CN103214121B - Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process - Google Patents
Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process Download PDFInfo
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- CN103214121B CN103214121B CN201310156506.7A CN201310156506A CN103214121B CN 103214121 B CN103214121 B CN 103214121B CN 201310156506 A CN201310156506 A CN 201310156506A CN 103214121 B CN103214121 B CN 103214121B
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Abstract
The invention discloses a method for recycling copper and iron in acid mine wastewater by a high-polymer chelating-precipitating agent two-step process, relates to a wastewater treatment method and provides a method for recycling copper and iron in acid mine wastewater by a high-polymer chelating-precipitating agent two-step process, and the method adopts the two-step process, is simple in process and free of secondary pollution, capable of changing the outlet slag into finished products and easily pressing and filtering the slag, so that the zero storage capacity is achieved, the outlet water can completely satisfy the standards and the outlet water can be recycled for mineral processing. The method comprises the following steps of: adding liquid caustic soda to the acid mine wastewater for entering a next stirring reaction slot after regulating the pH of the wastewater to 2.7; adding the high-polymer cheating copper-extracting agent for regulating the pH to 4.2-4.4; adding flocculating agent for carrying out sedimentation and solid-liquid separation, wherein the sediment is copper concentrate with 20%-30% of copper, and the liquid supernatant enters an ion-extracting reaction slot; the high-polymer cheating iron-extracting agent is added to regulate the pH to 8.2-8.5; and the flocculating agent is added for carrying out sedimentation and solid-liquid separation, wherein the sediment is iron concrete, and the liquid supernatant can reach the first-level emission standards and can be directly exhausted or recycled.
Description
Technical field
The present invention relates to method of wastewater treatment, especially relate to the method that high-molecule chelated precipitation agent two step method reclaims copper iron in acid wastewater in mine.
Background technology
Acidic mine waste water because its pH value is low, acidity large, and containing a large amount of heavy metals, can cause the severe contamination of mining area surrounding water.Wherein the comprehensive regulation compliance rate of national copper mine waster water is only 70%.Still have the unprocessed directly outer row of the waste water of about 30%, existing treatment unit operation ratio is also only 20%, mining and utilize the copper-containing acid waste water produced to become to pollute one of the most serious industry to water ecological environment.Therefore the copper-containing acid waste water treatment process of energy high-efficiency environment friendly is badly in need of.
The technique of current Treatment of Copper acid waste water mainly contains limestone vegetation method and sulphide precipitation.Chinese patent CN101974690A adopts calcium hydroxide to be separated rare earth element, Chinese patent CN102786133A adopts milk of lime to reclaim copper and iron in Acid mine, but limestone vegetation method can bring a large amount of sediment, and these sediments can not be utilized again, not there is Tailings Dam to account for a large amount of storage capacity, be landfilled rear chance acid exactly and have secondary pollution, and water outlet can not stably reaching standard discharge.
Sulfide method needs three sections of process, first with liquid caustic soda, iron is first precipitated, second step sulfide precipitates copper, 3rd step is adjusted to pH neutrality with liquid caustic soda again makes water up to standard, Chinese patent 201110408370 adopts waste water on Sulfide treatment ore deposit, but this process can produce a large amount of hydrogen sulfide secondary pollution, and scum cannot utilize again because water content is high, be account for storage capacity waste residue equally, sulfuration copper ashes is difficult to solid-liquid separation because particle is minimum.
Summary of the invention
The object of this invention is to provide a kind of employing two-step approach, there is technique simple, non-secondary pollution, slag tap and can become product, and easily press filtration, accomplish zero storage capacity, water outlet can allround fastness up to standard, water outlet the high-molecule chelated precipitation agent two step method of reuse ore dressing can reclaim the method for copper iron in acid wastewater in mine.
The present invention includes following steps:
1) in acid wastewater in mine, add liquid caustic soda, regulate after pH to 2.7 and enter next stirred tank, then add and high-molecule chelatedly propose copper agent, regulate pH to 4.2 ~ 4.4;
2) flocculation agent sedimentation is added again, solid-liquid separation, sediment is cupric 20% ~ 30% copper ore concentrates, and supernatant liquor enters carries iron reactive tank, adds high-molecule chelatedly to carry chalybeate, regulate pH to 8.2 ~ 8.5, add flocculation agent sedimentation, solid-liquid separation, sediment is iron ore concentrate, supernatant liquor can reach first discharge standard, can directly discharge or reuse.
