CN104909497A - Method for treating acid waste water of nonferrous metal mine - Google Patents
Method for treating acid waste water of nonferrous metal mine Download PDFInfo
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Abstract
The invention discloses a method for treating acid waste water of a nonferrous metal mine. The method mainly comprises four steps of oxidization treatment, membrane treatment, vulcanization treatment and neutralization treatment, wherein during the treatment of the acid waste water, divalent iron ions are oxidized into trivalent iron ions by adopting an oxidant or aeration manner at first, then an iron precipitation reaction is performed, a clear solution obtained after the reaction enters a membrane treatment system and is subjected to separation and concentration, the concentrated solution is subjected to vulcanization precipitation treatment to recover valuable metals, and the clear solution after vulcanization reaction is subjected to neutralization precipitation in a neutralization treatment unit. By adopting the method disclosed by the invention, according to the characteristics that the acid waste water of the nonferrous metal mine is low in pH value, contains various heavy metals and the like, the oxidation treatment, iron precipitation treatment, membrane treatment, vulcanization precipitation, coagulative precipitation and neutralization treatment technologies are combined together, and the acid waste water of the nonferrous metal mine is treated sequentially and synergistically step by step, so that the method has the advantages of being good in treatment effect, high in treatment efficiency, stable in system running, capable of recovering valuable resources in water, easy to realize industrial application and the like, and the treated waste water can be returned to production process flows to serve as regenerated water in use or is discharged with standards.
Description
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly a kind of nonferrous metal mine process for treating acidic waste water.
Background technology
Most of nonferrous metal mine belongs to polymetallic ore, ore contains the valuable elements such as copper, lead, zinc, gold and silver, molybdenum, these metallic elements are mainly based on secondary sulphide ores, these mineral are in recovery process, due to the acting in conjunction of air, water and bacterium, form sulfuric acid, metal sulfate, and the many kinds of metal ions in stripping ore, thus form the acid waste water containing copper, iron, zinc, manganese etc.After acid wastewater in mine enters environment, the pH value of water body can be made to change, destroy the natural shock absorption of water body, eliminate or suppress microbial growth, hinder self purification of water body, cause the phenomenons such as water body appearance is smelly, variable color, and structures and other mechanical means such as sour water meeting heavy corrosion pipeline, water pump, cement, bring huge threat to the health of people, life and production.At present, chemical precipitation method, ion exchange method, electrolytic process, membrane separation process etc. are mainly contained to the method for acid wastewater in mine process.Chemical precipitation method equipment is simple, technology maturation, but reaction produces the quantity of slag greatly, easily cause secondary pollution, and moisture percentage in sewage sludge is high, easily causes the waste of water resources.The heavy-metal acid waste water of ion exchange method suitable treatment lower concentration, treatment effect is better, but exchange resin regeneration used is frequent, and process cost is higher.Electrolytic process be applied to wastewater treatment have equipment simple, take up an area little, easy to operate, effectively reclaim the advantages such as valuable metal, but current consumption is large, and the shortcomings such as wastewater treatment capacity is little limit it and obtain range of application.Membrane separation process is applicable to process low-concentration heavy metal acid waste water, and producing water can cyclically utilizing, but condensed water needs process further.From upper, above-mentioned various treatment process is both advantageous and disadvantageous, limits the application of this method to a certain extent, and therefore, how studying a kind of process for treating acidic waste water that is pratical and feasible, economical rationality is the task of top priority that current nonferrous metal mine faces.
Summary of the invention
Object of the present invention is exactly the problems referred to above existed for existing treatment process, and provides the nonferrous metal mine process for treating acidic waste water that a kind of technical process is simple, treatment effect good, processing efficiency is high, stable.
The present invention is low according to nonferrous metal mine acid waste water pH value, containing heavy metal, sulfate concentration high, first adopt oxidizing reaction and precipitin reaction by the iron ion removing in waste water, then membrane processing method is selected to be concentrated by acid waste water, pure water qualified discharge or return in technical process, concentrated solution carries out sulfide precipitation process, reclaim the valuable resources such as Cu in waste water ion, the supernatant liquor after sulfide precipitation carries out neutralizing treatment.
