CN103214121A - 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
- Publication number
- CN103214121A CN103214121A CN2013101565067A CN201310156506A CN103214121A CN 103214121 A CN103214121 A CN 103214121A CN 2013101565067 A CN2013101565067 A CN 2013101565067A CN 201310156506 A CN201310156506 A CN 201310156506A CN 103214121 A CN103214121 A CN 103214121A
- Authority
- CN
- China
- Prior art keywords
- copper
- iron
- agent
- mine
- molecule chelated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
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 the acid wastewater in mine.
Background technology
Acidic mine waste water is low because of its pH value, acidity is big, and contains a large amount of heavy metals, can cause the mining area severe contamination of water body on every side.The comprehensive regulation compliance rate of wherein national copper mine waste water only is 70%.Still have that waste water about 30% is unprocessed directly to efflux, existing treatment unit operation ratio also only is 20%, mining and utilize the copper-containing acid waste water that is produced to become water ecological environment is polluted one of the most serious industry.Therefore be badly in need of the copper-containing acid waste water treatment process of energy high-efficiency environment friendly.
The technology of Treatment of Copper acid waste water mainly contains lime neutralisation and sulphide precipitation at present.Chinese patent CN101974690A adopts calcium hydroxide to separate rare earth element, Chinese patent CN102786133A adopts milk of lime to reclaim copper and iron in the acid mine, but the lime neutralisation can be brought a large amount of sediments, and these sediments can not be utilized once more, not to exist the mine tailing storehouse to account for a large amount of storage capacity, being met acid behind the landfill has secondary pollution exactly, and water outlet can not the stably reaching standard discharging.
Sulfide method needs three sections processing, at first iron is precipitated earlier with liquid caustic soda, second step precipitated copper with sulfide, the 3rd step was adjusted to pH neutrality with liquid caustic soda again makes water up to standard, Chinese patent 201110408370 adopts sulfide to administer waste water on the ore deposit, but this process can produce a large amount of hydrogen sulfide secondary pollutions, and scum can't utilize once more because of the water content height, be to account for the storage capacity waste residue equally, the sulfuration copper ashes is difficult to solid-liquid separation because of particle is minimum.
Summary of the invention
The purpose of this invention is to provide a kind of employing two-step approach, it is simple to have technology, non-secondary pollution, slagging tap to become product, and press filtration easily, accomplish zero storage capacity, water outlet is stably reaching standard comprehensively, but the high-molecule chelated precipitation agent two step method of water outlet reuse ore dressing reclaims the method for copper iron in the acid wastewater in mine.
The present invention includes following steps:
1) in acid wastewater in mine, adds liquid caustic soda, enter next stirred tank behind the adjusting pH to 2.7, add the high-molecule chelated copper agent of proposing again, regulate pH to 4.2～4.4;
2) add the flocculation agent sedimentation again, solid-liquid separation, sediment is cupric 20%～30% copper ore concentrates, and supernatant liquor enters carries the iron reactive tank, adds the high-molecule chelated chalybeate of carrying, regulate pH to 8.2～8.5, add the flocculation agent sedimentation, solid-liquid separation, sediment is an iron ore concentrate, supernatant liquor can reach first discharge standard, can directly discharge or reuse.
In step 1), it is 30% sodium hydroxide solution that described liquid caustic soda can adopt concentration; When entering next stirred tank behind the adjusting pH to 2.7, the effect with free acid during liquid caustic soda only plays can't produce precipitation slag; The described high-molecule chelated copper agent raw material composition by mass percentage of carrying can be: dimethyl sulphide is a water for dithiocarbamic acid 35%, ethylenediamine tetraacetic acid (EDTA) 15%, surplus.
In step 2) in, described flocculation agent is optional from polyacrylamide; It is 1,400 ten thousand cationic-type polyacrylamides that described polyacrylamide can adopt molecular weight; The described high-molecule chelated chalybeate raw material composition by mass percentage of carrying can be: sodium dimercaptosuccinate 40%, N, and N '-two (2-acrinyl) quadrol-N, N '-oxalic acid 25%, surplus are water.
