CN103695649A - Method for processing high-concentration chlorine-containing wastewater - Google Patents
Method for processing high-concentration chlorine-containing wastewater Download PDFInfo
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- CN103695649A CN103695649A CN201310681781.0A CN201310681781A CN103695649A CN 103695649 A CN103695649 A CN 103695649A CN 201310681781 A CN201310681781 A CN 201310681781A CN 103695649 A CN103695649 A CN 103695649A
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- zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for processing a high-concentration chlorine-containing wastewater. The method comprises the following steps: carrying out zinc neutralization and precipitation at 60-70 DEG C by using lime after preparation of liquid, and filtering after reacting, so as to obtain a zinc precipitate slag and filtrate; recovering metal zinc after washing the zinc precipitate slag; adding lime to the filtrate to neutralize until the pH is 8.5-9.0; standing for 24 hours to remove impurities such as arsenic, iron, lead, magnesium and the like; carrying out evaporating concentration and crystallization on the liquid after impurities are removed, so as obtain an industrial anhydrous calcium chloride product. Zinc and indium metals in the high-concentration chlorine-containing wastewater can be recovered by adopting the method, and a chlorine element in the wastewater is converted into a calcium chloride product, so that innocent treatment of the chlorine-containing wastewater is achieved, the problem of environment protection is solved, and economic benefits are achieved.
Description
Technical field
The present invention relates to non-ferrous metal metallurgy technical field, particularly a kind of method of processing high density chlorine-contained wastewater.
Background technology
At present, process the technological process of production that high indium high-iron zinc sulfide concentrate extracts zinc indium, output containing zinc 200g/L, iron 5g/L, the displaced liquid of chlorine 225g/L and the anti-molten iron of hydrochloric 180g/L, iron content 15g/L, by common direct discharging of waste water, to waste water processing station, with lime, neutralize, do not reclaim metallic zinc and hydrochloric acid, industrial wastewater treatment system is caused to very large puzzlement, not only cause zinc metal loss, and cause and carry indium production cost and increase, cause trade effluent chlorine ion concentration high and can not return to production station and recycle simultaneously.
Summary of the invention
The object of this invention is to provide a kind of method of processing high density chlorine-contained wastewater; the method can reclaim the metallic zinc in high density chlorine-contained wastewater; chlorion obtains harmless treatment and transfers calcium chloride product to, realizes the chlorion open circuit of system, has effectively protected environment.
The present invention is achieved through the following technical solutions above-mentioned purpose: a kind of method of processing high density chlorine-contained wastewater, comprises the steps:
(1) dosing: by containing zinc 200g/L, iron 5g/L, the displaced liquid of chlorine 225g/L and the anti-molten iron of hydrochloric 180g/L, iron content 15g/L 1:1～1:1.5 mixing by volume dosing, obtain mixed solution;
(2) the heavy zinc of neutralization: under 60～70 ℃ of conditions of temperature of reaction, toward adding in mixed solution lime and hydrogen peroxide to sink zinc, lime consumption is 1.40～1.46 times of theoretical amount, hydrogen peroxide add-on is 3.8%～4.0% of mixeding liquid volume, heavy zinc reaction is 3 hours, then filter, obtain heavy cadmia and filtered liquid;
(3) heavy cadmia washing: at normal temperatures, heavy cadmia is washed after 30min by liquid-solid ratio 3:1 with tap water, filter, heavy cadmia reclaims metallic zinc;
(4) filtered liquid removal of impurities: at normal temperatures, add simultaneously stirring and adjusting filtered liquid pH value to 8.5～9.0 of lime, more standing 24h, remove the impurity such as arsenic in filtered liquid, iron, lead, magnesium, obtain calcium chloride solution;
(5) calcium chloride product output: after the crystallization of calcium chloride solution concentration and evaporation, xln is heated in stoving oven to 170 ℃ and be incubated 3 hours, obtains industrial calcium chloride product.