The present invention includes following steps:
(1), oxidizing reaction: acid waste water adopts the mode adding oxygenant or pass into air aeration oxidation, the oxidation of divalent iron ion with reducing metal ion is become the ferric ion of oxidative metal ion, if reducing metal ion content is less in waste water, directly next step reaction can be carried out;
(2) heavy iron reaction: the waste water after oxidizing reaction is by adding alkaline reagents, pH value is adjusted between 3.5 ~ 4.0, reaction times is at least 20min, ferric ion is transformed into ironic hydroxide precipitate down completely, or add phosphoric acid salt control waste water ph between 1.5 ~ 2.5, reaction times is at least 30min, ferric ion is transformed into tertiary iron phosphate precipitation to go down, coagulated agent can be added during reaction and promote precipitation, if without ferric ion in waste water, can directly enter film treatment step.
(3), solid-liquid separation: the throw out of heavy iron reaction carries out solid-liquid separation by the solid-liquid separation method of thickener, settling tank, filter, whizzer, clear liquid after separation enters film treatment step, solid after separation is purified further, prepares molysite product.
(4), film process: first the clear liquid after solid-liquid separation carries out uf processing, then reverse osmosis is entered into or nanofiltration membrane treatment system carries out film process, after process output pure water in and qualified discharge or return technical process, the concentrated solution of output is for further processing;
(5), sulfidizing: the concentrated solution of film process output is under whipped state, add sulfiding reagent or heavy metal chelant, reaction times is at least 20min, makes the cupric ion in waste liquid or other heavy metal ion generate throw out hard to tolerate, then adds coagulated agent and promotes precipitation;
(6), solid-liquid separation: the slag-water slurry after sulfidizing carries out solid-liquid separation by the solid-liquid separation method of settling tank, filter, whizzer, the solid separated is by purifying further, prepare metal product, the clear liquid after separation enters neutralizing treatment step;
(7), neutralizing treatment: the clear liquid after solid-liquid separation carries out neutralizing treatment by adding between alkaline reagents adjust ph to 7 ~ 9, and the neutralizing treatment reaction times is at least 30min, then adds coagulated agent and carries out coagulating sedimentation;
(8), solid-liquid separation: the slag-water slurry after neutralizing treatment carries out solid-liquid separation by the solid-liquid separation method of thickener, settling tank, filter, whizzer, in and slag be delivered to slag field and carry out storing up or turn back to heavy iron reactions steps and neutralizing treatment step, standard emission of clear or return in technical process.
In described step (1), oxygenant is hydrogen peroxide, chlorinated lime, clorox or ozone.
In described step (2), alkaline reagents is unslaked lime, white lime, calcium carbonate, sodium carbonate or sodium hydroxide, and phosphoric acid salt is sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC or ammonium phosphate, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
In described step (4), ultrafiltration, reverse osmosis or nanofiltration treatment system are one or more levels treatment unit, and ultra-filtration membrane, reverse osmosis membrane or nanofiltration membrane adopt acidproof, resistant to pollution film.
In described step (5), sulfiding reagent is inorganic sulphide or organic sulfide medicament, such as sodium sulphite, iron sulphide or sulfurated lime, heavy metal chelant is xanthate class, dithiocarbamate salt derivative or other heavy metal chelants, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
In described step (7), alkaline reagents is unslaked lime, white lime, calcium carbonate, sodium carbonate or sodium hydroxide, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
Beneficial effect of the present invention:
The present invention is low according to nonferrous metal mine acid waste water pH, containing features such as various heavy, by oxide treatment, heavy iron process, film process, sulfide precipitation, coagulating sedimentation and neutralizing treatment combine with technique together, orderly substep is collaborative to be processed nonferrous metal mine acid waste water, have that treatment effect is good, processing efficiency is high, system run all right, can valuable resource in recycle-water, be easy to the advantages such as industrial application, the waste water after process can return the technological process of production and use or qualified discharge as reuse water.
