CN102730880A - Method for treating arsenic-containing wastewater with high acidity from zinc smelting - Google Patents
Method for treating arsenic-containing wastewater with high acidity from zinc smelting Download PDFInfo
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- CN102730880A CN102730880A CN2012101868968A CN201210186896A CN102730880A CN 102730880 A CN102730880 A CN 102730880A CN 2012101868968 A CN2012101868968 A CN 2012101868968A CN 201210186896 A CN201210186896 A CN 201210186896A CN 102730880 A CN102730880 A CN 102730880A
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Abstract
The present invention relates to a method for treating arsenic-containing wastewater with high acidity from nonferrous metal zinc smelting. The method includes steps of pre-detection, wastewater oxidation, neutralization mixing and filtering recovery. The method for treating arsenic-containing wastewater with high acidity from nonferrous metal zinc smelting can realize arsenic content in waste water of 0.0004g / L and arsenic removal rate reaching 99%.A small amount of waste residue is generated in the treatment process of wastewater, and the amount of generated waste residue only accounts for 20% of the waste residue generated in a ''lime-ferric salt-oxidation'' method; and the waste residue can be sent to a dressing plant for flotation, so as to recover zinc, and the remaining ferric arsenate concentrate with high arsenic content can be sold as materials for recovering arsenic. pH of the solution can be controlled in the wastewater treatment process to inhibit precipitation of zinc, with most zinc remaining in the solution; and zinc loss rate is only at 10%. The wastewater can be used as an electrolytic zinc plant electrolyte complementary water to be recycled and further recover Zn in the wastewater. In addition, the method fully employs characteristics of high acidity and high iron content of the wastewater, and no acid reagent or iron salt is needed to be added, thereby reducing input of auxiliary materials and reducing the cost of wastewater treatment.
Description
Technical field
The present invention relates to a kind of treatment process of peracid arsenic-containing waste water, be applicable to the processing of non-ferrous metal zinc smelting peracid arsenic-containing waste water.
Background technology
Tradition zinc is smelted peracid arsenic-containing waste water treatment process has " lime-molysite-oxidation " method and " red arsenic " method etc." lime-molysite-oxidation " method is a kind of more common arsenic-containing waste water treatment process, and this method at first adds oxygenant (ydrogen peroxide 50, aeration, potassium permanganate, Youxiaolin etc.) in the waste water, with the As in the waste water
3+Be oxidized to As
5+, in waste water, add unslaked lime then, regulate waste water ph, calcium salt and arsenic generate the Tricalcium arsenate deposition, in waste water, add molysite at last, remove the arsenic in the waste water through reactions such as coagulation, co-precipitation.Disclose a kind of " high density arsenic-containing waste water treatment process " like patent documentation CN102234161A, this method comprises among (1) PH and regulates: through the adding plaster of Paris or milk of lime in the arsenic-containing waste water are regulated its pH value; (2) waste water arsenic preoxidation: arsenic-containing waste water is carried out aeration agitation add oxygenant simultaneously, add the oxygenant continued and stir; (3) calcium arsenic slag dissolved air flotation: add organic floculant and slowly stirred 3 ~ 10 minutes; Through pressure air-dissolving or injecting dissolve gas arsenic-containing waste water is at this moment carried out the dissolved air flotation first time subsequently; Thereby combine come-up to separate arsenic slag aggregation in the arsenic-containing waste water and micro bubble, the arsenic slag of come-up is collected press filtration reclaim with clear liquid; (4) iron arsenic slag dissolved air flotation: add inorganic coagulant and stir; Then hydraulic detention time is 10 ~ 30 minutes; Add caustic soda again and regulate waste water PH to 7 ~ 13, add organic floculant again and slowly stirred 3 ~ 10 minutes, through pressure air-dissolving or injecting dissolve gas arsenic-containing waste water is at this moment carried out the dissolved air flotation second time subsequently; Thereby combine come-up to separate arsenic slag aggregation in the arsenic-containing waste water and micro bubble, the arsenic slag of come-up is collected press filtration reclaim with clear liquid; (5) clear liquid membrane filtration carries out the clear liquid membrane filtration to the clear liquid behind the removing arsenic slag, and the water outlet after the filtration reaches emission standard.