Compare with existing processes, the present invention does not adopt first deironing, carries copper again, and last redeposition three-step approach up to standard, but directly carry copper is earlier carried iron after carrying copper again, carries iron and finishes technology and just finish, be i.e. two-step approach.The traditional technology sulfide method then must use earlier alkali precipitation iron, otherwise adds the sulfide precipitation that can generate iron and copper behind the sulfide simultaneously, and copper is not only heavy clean but also the reagent consumption amount is very big, and the sediment cupric hangs down can not become copper ore concentrates.And the high-molecular chelating agent that the present invention uses can directly earlier settle out copper in iron-containing liquor because copper is had extremely strong selectivity, and reaction process does not produce hydrogen sulfide.Carrying copper, propose iron reaction after, sediment is the product that can utilize once more, rather than accounts for the waste residue of storage capacity, can accomplish zero storage capacity.Carry copper and propose iron reaction and all do not have gas outputs such as hydrogen sulfide, no gas secondary pollution.Institute's with medicament is the high-molecule chelated copper agent of carrying, the high-molecule chelated chalybeate of carrying, and liquid caustic soda (30%NaOH), polyacrylamide flocculant (molecular weight 1,400 ten thousand is cationic).
Embodiment
Following examples will the present invention is further illustrated.
Specific embodiment of the present invention is: copper-containing acid waste water enters the liquid caustic soda regulating tank behind the surge tank current stabilization, add 30% concentration liquid caustic soda, stirring reaction, control overflow port pH is 2.6～2.7, overflow enters puies forward the copper retort, add high-molecule chelated copper agent (the high-molecule chelated copper agent product of carrying that can adopt Fujian Green's nobelium Bel Environmental Protection Technology Co., Ltd to produce of carrying, the high-molecule chelated copper agent raw material by mass percentage of carrying consists of: dimethyl sulphide is for dithiocarbamic acid 35%, ethylenediamine tetraacetic acid (EDTA) 15%, surplus is a water), stirring reaction, control overflow port pH is 4.2～4.4, link and control and stable pH value by controlling high-molecule chelated copper agent dosing pump flow and the pH meter carried, overflow enters the copper ashes thickener, add flocculation agent before advancing thickener, underflow carries out press filtration after the thickener sedimentation, obtain the copper filter cake, the overflow of copper thickener supernatant liquor enters carries iron flask, add high-molecule chelated chalybeate (the high-molecule chelated chalybeate product of carrying that can adopt Fujian Green's nobelium Bel Environmental Protection Technology Co., Ltd to produce of carrying, the 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 a water), stirring reaction, control overflow port pH is 8.2～8.5, with last same, link by control NB-2 dosing pump flow and pH meter and to control and stable pH value, overflow enters the scum thickener, add the flocculation agent polyacrylamide before advancing thickener, underflow carries out press filtration after the thickener sedimentation, obtain the iron filter cake, but iron thickener supernatant liquor overflow 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 after liquid caustic soda (30%NaOH) is adjusted to pH2.7 and carries the copper jar, adds the high-molecule chelated copper agent stirring 10～15min that carries, add the flocculation agent polyacrylamide through the 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 meet the copper ore concentrates standard.The water outlet of copper thickener enters carries iron flask, add the high-molecule chelated chalybeate of carrying and stir 10～15min, add the flocculation agent polyacrylamide through the 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 fully.
Claims (6)
1. high-molecule chelated precipitation agent two step method reclaims the method for copper iron in the acid wastewater in mine, it is characterized in that may further comprise the steps:
1) in acid wastewater in mine, adds liquid caustic soda, enter next stirred tank behind the adjusting pH to 2.7, add the high-molecule chelated copper agent of proposing again, regulate pH to 4.2～4.4;
2) add the flocculation agent sedimentation again, solid-liquid separation, sediment is cupric 20%～30% copper ore concentrates, and supernatant liquor enters carries the iron reactive tank, adds the high-molecule chelated chalybeate of carrying, regulate pH to 8.2～8.5, add the flocculation agent sedimentation, solid-liquid separation, sediment is an iron ore concentrate, supernatant liquor can reach first discharge standard, can directly discharge or reuse.
2. high-molecule chelated according to claim 1 precipitation agent two step method reclaims the method for copper iron in the acid wastewater in mine, it is characterized in that in step 1), and described liquid caustic soda employing concentration is 30% sodium hydroxide solution.
3. high-molecule chelated according to claim 1 precipitation agent two step method reclaims the method for copper iron in the acid wastewater in mine, it is characterized in that in step 1) the described high-molecule chelated copper agent raw material by mass percentage of carrying consists of: dimethyl sulphide is a water for dithiocarbamic acid 35%, ethylenediamine tetraacetic acid (EDTA) 15%, surplus.