Accompanying drawing explanation
Fig. 1 is schema of the present invention.
Embodiment
With reference to accompanying drawing 1, the present invention includes following steps:
(1), oxidizing reaction: acid waste water adopts the mode adding oxygenant or pass into air aeration oxidation, the oxidation of divalent iron ion with reducing metal ion is become the ferric ion of oxidative metal ion, if reducing metal ion content is less in waste water, directly next step reaction can be carried out;
(2) heavy iron reaction: the waste water after oxidizing reaction is by adding alkaline reagents, pH value is adjusted between 3.5 ~ 4.0, reaction times is at least 20min, ferric ion is transformed into ironic hydroxide precipitate down completely, or add phosphoric acid salt control waste water ph between 1.5 ~ 2.5, reaction times is at least 30min, ferric ion is transformed into tertiary iron phosphate precipitation to go down, coagulated agent can be added during reaction and promote precipitation, if without ferric ion in waste water, can directly enter film treatment step.
(3), solid-liquid separation: the throw out of heavy iron reaction carries out solid-liquid separation by the solid-liquid separation method of thickener, settling tank, filter, whizzer, clear liquid after separation enters film treatment step, solid after separation is purified further, prepares molysite product.
(4), film process: first the clear liquid after solid-liquid separation carries out uf processing, then reverse osmosis is entered into or nanofiltration membrane treatment system carries out film process, after process output pure water in and qualified discharge or return technical process, the concentrated solution of output is for further processing;
(5), sulfidizing: the concentrated solution of film process output is under whipped state, add sulfiding reagent or heavy metal chelant, reaction times is at least 20min, makes the cupric ion in waste liquid or other heavy metal ion generate throw out hard to tolerate, then adds coagulated agent and promotes precipitation;
(6), solid-liquid separation: the slag-water slurry after sulfidizing carries out solid-liquid separation by the solid-liquid separation method of settling tank, filter, whizzer, the solid separated is by purifying further, prepare metal product, the clear liquid after separation enters neutralizing treatment step;
(7), neutralizing treatment: the clear liquid after solid-liquid separation carries out neutralizing treatment by adding between alkaline reagents adjust ph to 7 ~ 9, and the neutralizing treatment reaction times is at least 30min, then adds coagulated agent and carries out coagulating sedimentation;
(8), solid-liquid separation: the slag-water slurry after neutralizing treatment carries out solid-liquid separation by the solid-liquid separation method of thickener, settling tank, filter, whizzer, in and slag be delivered to slag field and carry out storing up or turn back to heavy iron reactions steps and neutralizing treatment step, standard emission of clear or return in technical process.
In described step (1), oxygenant is hydrogen peroxide, chlorinated lime, clorox or ozone.
In described step (2), alkaline reagents is unslaked lime, white lime, calcium carbonate, sodium carbonate or sodium hydroxide, and phosphoric acid salt is sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC or ammonium phosphate, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
In described step (4), ultrafiltration, reverse osmosis or nanofiltration treatment system are one or more levels treatment unit, and ultra-filtration membrane, reverse osmosis membrane or nanofiltration membrane adopt acidproof, resistant to pollution film.