High density chlorine-contained wastewater of the present invention refers to output displaced liquid and anti-molten iron from zinc indium smelting process, and wherein chloride ion content reaches high density chlorine-contained wastewater more than 150g/L.
Unless otherwise indicated, per-cent of the present invention is mass percent, and each component concentration percentage ratio sum is 100%.
The invention has the advantages that:
By adopting in cheap lime and mixed solution, zinc precipitated metal is in solid, and with chloride liquid separation, the processing by heavy cadmia, makes the zinc metal in high density chlorine-contained wastewater obtain efficient recovery; Solution after heavy zinc, by lime, regulate pH value rear standing, reached the object of low-cost removal of impurities, calcium chloride solution after removal of impurities obtains calcium chloride product after evaporating, concentrating and crystallizing is dry, zinc metal recovery and the harmless treatment of high density chlorine-contained wastewater have been realized, solve chlorion balance and the open circuit of system, for the normal production of zinc indium smelting process, created favourable condition, there is good economic benefit and environmental benefit.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the method for processing high density chlorine-contained wastewater of the present invention.
Embodiment
By drawings and Examples, technical scheme of the present invention is described further below.
Embodiment 1
The present embodiment is the first example of the method for processing high density chlorine-contained wastewater of the present invention, comprises the steps:
(1) dosing: by the displaced liquid 10m containing zinc 200g/L, iron content 5g/L, chloride 225g/L
3anti-molten iron 10m with hydrochloric 180g/L, iron content 15g/L
3, at volume 30m
3tempering tank mixing dosing, obtain the zinc chloride acid mixed solution 20m containing zinc 100g/L, iron content 2.5g/L, hydrochloric 90g/L
3;
(2) the heavy zinc of neutralization: under 60 ℃ of conditions of temperature of reaction, at 20m
3in mixed solution, add 4450 kilograms, lime and hydrogen peroxide 0.76m
3sink zinc, heavy zinc reaction is 3 hours, then filters, obtain moisture 43%, containing 6.8 tons of the heavy cadmias of hygrometric state and the filtered liquid 17.2m of zinc 51%
3;
(3) heavy cadmia washing: at normal temperatures, heavy cadmia is washed after 30min by liquid-solid ratio 3:1 with tap water, filter, heavy cadmia reclaims metallic zinc;
(4) filtered liquid removal of impurities: at normal temperatures, add 420 kilograms, lime, stirring and adjusting filtered liquid pH value to 8.5, more standing 24h simultaneously, removes the impurity such as the plumbous magnesium of arsenic iron in filtered liquid, obtains calcium chloride solution;
(5) calcium chloride product output: calcium chloride solution 17.2m
3after concentration and evaporation crystallization, xln is heated in stoving oven to 170 ℃ and be incubated 3 hours, obtains 6172 kilograms of industrial calcium chloride products.
Embodiment 2
The present embodiment is the second example of the method for processing high density chlorine-contained wastewater of the present invention, comprises the steps:
(1) dosing: by the displaced liquid 12m containing zinc 200g/L, iron content 5g/L, chloride 225g/L
3anti-molten iron 10m with hydrochloric 180g/L, iron content 15g/L
3, at volume 30m
3tempering tank mixing dosing, obtain the zinc chloride acid mixed solution 22m containing zinc 109g/L, iron content 2.7g/L, hydrochloric 82g/L
3;
(2) the heavy zinc of neutralization: under 65 ℃ of conditions of temperature of reaction, at 22m
3in mixed solution, add 5075 kilograms, lime and hydrogen peroxide 0.86m
3sink zinc, heavy zinc reaction is 3 hours, then filters, obtain moisture 45%, containing 8.7 tons of the heavy cadmias of hygrometric state and the filtered liquid 18.8m of zinc 50%
3;
(3) heavy cadmia washing: at normal temperatures, heavy cadmia is washed after 30min by liquid-solid ratio 3:1 with tap water, filter, heavy cadmia reclaims metallic zinc;
(4) filtered liquid removal of impurities: at normal temperatures, add 450 kilograms, lime, stirring and adjusting filtered liquid pH value to 8.8, more standing 24h simultaneously, removes the impurity such as the plumbous magnesium of arsenic iron in filtered liquid, obtains calcium chloride solution;
(5) calcium chloride product output: calcium chloride solution 18.8m
3after concentration and evaporation crystallization, xln is heated in stoving oven to 170 ℃ and be incubated 3 hours, obtains 7030 kilograms of industrial calcium chloride products.