Though " lime-molysite-oxidation " method has characteristics such as technology is flexible, easy and simple to handle, cost for wastewater treatment is cheap, be present comparative maturity and widely used arsenic-containing waste water treatment process, also there are many defectives in this method.At first; This method with in waste water in acid be main; Most metals ion and arsenic are with the form and the calcium ion coprecipitation of vitriol, sulphite, arsenate and arsenite; Still have the metals ion and the arsenic of few part to remain in the waste water, the clearance of arsenic is merely about 95%, the waste water after the processing still difficulty reach the national environmental protection emission standard; Secondly, it is very unstable that the part of generation contains the arsenic throw out, and arsenic is released out again easily and causes secondary pollution; Once more, a large amount of arsenic-containing waste residues of wastewater treatment process output, difficulty is all compared in depositing and handling of arsenic-containing waste residue; At last, can cause most of valuable metal Zn to get in the waste residue valuable metal resource that waste is valuable in the wastewater treatment process.
" red arsenic " method is to generate the red arsenic deposition with arsonium ion reaction in vulcanizing agent (sodium sulphite, sulphur hydrogenation receive etc.) and the waste water, thereby reaches the purpose of removing arsenic." red arsenic " method has characteristics such as technology is simple, treatment capacity big, reaction is fast, but " red arsenic " method has strict requirement to the pH value, and the improper meeting of pH value control causes that arsenic gets into water body once more, and generates H
2S forms secondary pollution.
The arsenic clearance is lower, easy to be produced secondary pollution, the waste residue amount is big and utilizes problems such as difficulty, the big recovery difficulty of valuable metal loss amount to become the important factor that restriction zinc smelting enterprise develops.
Summary of the invention
The present invention provide a kind of solve non-ferrous metal zinc smelt arsenic clearance in the peracid arsenic-containing waste water treating processes lower, be prone to produce secondary pollution, the waste residue amount is big and utilizes the method for problems such as difficulty, the big recovery difficulty of valuable metal loss amount.
A kind of method of handling zinc smelting peracid arsenic-containing waste water of the present invention may further comprise the steps:
1) pre-detection: the peracid arsenic-containing waste water carries pipe special to get into the sewage storagetank by production plant through waste water, detects waste water pH value and As, As
3+, Zn, Fe, Fe
2+Content;
2) wastewater oxidation: waste water in the sewage storagetank is taken out toward the oxidizing reaction steel basin, according to Fe in the waste water by vertical mortar pump
2+And As
3+Content, in the oxidizing reaction groove, add proper amount of oxidant H
2O
2, open stirrer simultaneously and at the uniform velocity stir, every in 10 ~ 20 minutes detection waste water the ionic forms changing conditions of Fe and As, reach As up to the ionic forms of Fe and As
3+≤0.0005g/L, Fe
3+Stop oxidation during content>=total As content, and detect the pH value of waste water this moment;
3) neutralization is stirred: by vertical mortar pump the waste water in the oxidation reaction groove is taken out toward the neutralization reaction groove; Acidity based on waste water; Drop into nertralizer NaOH and regulate the waste water pH value, open mixer simultaneously and at the uniform velocity stir, whenever detected the content situation of waste water pH value and As at a distance from 0.5 ~ 1.5 hour;, in 4-5 scopes, stop neutralization during and total As content≤0.0005g/L and stir until the waste water pH value;
4) press filtration is reclaimed: by vertical mortar pump the liquid in the neutralization reaction groove is taken out toward the plate-and-frame filter press press filtration; Water is sent to the thickener clarification after the purification that obtains after the press filtration; The thickener supernatant is sent to the electrolytic zinc workshop and makes to replenish the electrolytic solution water; After trace mud and press filtration sludge silt sent the dressing-works flotation separation to reclaim zinc, remainder contained the higher ferric arsenate concentrate of arsenic and sells as the raw material that reclaims arsenic.