In described step (5), sulfiding reagent is inorganic sulphide or organic sulfide medicament, such as sodium sulphite, iron sulphide or sulfurated lime, heavy metal chelant is xanthate class, dithiocarbamate salt derivative or other heavy metal chelants, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
In described step (7), alkaline reagents is unslaked lime, white lime, calcium carbonate, sodium carbonate or sodium hydroxide, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
Specific examples 1:
Certain nonferrous metal mine acid waste water, pH is 2.6, Cu be 263.51mg/L, Fe be 1235.47mg/L, Zn be 4.52mg/L, Ni be 6.64mg/L, As is 2.12mg/L, SO
4 2-for 15360.43mg/L, other heavy metal ion in addition containing trace.Get 5L waste water and be placed in steel basin, open and stir, add the hydrogen peroxide solution 20mL of 30%, reaction 30min, waste water ph is adjusted to 3.5 by the milk of lime then adding mass concentration 10%, reaction 30min, then the PAM reagent 5mL adding mass concentration 0.5 ‰ carries out coagulating sedimentation, filter after having reacted, then filtrate is passed in reverse osmosis membrane processing device, the pure water produced after reverse-osmosis treated is placed in the milk of lime that steel basin adds mass concentration 10% and waste water ph is adjusted to 8.0, the concentrated solution produced after reverse-osmosis treated is placed in vulcanization reaction steel basin, filter after adding the sodium sulfide solution 25mL stirring reaction 30min of mass concentration 10%, copper products is prepared after being washed by filter residue, filtrate is placed in steel basin, waste water ph is adjusted to 8.0 by the milk of lime adding mass concentration 10%, reaction 30min, then the PAM reagent 5mL adding mass concentration 0.5 ‰ carries out coagulating sedimentation, filter after having precipitated.After reverse-osmosis treated, the pure water of output and concentrated solution are after treatment, wastewater pH is between 7 ~ 9, Cu < 0.5mg/L, Fe is < 0.3mg/L, Zn < 0.5mg/L, Ni < 0.5mg/L, As < 0.1mg/L, SO
4 2-for < 250mg/L, after process, water quality can reach reuse or emission standard.
Specific examples 2:
Certain nonferrous metal mine acid waste water, pH is 2.3, Cu be 263.51mg/L, Fe be 1235.47mg/L, Zn be 4.52mg/L, Ni be 6.64mg/L, As is 2.12mg/L, SO
4 2-for 15360.43mg/L, other heavy metal ion in addition containing trace.Get 5L waste water and be placed in aerator tank, open aerating system, reaction 60min, then the sodium dihydrogen phosphate 100mL adding mass concentration 20% is added, reaction 30min, then the PAM reagent 5mL adding mass concentration 0.5 ‰ carries out coagulating sedimentation, filter after having reacted, filter residue prepares tertiary iron phosphate product after dilute phosphoric acid and washing are purified, filtrate is passed in reverse osmosis membrane processing device, the pure water produced after reverse-osmosis treated is placed in the milk of lime that steel basin adds mass concentration 10% and waste water ph is adjusted to 8.0, the concentrated solution produced after reverse-osmosis treated is placed in replacement(metathesis)reaction steel basin, add containing organosulfur, carboxyl, filter after the heavy metal chelant 10mL stirring reaction 20min of amino groups, copper products is prepared by after filter residue pickling and washing, filtrate is placed in steel basin, waste water ph is adjusted to 8.0 by the milk of lime adding mass concentration 10%, reaction 30min, then the PAM reagent 5mL adding mass concentration 0.5 ‰ carries out coagulating sedimentation, filter after having precipitated.After reverse-osmosis treated, the pure water of output and concentrated solution are after treatment, wastewater pH is between 7 ~ 9, Cu < 0.5mg/L, Fe is < 0.3mg/L, Zn < 0.5mg/L, Ni < 0.5mg/L, As < 0.1mg/L, after process, water quality can reach reuse or emission standard.
