CN101613150A - A kind of method for the treatment of high-arsenious solution with low cost - Google Patents
A kind of method for the treatment of high-arsenious solution with low cost Download PDFInfo
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- CN101613150A CN101613150A CN200910094781A CN200910094781A CN101613150A CN 101613150 A CN101613150 A CN 101613150A CN 200910094781 A CN200910094781 A CN 200910094781A CN 200910094781 A CN200910094781 A CN 200910094781A CN 101613150 A CN101613150 A CN 101613150A
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Abstract
A kind of method for the treatment of high-arsenious solution with low cost belongs to hydrometallurgy and environmental technology field.With total arsenic content greater than the high arsenic containing solution of 0.5g/l at pH value 5～6, under 15～60 ℃ the condition, by weight As/Cu
2+=5～6 add and to contain cupric soluble salt, blast air continuously and solution are seethed carry out oxidation in 2～3 hours.Contain preferably CuSO of cupric soluble salt
4Beneficial effect: the 1. Cu of Jia Ruing
2+Only play the katalysis that trivalent arsenic is oxidized to pentavalent arsenic, so add-on is few, simultaneously displacement such as available zinc powder iron filings is reclaimed after the precipitation dearsenification.2. to carry out the oxidation dearsenification be a successive processes owing to constantly blast air, till reaching the required purification degree of depth, so operation is simple.3. the purifying treatment cost of arsenic is significantly less than other oxygenant method.4. with in the hydrometallurgy use Fe (OH)
3The arsenic-adsorbing co-precipitation is compared, and other valuable metal that causes loses in slag approximately and hangs down 10%.
Description
Technical field
The invention belongs to hydrometallurgy and environmental technology field.
Background technology
Arsenic all is that objectionable constituent must be separated and removed in the overwhelming majority's metallurgical process and wastewater treatment.Generally speaking, As mainly exists with trivalent in the aqueous solution, accounts for more than 80% of total arsenic amount.When hydrometallurgy adopts the metal replacement method, be easy to generate H
3As and endanger operator.When adopting absorption method or generating the difficulty soluble salt precipitation, because arsenus acid (As
3+) the dissociation equilibrium constant much smaller than arsenic acid (As5
+), thereby trivalent arsenic is difficult for generating difficulty soluble salt by hydrolysis and is removed, and pentavalent arsenic is removed easily far beyond trivalent arsenic.Adopt the dearsenification of sulfuration method, must under peracid, carry out, and other valuable metal composition precipitation that also can cure, not easily separated with arsenic.Use the extraction process arsenic removal, also do not have the selective extractant of arsenic to occur so far.In the purification of hydrometallurgy and other arsenic-containing waste water, all as far as possible earlier trivalent arsenic is oxidized to pentavalent arsenic for this reason, improves the purification degree of depth by ionic adsorption or generation indissoluble arsenate again.
Trivalent arsenic is oxidized to pentavalent arsenic, uses KnMO usually
4, O
3(ozone), MnO
2, H
2O
2, Ca (OCl)
2Strong oxidizers such as (chlorinated lime).KnMO
4And O
3Though be strong oxidizer, can under any circumstance trivalent arsenic is oxidized to pentavalent arsenic, but the oxidation cost is too high, is containing more than the arsenic 5g/l, in the solution of complicated component, consume very big, all try one's best when industrial production or liquid waste disposal few with or need not.MnO
2, H
2O
2, Ca (OCl)
2Be weaker than the former etc. oxidation capacity, use the pH value scope also narrower, add-on is big, and the oxidation cost is higher.Trivalent arsenic is oxidized to pentavalent arsenic in addition, and pentavalent arsenic also is a kind of oxygenant, when complicated and arsenic content is high when solution composition, can be reduced to trivalent arsenic again.And above-mentioned oxygenant is quantitative adding, does not have continuity, reach certain depth, must constantly add, and this certainly will will add excessive oxygenant, increases processing cost.
In zinc hydrometallurgy is produced, adopt and add Cu
2+The way that blasts air purifies ZnSO
4Solution.This method is at the Fe2 in the solution
+Be oxidized to Fe3
+, the oxidation behavior of arsenic in the solution is not studied and measured, the arsenic content in the solution is generally all less than 1g/l in addition.
Summary of the invention
The object of the present invention is to provide a kind of method for the treatment of high-arsenious solution with low cost.
The inventive method is: with total arsenic content greater than the high arsenic containing solution of 0.5g/l at pH value 5～6, under 15～60 ℃ the condition, by weight As/Cu
2+=5～6 add and to contain cupric soluble salt, blast air continuously and solution are seethed carry out oxidation in 2～3 hours.Contain preferably CuSO of cupric soluble salt
4Air amount of blasting and speed and oxidation rate are irrelevant.
The inventive method has following beneficial effect:
1. the Cu of Jia Ruing
2+Only play the katalysis that trivalent arsenic is oxidized to pentavalent arsenic, so add-on is few, simultaneously displacement such as available zinc powder iron filings is reclaimed after the precipitation dearsenification.
2. to carry out the oxidation dearsenification be a successive processes owing to constantly blast air, till reaching the required purification degree of depth, so operation is simple.
3. the purifying treatment cost of arsenic is significantly less than other oxygenant method.