Adopt present method to handle non-ferrous metal zinc and smelt the peracid arsenic-containing waste water; Trivalent arsenic is oxidized to pentavalent arsenic in the waste water, and oxidation of divalent is a ferric iron, molysite and the arsenic flocculation single step reaction of going forward side by side; Generate the ferric arsenate salt of indissoluble; After this method was handled, arsenic content was about 0.0004g/L in the waste water, and the clearance of arsenic is up to 99%; Throw outs such as ferric arsenate are water insoluble, and advantages of higher stability is arranged, and arsenic is difficult for being discharged again; The waste residue amount that in wastewater treatment process, produces is few, is merely about 20% of " lime-molysite-oxidation " quantity of slag that method is produced, and the factory's flotation separation recovery zinc of can sending to be elected, and remainder contains the higher ferric arsenate concentrate of arsenic and sells as the raw material that reclaims arsenic; Can stablize the control solution PH in the wastewater treatment process, suppress the deposition of zinc, most of zinc is still stayed in the solution, and the rate of loss of zinc only about 10%, is replenished with water circulation use with further recovery zinc wherein as electrolytic zinc workshop electrolytic solution.In addition, this method makes full use of the characteristics that waste water acidity is high, iron-holder is high, need not add acid reagent and molysite again, has reduced the input of subsidiary material, reduces cost for wastewater treatment.
Description of drawings
Fig. 1 is a method process flow sheet of the present invention.
Embodiment
As shown in Figure 1, the present invention includes waste water pH value and As, As
3+, Zn, Fe, Fe
2+Content pre-detection operation, add proper amount of oxidant H
2O
2Open the wastewater oxidation operation that stirrer at the uniform velocity stirs simultaneously; In dropping into that neutralizing agent NaOH regulates that the waste water pH value opens simultaneously that stirrer at the uniform velocity stirs and agitating procedure, and the press filtration recovery process that press filtration and the supernatant, micro-mud, the sludge silt that obtain through the thickener clarification are reclaimed.Wherein equipment comprises sewage storagetank, oxidizing reaction steel basin, neutralization reaction steel basin, plate-and-frame filter press, vertical mortar pump etc.The concrete operations step is following:
At first carry pipe special to get into the sewage storagetank by production plant through waste water the peracid arsenic-containing waste water, detect waste water pH value and As, As
3+, Zn, Fe, Fe
2+Content;
Secondly by vertical mortar pump waste water in the sewage storagetank is taken out toward the oxidizing reaction steel basin, according to Fe in the waste water
2+And As
3+Content, in the oxidizing reaction groove, add proper amount of oxidant H
2O
2, open stirrer simultaneously and at the uniform velocity stir, every in 15 minutes detection waste water the ionic forms changing conditions of Fe and As, until As
3+≤0.0005g/L, Fe
3+Content>=total As content, and detect the pH value of waste water at this moment;
By vertical mortar pump the waste water in the oxidizing reaction groove is taken out toward the neutralization reaction groove again; Acidity according to waste water; Drop into neutralizing agent NaOH and regulate the waste water pH value, open stirrer simultaneously and at the uniform velocity stir, whenever detected the content situation of waste water pH value and As at a distance from 1 hour; Until the waste water pH value in 4 ~ 5 scopes, and total As content≤0.0005g/L;
By vertical mortar pump the liquid in the neutralization reaction groove is taken out toward the plate-and-frame filter press press filtration at last; Water is sent to the thickener clarification after the purification that obtains after the press filtration; The thickener supernatant is sent to the electrolytic zinc workshop and makes to replenish the electrolytic solution water; After trace mud and press filtration sludge silt sent the dressing-works flotation separation to reclaim zinc, remainder contained the higher ferric arsenate concentrate of arsenic and sells as the raw material that reclaims arsenic.
