 | 2008-01-23 | 江西铜业集团公司 | Self-purification process for silver electrolytic solution |
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