4. high-molecule chelated according to claim 1 precipitation agent two step method reclaims the method for copper iron in the acid wastewater in mine, it is characterized in that in step 2) in, described flocculation agent is selected from polyacrylamide.
5. reclaim the method for copper iron in the acid wastewater in mine as high-molecule chelated precipitation agent two step method as described in the claim 4, it is characterized in that it is 1,400 ten thousand cationic-type polyacrylamides that described polyacrylamide adopts molecular weight.
6. high-molecule chelated according to claim 1 precipitation agent two step method reclaims the method for copper iron in the acid wastewater in mine, it is characterized in that in step 2) in, the 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103214121A true CN103214121A (en) | 2013-07-24 |
| CN103214121B CN103214121B (en) | 2014-12-24 |
Family
ID=48812347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310156506.7A Expired - Fee Related 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103214121B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478060A (en) * | 2014-11-27 | 2015-04-01 | 长沙矿冶研究院有限责任公司 | Chemical agent and process for treating wastewater containing thallium and heavy metals |
| 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 |
| CN107176711A (en) * | 2017-04-20 | 2017-09-19 | 东北大学 | The technique of copper in a kind of high efficiente callback high concentration berberine waste water |
Families Citing this family (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 |
Citations (4)
| 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 |
| US20070045189A1 (en) * | 2005-08-31 | 2007-03-01 | General Electric Company | Acid mine water demineralization methods |
| 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 |
-
2013
- 2013-04-27 CN CN201310156506.7A patent/CN103214121B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| US20070045189A1 (en) * | 2005-08-31 | 2007-03-01 | General Electric Company | Acid mine water demineralization methods |
| 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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478060A (en) * | 2014-11-27 | 2015-04-01 | 长沙矿冶研究院有限责任公司 | Chemical agent and process for treating wastewater containing thallium and heavy metals |
| 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 |
| CN107176711A (en) * | 2017-04-20 | 2017-09-19 | 东北大学 | The technique of copper in a kind of high efficiente callback high concentration berberine waste water |
| CN107176711B (en) * | 2017-04-20 | 2020-10-16 | 东北大学 | Process for efficiently recovering copper in high-concentration berberine wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103214121B (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102730885B (en) | Efficient flocculent precipitate purification method for polymetallic ore benefication wastewater | |
| CN101648759B (en) | Recycling processing method for wastewater produced by processing stainless steel | |
| CN107601779B (en) | Method and device for treating and recycling mine copper-containing acidic wastewater | |
| CN103588235B (en) | Method for producing polyaluminium sulfate by using red mud slag | |
| CN103214121B (en) | Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process | |
| CN104086030B (en) | A kind for the treatment of process of steel industry pickling waste waters | |
| CN103351066A (en) | Novel wet flue gas desulfurization wastewater treatment method and system | |
| CN102115890B (en) | Total recycling method of PCB (printed circuit board) nitric acid type tin-lead stripping waste liquid | |
| CN102153217B (en) | Electroplating integrated wastewater treatment method | |
| CN108218025A (en) | The method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes | |
| CN105439326A (en) | Treatment method of chemical nickel-plating wastewater | |
| CN102115284A (en) | Method for treating manganese-containing wastewater generated during electrolytic manganese processing | |
| CN102766883B (en) | Spent solder stripper recovery method and equipment | |
| CN104230010A (en) | Softening method for coal gasification grey water with high temporary hardness | |
| CN103626322A (en) | Double-alkali neutralization treatment method of heavy metal-containing acidic wastewater | |
| CN103771630A (en) | Process for treating and recycling mine acid heavy metal wastewater | |
| CN105776655A (en) | Method for producing copper concentrates and prussian blue by means of mine copper cyanide wastewater | |
| CN103495589B (en) | A kind of plating waste residue recoverying and utilizing method | |
| CN102417255B (en) | Efficient and economic mercury-containing waste water treatment method | |
| CN103253800A (en) | Method for treating gold production sewage | |
| CN104058517A (en) | Metallurgical industry cold rolling acid wastewater treatment system device and process thereof | |
| CN102167436B (en) | Electroplating wastewater treating agent | |
| CN204529926U (en) | The ion-exchange dechlorination system of solution of zinc sulfate in wet method zinc abstraction | |
| CN105692954A (en) | Method of reducing residue yield during acidic wastewater treatment | |
| CN105585146A (en) | A process of treating mine wastewater through applying a membrane technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20160427 |