4. because the arsenic that present method is handled mainly generates the indissoluble arsenate is removed, so and usefulness Fe (OH) in the hydrometallurgy
3The arsenic-adsorbing co-precipitation is compared, and other valuable metal that causes loses in slag approximately and hangs down 10%.
Embodiment
Embodiment 1. is containing As3
+6.1g/l total arsenic content is 7g/l, organism 3.5g/l, Zn100g/l, Fe2
+200mg/l,, pH value is in 5.4 the sulphuric acid soln, to press As/Cu2
+=5 add CuSO
45H
2O blasted atmospheric oxidation 3 hours continuously at 50 ℃.Total arsenic-removing rate reaches 94.5%.Zn loss 11% is compared minimizing 14% with the Zn loss 25% of ironic hydroxide absorption method.
2. couples of embodiment always contain arsenic 1.1g/l, contain Zn134g/l, Fe860mg/l, Ge250mg/l, and PH is 2.5 sulfuric acid industry leach liquor, and behind N235 kerosene system extracted germanium, transferring pH value is 5.6, presses As/Cu2
+=5.5 add CuSO45H2O, blast air (15 liters/second) continuously 2.5 hours at 25 ℃, filter, and slag contains zinc 15%, and filtrate contains arsenic 55mg/l.
Embodiment 3. is with As
2O
3Vitriolization is made into and contains As15g/l, Zn50g/l, and Fe1.5g/l, the solution of PH5.2 is divided into two groups.Transfer pH value to 8-9 for one group, zinc, the most of hydrolytic precipitation of iron filter rear filtrate and contain arsenic 10.5g/l.Press As/Cu2 for second group
+=6 add CuSO
45H2O heats to 40 ℃ and blasted air continuously 3.5 hours, filters rear filtrate and contains arsenic 200mg/l, Zn45g/l, Fe50mg/l.As seen present method effect of removing arsenic is obvious
Embodiment 4. contains arsenic 200mg/l with embodiment 3, Zn45g/l, and the filtrate of Fe50mg/l is transferred pH value 3.5-4.0, adds the capacity zinc powder at 80 ℃, mechanical stirring 2 hours, solution contains arsenic 0.1mg/l, and replacement slag contains more than the Cu20%.
Embodiment 5. is containing As3
+4g/l, total arsenic content is 4.5g/l, organism 3g/l, Zn100g/l, Fe2
+220mg/l, pH value in 5 the sulphuric acid soln, press As/Cu2
+=5 add CuCl
24H
2O blasted atmospheric oxidation 3 hours continuously at 16 ℃.Total arsenic-removing rate reaches 94.2%.
Above embodiment only is for present method is described further, and the scope of present method is not subjected to the limitation of illustrated embodiment.
Claims (3)
1, a kind of method for the treatment of high-arsenious solution with low cost is characterized in that: with total arsenic content greater than the high arsenic containing solution of 0.5g/l at pH value 5～6, under 15～60 ℃ the condition, by weight As/Cu
2+=5～6 add and to contain cupric soluble salt, blast air continuously and solution are seethed carry out oxidation in 2～3 hours.
2, as the said method of claim 1, it is characterized in that containing cupric soluble salt is CuSO
4
3, as the said method of claim 1, it is characterized in that: blast air continuously with 15 liters/second at 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100947814A CN101613150B (en) | 2009-07-30 | 2009-07-30 | Method for treating high-arsenious solution with low cost |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100947814A CN101613150B (en) | 2009-07-30 | 2009-07-30 | Method for treating high-arsenious solution with low cost |
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| CN101613150A true CN101613150A (en) | 2009-12-30 |
| CN101613150B CN101613150B (en) | 2011-03-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496000A (en) * | 2014-12-16 | 2015-04-08 | 浙江工业大学 | Method for removing and recovering arsenic and antimony in water body by replacement of copper powder |
| CN104609593A (en) * | 2014-12-16 | 2015-05-13 | 浙江工业大学 | Method for copper powder displacement removal and recovery of arsenic in water body |
| CN109763000A (en) * | 2018-12-10 | 2019-05-17 | 六盘水中联工贸实业有限公司 | A method of from height containing air oxidation removal arsenic in arsenic, zinc acid solution |
| CN110563058A (en) * | 2019-09-19 | 2019-12-13 | 昆明理工大学 | Method for treating arsenic in colored smelting waste acid by using modified red mud and CuO powder |
-
2009
- 2009-07-30 CN CN2009100947814A patent/CN101613150B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496000A (en) * | 2014-12-16 | 2015-04-08 | 浙江工业大学 | Method for removing and recovering arsenic and antimony in water body by replacement of copper powder |
| CN104609593A (en) * | 2014-12-16 | 2015-05-13 | 浙江工业大学 | Method for copper powder displacement removal and recovery of arsenic in water body |
| CN104609593B (en) * | 2014-12-16 | 2016-06-15 | 浙江工业大学 | The method that the displacement of a kind of copper powder is removed and reclaimed arsenic in water body |
| CN109763000A (en) * | 2018-12-10 | 2019-05-17 | 六盘水中联工贸实业有限公司 | A method of from height containing air oxidation removal arsenic in arsenic, zinc acid solution |
| CN110563058A (en) * | 2019-09-19 | 2019-12-13 | 昆明理工大学 | Method for treating arsenic in colored smelting waste acid by using modified red mud and CuO powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101613150B (en) | 2011-03-16 |
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