Embodiment 3
The present embodiment is a kind of the 3rd example of processing the method for high density chlorine-contained wastewater of the present invention, comprises the steps:
(1) dosing: by the displaced liquid 15m containing zinc 200g/L, iron content 5g/L, chloride 225g/L
3anti-molten iron 10m with hydrochloric 180g/L, iron content 15g/L
3, at volume 30m
3tempering tank mixing dosing, obtain the zinc chloride acid mixed solution 25m containing zinc 120g/L, iron content 3g/L, hydrochloric 72g/L
3;
(2) the heavy zinc of neutralization: under 70 ℃ of conditions of temperature of reaction, at 25m
3in mixed solution, add 5870 kilograms, lime and hydrogen peroxide 1.0m
3sink zinc, heavy zinc reaction is 3 hours, then filters, obtain moisture 44%, containing 10.9 tons of the heavy cadmias of hygrometric state and the filtered liquid 20.9m of zinc 49%
3;
(3) heavy cadmia washing: at normal temperatures, heavy cadmia is washed after 30min by liquid-solid ratio 3:1 with tap water, filter, heavy cadmia reclaims metallic zinc;
(4) filtered liquid removal of impurities: at normal temperatures, add 530 kilograms, lime, stirring and adjusting filtered liquid pH value to 9.0, more standing 24h simultaneously, removes the impurity such as the plumbous magnesium of arsenic iron in filtered liquid, obtains calcium chloride solution;
(5) calcium chloride product output: calcium chloride solution 20.9m
3after concentration and evaporation crystallization, xln is heated in stoving oven to 170 ℃ and be incubated 3 hours, obtains 7968 kilograms of industrial calcium chloride products.
Claims (1)
1. a method of processing high density chlorine-contained wastewater, is characterized in that, the method comprises the steps:
(1) dosing: by containing zinc 200g/L, iron 5g/L, the displaced liquid of chlorine 225g/L and anti-molten iron 1:1～1:1.5 mixing by volume dosing of hydrochloric 180g/L, iron 15g/L, obtain mixed solution;
(2) the heavy zinc of neutralization: under 60～70 ℃ of conditions of temperature of reaction, toward adding in mixed solution lime and hydrogen peroxide to sink zinc, lime consumption is 1.40～1.46 times of theoretical amount, hydrogen peroxide add-on is 3.8～4.0% of mixeding liquid volume, heavy zinc reaction is 3 hours, then filter, obtain heavy cadmia and filtered liquid;
(3) heavy cadmia washing: at normal temperatures, heavy cadmia is washed after 30min by liquid-solid ratio 3:1 with tap water, filter, heavy cadmia reclaims metallic zinc;
(4) filtered liquid removal of impurities: at normal temperatures, add lime stirring and adjusting filtered liquid pH value to 8.5～9.0 simultaneously, more standing 24h, remove arsenic, iron, lead, magnesium addition in filtrate, obtain calcium chloride solution;
(5) calcium chloride product output: calcium chloride solution, after concentration and evaporation crystallization, is heated to xln 170 ℃ and be incubated 3 hours in stoving oven, obtains industrial calcium chloride product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060301A (en) * | 2014-05-08 | 2014-09-24 | 昆明有色冶金设计研究院股份公司 | System and method for treating waste electrolyte |
| CN104060301B (en) * | 2014-05-08 | 2016-11-30 | 昆明有色冶金设计研究院股份公司 | A kind of waste electrolyte processing system and method |