In wastewater treatment process, oxygenant H
2O
2Under acidic conditions with As
3+Be oxidized to As
5+, Fe
2+Be oxidized to Fe
3+, main chemical reactions is H
2O
2+ As
3+→ As
5+, H
2O
2+ Fe
2+→ Fe
3+Neutralizing agent NaOH and Fe
3+Generate Fe (OH)
3Deposition with the arsenic flocculation single step reaction of going forward side by side, generates the salts such as ferric arsenate of indissoluble, and main chemical reactions is NaOH+Fe
3+→ Fe (OH)
3↓, H
3AsO
4+ Fe (OH)
3→ FeAsO
4↓+3H
2O, thus reach the purpose of from waste water, removing arsenic.The whole process of wastewater treatment is owing to controlled the pH value of waste water, and most of zinc is still stayed in the liquid, creates favorable conditions for further reclaiming zinc.
The waste water that produces in the zinc metallurgical process not only acidity is high; And contain contents of many kinds of heavy metal ion, use " lime-molysite-oxidation style " to handle, the lime material amount of input is big; Cost is high, processing power is low; The sludge quantity that produces is big and be difficult to disposal, though the water recycle after the processing, valuable metal Zn loss is serious.Adopt the inventive method to handle the peracid arsenic-containing waste water, the clearance of As reaches 99%, and the arsenic-containing waste residue amount is merely about 20% of " lime-molysite-oxidation " quantity of slag that method is produced, and the zinc rate of loss is about 10%.
The present invention further specifies below in conjunction with examples comparative.
Instance 1: sample is certain zinc smeltery peracid arsenic-containing waste water sample (50m3), contains H in this wastewater sample
+40.56g/L, contain As 5.16g/L, contain Zn 32.77g/L, contain Fe 5.67g/L, contain Fe
2+5.24g/L, with the two portions that are divided into of this peracid arsenic-containing waste water sample equalization, adopt " lime-molysite-oxidation " method and the inventive method to handle respectively, result sees table 1, table 2 for details.
Table 1 " lime-molysite-oxidation " method result
Table 2 the inventive method result
Can be known that by table 1 " lime-molysite-oxidation " method As clearance is (5.16-0.52)/5.16 * 100%=89.92%, the Zn rate of loss is (32.77-6.16)/32.77 * 100%=81.20%; Sludge quantity is 1325.00kg.
Can be known that by table 2 the inventive method As clearance is (5.16-0.0003)/5.16 * 100%=99.99%, the Zn rate of loss is (32.77-29.18)/32.77 * 100%=10.96%; The mud quantity of slag is 268kg, is about 20% of " lime-molysite-oxidation " quantity of slag that method is produced.
Contrast table 1 can know with table 2, and the inventive method is than " lime-molysite-oxidation " method and " red arsenic " method, and As clearance height, non-secondary pollution, sludge quantity and Zn rate of loss clear superiority such as is less arranged.
Claims (1)
1. handle the method that zinc is smelted the peracid arsenic-containing waste water for one kind, it is characterized in that: may further comprise the steps
A) pre-detection: the peracid arsenic-containing waste water carries pipe special to get into the sewage storagetank by production plant through waste water, detects waste water pH value and As, As
3+, Zn, Fe, Fe
2+Content;
B) wastewater oxidation: waste water in the sewage storagetank is taken out toward the oxidizing reaction steel basin, according to Fe in the waste water by vertical mortar pump
2+And As
3+Content, in the oxidizing reaction groove, add proper amount of oxidant H
2O
2, open stirrer simultaneously and at the uniform velocity stir, every in 10-20 minutes detection waste water the ionic forms changing conditions of Fe and As, reach As up to the ionic forms of Fe and As
3+≤0.0005g/L, Fe
3+Stop oxidation during content>=total As content, and detect the pH value of waste water this moment;
C) neutralization is stirred: by vertical mortar pump the waste water in the oxidation reaction groove is taken out toward the neutralization reaction groove; Acidity based on waste water; Drop into nertralizer NaOH and regulate the waste water pH value, open mixer simultaneously and at the uniform velocity stir, whenever detected the content situation of waste water pH value and As at a distance from 0.5-1.5 hours; Until the waste water pH value in 4-5 scopes, and total As content≤0.0005g/L;
D) press filtration is reclaimed: by vertical mortar pump the liquid in the neutralization reaction groove is taken out toward the plate-and-frame filter press press filtration; Water is sent to the thickener clarification after the purification that obtains after the press filtration; The thickener supernatant is sent to the electrolytic zinc workshop and makes to replenish the electrolytic solution water; Trace mud and press filtration sludge silt send the dressing-works flotation separation to reclaim zinc, and remainder contains the higher ferric arsenate concentrate of arsenic and sells as the raw material that reclaims arsenic.