In step 1), described liquid caustic soda can adopt concentration be 30% sodium hydroxide solution; When entering next stirred tank after regulating pH to 2.7, during liquid caustic soda only plays, precipitation slag can't be produced with the effect of free acid; Described high-molecule chelated copper agent raw material composition by mass percentage of carrying can be: dimethyl thio dithiocarbamic acid 35%, ethylenediamine tetraacetic acid (EDTA) 15%, surplus are water.
In step 2) in, described flocculation agent is optional from polyacrylamide; Described polyacrylamide can adopt molecular weight to be 1,400 ten thousand cationic-type polyacrylamides; Described high-molecule chelated chalybeate raw material composition by mass percentage of carrying can be: sodium dimercaptosuccinate 40%, N, N '-two (2-acrinyl) quadrol-N, N '-oxalic acid 25%, surplus are water.
Compared with existing technique, the present invention does not adopt first deironing, then carries copper, the three-step approach that last redeposition is up to standard, but directly first carries copper, carries iron again after carrying copper, carries iron and completes technique and just complete, be i.e. two-step approach.Traditional technology sulfide method, then must first use alkali precipitation iron, otherwise can generate the sulfide precipitation of iron and copper after adding sulfide simultaneously, and copper not only sinks clean but also reagent consumption amount is very large, and sediment cupric is low can not become copper ore concentrates.And the high-molecular chelating agent that the present invention uses is because have extremely strong selectivity to copper, directly first copper can be settled out in iron-containing liquor, and reaction process does not produce hydrogen sulfide.Carrying copper, after proposing iron reaction, sediment is the product that can again utilize, instead of accounts for the waste residue of storage capacity, can accomplish zero storage capacity.Carry copper and propose iron reaction all without gas outputs such as hydrogen sulfide, without gas secondary pollution.Institute's with medicament is high-molecule chelatedly propose copper agent, high-molecule chelatedly carries chalybeate, and liquid caustic soda (30%NaOH), polyacrylamide flocculant (molecular weight 1,400 ten thousand is cationic).
Embodiment
The present invention is further illustrated for following examples.
Specific embodiment of the present invention is: copper-containing acid waste water enters liquid caustic soda regulating tank after surge tank current stabilization, add 30% concentration liquid caustic soda, stirring reaction, controlling water kick mouth pH is 2.6 ~ 2.7, overflow enters puies forward copper retort, add and high-molecule chelatedly propose copper agent (what Fujian Green's nobelium Bel Environmental Protection Technology Co., Ltd can be adopted to produce high-molecule chelatedly carries copper agent product, high-molecule chelated copper agent raw material by mass percentage of carrying consists of: dimethyl thio dithiocarbamic acid 35%, ethylenediamine tetraacetic acid (EDTA) 15%, surplus is water), stirring reaction, controlling water kick mouth pH is 4.2 ~ 4.4, by controlling high-molecule chelatedly to carry copper agent dosing pump flow and pH meter links control and stablize pH value, overflow enters copper ashes thickener, flocculation agent is added before entering thickener, after thickener sedimentation, underflow carries out press filtration, obtain copper filter cake, the overflow of copper thickener supernatant liquor enters carries iron flask, add and high-molecule chelatedly carry chalybeate (what Fujian Green's nobelium Bel Environmental Protection Technology Co., Ltd can be adopted to produce high-molecule chelatedly carries chalybeate product, high-molecule chelated chalybeate raw material by mass percentage of carrying consists of: sodium dimercaptosuccinate 40%, N, N '-two (2-acrinyl) quadrol-N, N '-oxalic acid 25%, surplus is water), stirring reaction, controlling water kick mouth pH is 8.2 ~ 8.5, with upper same, link control and stablize pH value by control NB-2 dosing pump flow and pH meter, overflow enters scum thickener, flocculation agent polyacrylamide is added before entering thickener, after thickener sedimentation, underflow carries out press filtration, obtain iron filter cake, the overflow of iron thickener supernatant liquor can qualified discharge or reuse.
Below provide specific embodiment: the total copper concentration of copper-containing acid waste water is 300 ~ 500mg/L, total iron 250 ~ 500mg/L, pH2.1, enters and carries copper tank after liquid caustic soda (30%NaOH) is adjusted to pH2.7, add high-molecule chelated carry copper agent stir 10 ~ 15min, add flocculation agent polyacrylamide through thickener sedimentation, water outlet cupric 0.3 ~ 7mg/L, iron content 250 ~ 300mg/L, copper ashes cupric 28% ~ 31%, copper recovery 98% ~ 99%, copper ashes meets copper ore concentrates standard.The water outlet of copper thickener enters carries iron flask, add high-molecule chelated chalybeate of carrying and stir 10 ~ 15min, add flocculation agent polyacrylamide through thickener sedimentation, water outlet cupric 0.01 ~ 0.08mg/L, iron content 0.41 ~ 1.52mg/L, scum iron content 35% ~ 46%, iron recovery 82% ~ 85%, all indexs of water outlet meet national grade one discharge standard completely.