| CN106521163A (en) * | 2016-11-05 | 2017-03-22 | 北京工业大学 | Method for copper-bearing waste chloride solution precious metal enrichment |
| CN106882884A (en) * | 2017-02-16 | 2017-06-23 | 华电电力科学研究院 | A kind of method of chlorion in recycling waste water |
| CN107142379A (en) * | 2017-06-07 | 2017-09-08 | 云南金鼎锌业有限公司 | A kind of zinc comprehensive recovering process |
| CN115557647A (en) * | 2022-10-25 | 2023-01-03 | 广西华锡矿业有限公司再生资源分公司 | Method for reducing arsenic content in high-arsenic ion beneficiation wastewater |
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| US6361753B1 (en) * | 1995-12-26 | 2002-03-26 | Joseph B. Cashman | Converting zinc chloride to zinc oxide during the hydrometallurgical processing of flue dust |
| US6770249B1 (en) * | 1999-09-27 | 2004-08-03 | Chester W. Whitman | Process to selectively recover metals from waste dusts, sludges and ores |
| CN1639360A (en) * | 2002-01-23 | 2005-07-13 | 萨普工业公司 | Method for the separation of zinc and a second metal which does not form an anionic complex in the presence of chloride ions |
| CN101709382A (en) * | 2009-12-17 | 2010-05-19 | 新乡超能电源有限公司 | Recovery and comprehensive treatment process of valuable metals in zinciferous materials |
| CN101818252A (en) * | 2009-08-28 | 2010-09-01 | 麦强 | Non-volatile method for extracting zinc, iron and indium from solution of zinc, iron and indium |
-
2013
- 2013-12-13 CN CN201310681781.0A patent/CN103695649A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361753B1 (en) * | 1995-12-26 | 2002-03-26 | Joseph B. Cashman | Converting zinc chloride to zinc oxide during the hydrometallurgical processing of flue dust |
| US6770249B1 (en) * | 1999-09-27 | 2004-08-03 | Chester W. Whitman | Process to selectively recover metals from waste dusts, sludges and ores |
| CN1639360A (en) * | 2002-01-23 | 2005-07-13 | 萨普工业公司 | Method for the separation of zinc and a second metal which does not form an anionic complex in the presence of chloride ions |
| CN101818252A (en) * | 2009-08-28 | 2010-09-01 | 麦强 | Non-volatile method for extracting zinc, iron and indium from solution of zinc, iron and indium |
| CN101709382A (en) * | 2009-12-17 | 2010-05-19 | 新乡超能电源有限公司 | Recovery and comprehensive treatment process of valuable metals in zinciferous materials |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060301A (en) * | 2014-05-08 | 2014-09-24 | 昆明有色冶金设计研究院股份公司 | System and method for treating waste electrolyte |
| CN104060301B (en) * | 2014-05-08 | 2016-11-30 | 昆明有色冶金设计研究院股份公司 | A kind of waste electrolyte processing system and method |
| CN106521163A (en) * | 2016-11-05 | 2017-03-22 | 北京工业大学 | Method for copper-bearing waste chloride solution precious metal enrichment |
| CN106882884A (en) * | 2017-02-16 | 2017-06-23 | 华电电力科学研究院 | A kind of method of chlorion in recycling waste water |
| CN106882884B (en) * | 2017-02-16 | 2019-08-20 | 华电电力科学研究院 | A kind of method of chloride ion in recycling waste water |
| CN107142379A (en) * | 2017-06-07 | 2017-09-08 | 云南金鼎锌业有限公司 | A kind of zinc comprehensive recovering process |
| CN115557647A (en) * | 2022-10-25 | 2023-01-03 | 广西华锡矿业有限公司再生资源分公司 | Method for reducing arsenic content in high-arsenic ion beneficiation wastewater |
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Application publication date: 20140402 |