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|---|---|---|---|
| CN2012101868968A CN102730880A (en) | 2012-06-07 | 2012-06-07 | Method for treating arsenic-containing wastewater with high acidity from zinc smelting |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435188A (en) * | 2013-08-30 | 2013-12-11 | 昆明理工大学 | Treatment method of high-arsenic wastewater in copper smelting |
| CN104787932A (en) * | 2015-04-29 | 2015-07-22 | 铜陵化学工业集团有限公司 | Treatment method of industrial arsenic wastewater |
| CN105254061A (en) * | 2015-10-13 | 2016-01-20 | 桂林市春晓环保科技有限公司 | Treatment method of beneficiation wastewater |
| CN110540317A (en) * | 2019-08-16 | 2019-12-06 | 上海电力大学 | Method for separating and recycling acid waste water containing arsenic and nickel |
| CN110745988A (en) * | 2019-10-23 | 2020-02-04 | 长春黄金研究院有限公司 | Arsenic-containing waste acid treatment method |
| CN112028325A (en) * | 2020-09-07 | 2020-12-04 | 山东恒邦冶炼股份有限公司 | Method for comprehensively treating non-ferrous smelting acidic high-chlorine wastewater |
| CN112028331A (en) * | 2020-09-15 | 2020-12-04 | 昆明理工大学 | Method for treating arsenic-containing waste acid by using hematite and manganese sand |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623921A (en) * | 2003-12-04 | 2005-06-08 | 陈小华 | Process for removing arsenic in water using oxydol as oxidative agent |
Non-Patent Citations (1)
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|---|
| 谭永仁等: "氧化-控pH中和法处理南丹县吉朗铟业有限公司锌冶炼高酸含砷废水", 《有色金属》, vol. 62, no. 1, 28 February 2010 (2010-02-28), pages 96 - 98 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435188A (en) * | 2013-08-30 | 2013-12-11 | 昆明理工大学 | Treatment method of high-arsenic wastewater in copper smelting |
| CN104787932A (en) * | 2015-04-29 | 2015-07-22 | 铜陵化学工业集团有限公司 | Treatment method of industrial arsenic wastewater |
| CN105254061A (en) * | 2015-10-13 | 2016-01-20 | 桂林市春晓环保科技有限公司 | Treatment method of beneficiation wastewater |
| CN110540317A (en) * | 2019-08-16 | 2019-12-06 | 上海电力大学 | Method for separating and recycling acid waste water containing arsenic and nickel |
| CN110745988A (en) * | 2019-10-23 | 2020-02-04 | 长春黄金研究院有限公司 | Arsenic-containing waste acid treatment method |
| CN112028325A (en) * | 2020-09-07 | 2020-12-04 | 山东恒邦冶炼股份有限公司 | Method for comprehensively treating non-ferrous smelting acidic high-chlorine wastewater |
| CN112028331A (en) * | 2020-09-15 | 2020-12-04 | 昆明理工大学 | Method for treating arsenic-containing waste acid by using hematite and manganese sand |
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Application publication date: 20121017 |