Claims (4)
1. high-molecule chelated precipitation agent two step method reclaims the method for copper iron in acid wastewater in mine, it is characterized in that comprising the following steps:
1) in acid wastewater in mine, add liquid caustic soda, regulate after pH to 2.7 and enter next stirred tank, then add and high-molecule chelatedly propose copper agent, regulate pH to 4.2 ~ 4.4; Described high-molecule chelated copper agent raw material by mass percentage of carrying consists of: dimethyl thio dithiocarbamic acid 35%, ethylenediamine tetraacetic acid (EDTA) 15%, surplus are water;
2) flocculation agent sedimentation is added again, solid-liquid separation, sediment is cupric 20% ~ 30% copper ore concentrates, and supernatant liquor enters carries iron reactive tank, adds high-molecule chelatedly to carry chalybeate, regulate pH to 8.2 ~ 8.5, add flocculation agent sedimentation, solid-liquid separation, sediment is iron ore concentrate, supernatant liquor can reach first discharge standard, can directly discharge or reuse; Described high-molecule chelated chalybeate raw material by mass percentage of carrying consists of: sodium dimercaptosuccinate 40%, N, N '-two (2-acrinyl) quadrol-N, N '-oxalic acid 25%, surplus are water.
2. high-molecule chelated precipitation agent two step method reclaims the method for copper iron in acid wastewater in mine as claimed in claim 1, it is characterized in that in step 1) in, described liquid caustic soda adopts concentration to be the sodium hydroxide solution of 30%.
3. high-molecule chelated precipitation agent two step method reclaims the method for copper iron in acid wastewater in mine as claimed in claim 1, it is characterized in that in step 2) in, described flocculation agent is selected from polyacrylamide.
4. high-molecule chelated precipitation agent two step method reclaims the method for copper iron in acid wastewater in mine as claimed in claim 3, it is characterized in that described polyacrylamide adopts molecular weight to be 1,400 ten thousand cationic-type polyacrylamides.
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| CN201310156506.7A CN103214121B (en) | 2013-04-27 | 2013-04-27 | Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503085A (en) * | 2018-04-20 | 2018-09-07 | 广东华矿高新技术有限公司 | The fractional precipitation process of iron/copper in a kind of recycling acidic mine waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104478060B (en) * | 2014-11-27 | 2016-06-15 | 长沙矿冶研究院有限责任公司 | A kind of process contains medicament and the technique of thallium and other heavy metal wastewater therebies |
| CN104876369A (en) * | 2015-06-09 | 2015-09-02 | 长春黄金研究院 | Comprehensive treatment process of acid wastewater of nonferrous metal mine |
| CN104961269A (en) * | 2015-06-09 | 2015-10-07 | 长春黄金研究院 | Nonferrous metal mine acidic wastewater comprehensive treatment method |
| CN107176711B (en) * | 2017-04-20 | 2020-10-16 | 东北大学 | Process for efficiently recovering copper in high-concentration berberine wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651491A (en) * | 2004-12-28 | 2005-08-10 | 华南理工大学 | Preparation method of amino dithio carboxylic acid polymer chelating agent |
| EP1772432A1 (en) * | 2004-03-05 | 2007-04-11 | Hosoda Electric Co., Ltd. | Acidic water producing device, acidic water producing method, and acidic water |
| CN102311189A (en) * | 2011-08-12 | 2012-01-11 | 马前 | System for treatment of acid mine drainage and resource recovery of iron, aluminum, copper and zinc in drainage |
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| US20070045189A1 (en) * | 2005-08-31 | 2007-03-01 | General Electric Company | Acid mine water demineralization methods |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1772432A1 (en) * | 2004-03-05 | 2007-04-11 | Hosoda Electric Co., Ltd. | Acidic water producing device, acidic water producing method, and acidic water |
| CN1651491A (en) * | 2004-12-28 | 2005-08-10 | 华南理工大学 | Preparation method of amino dithio carboxylic acid polymer chelating agent |
| CN102311189A (en) * | 2011-08-12 | 2012-01-11 | 马前 | System for treatment of acid mine drainage and resource recovery of iron, aluminum, copper and zinc in drainage |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503085A (en) * | 2018-04-20 | 2018-09-07 | 广东华矿高新技术有限公司 | The fractional precipitation process of iron/copper in a kind of recycling acidic mine waste water |
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