Claims (7)
1. a nonferrous metal mine process for treating acidic waste water, the method comprises the following steps:
(1), oxidizing reaction: acid waste water adopts the mode adding oxygenant or pass into air aeration oxidation, the oxidation of divalent iron ion with reducing metal ion is become the ferric ion of oxidative metal ion, if reducing metal ion content is less in waste water, directly next step reaction can be carried out;
(2) heavy iron reaction: the waste water after oxidizing reaction is by adding alkaline reagents, pH value is adjusted between 3.5 ~ 4.0, reaction times is at least 20min, ferric ion is transformed into ironic hydroxide precipitate down completely, or add phosphoric acid salt control waste water ph between 1.5 ~ 2.5, reaction times is at least 30min, ferric ion is transformed into tertiary iron phosphate precipitation to go down, coagulated agent can be added during reaction and promote precipitation, if without ferric ion in waste water, can directly enter film treatment step;
(3), solid-liquid separation: the throw out of heavy iron reaction carries out solid-liquid separation by the solid-liquid separation method of thickener, settling tank, filter, whizzer, clear liquid after separation enters film treatment step, solid after separation is purified further, prepares molysite product;
(4), film process: first the clear liquid after solid-liquid separation carries out uf processing, then reverse osmosis is entered into or nanofiltration membrane treatment system carries out film process, after process output pure water in and qualified discharge or return technical process, the concentrated solution of output is for further processing;
(5), sulfidizing: the concentrated solution of film process output is under whipped state, add sulfiding reagent or heavy metal chelant, reaction times is at least 20min, makes the cupric ion in waste liquid or other heavy metal ion generate throw out hard to tolerate, then adds coagulated agent and promotes precipitation;
(6), solid-liquid separation: the slag-water slurry after sulfidizing carries out solid-liquid separation by the solid-liquid separation method of settling tank, filter, whizzer, the solid separated is by purifying further, prepare metal product, the clear liquid after separation enters neutralizing treatment step;
(7), neutralizing treatment: the clear liquid after solid-liquid separation carries out neutralizing treatment by adding between alkaline reagents adjust ph to 7 ~ 9, and the neutralizing treatment reaction times is at least 30min, then adds coagulated agent and carries out coagulating sedimentation;
(8), solid-liquid separation: the slag-water slurry after neutralizing treatment carries out solid-liquid separation by the solid-liquid separation method of thickener, settling tank, filter, whizzer, in and slag be delivered to slag field and carry out storing up or turn back to heavy iron reactions steps and neutralizing treatment step, standard emission of clear or return in technical process.
2. a kind of nonferrous metal mine process for treating acidic waste water according to claim 1, it is characterized in that: in described step (1), oxygenant is hydrogen peroxide, chlorinated lime, clorox or ozone.
3. a kind of nonferrous metal mine process for treating acidic waste water according to claim 1, it is characterized in that: in described step (2), alkaline reagents is unslaked lime, white lime, calcium carbonate, sodium carbonate or sodium hydroxide, phosphoric acid salt is sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC or ammonium phosphate, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
4. a kind of nonferrous metal mine process for treating acidic waste water according to claim 1, it is characterized in that: in described step (4), ultrafiltration, reverse osmosis or nanofiltration treatment system are one or more levels treatment unit, and ultra-filtration membrane, reverse osmosis membrane or nanofiltration membrane adopt acidproof, resistant to pollution film.
5. a kind of nonferrous metal mine process for treating acidic waste water according to claim 1, it is characterized in that: in described step (5), sulfiding reagent is inorganic sulphide or organic sulfide medicament, heavy metal chelant is xanthate class, dithiocarbamate salt derivative or other heavy metal chelants, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
6. a kind of nonferrous metal mine process for treating acidic waste water according to claim 5, is characterized in that: inorganic sulphide is sodium sulphite, iron sulphide or sulfurated lime.
7. a kind of nonferrous metal mine process for treating acidic waste water according to claim 1, it is characterized in that: in described step (7), alkaline reagents is unslaked lime, white lime, calcium carbonate, sodium carbonate or sodium hydroxide, and coagulating agent is inorganic salt coagulating agent or high-molecular coagulant adopting.
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| CN106186452A (en) * | 2016-09-27 | 2016-12-07 | 江苏亚欧环境工程有限公司 | Acidic mine waste water processing system |
| CN106745979A (en) * | 2016-12-15 | 2017-05-31 | 攀枝花钢城集团有限公司 | Strontium ferrite powder process for treating acidic waste water |
| CN106830432A (en) * | 2017-03-07 | 2017-06-13 | 中冶节能环保有限责任公司 | A kind of iron content high alkalinity mine water treatment technique high and system |
| CN106848472A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of method that lithium is reclaimed in waste lithium iron phosphate battery |
| CN107010678A (en) * | 2017-03-30 | 2017-08-04 | 余美媟 | Contain the Processing tecchnics of slight heavy metal contaminants in a kind of water body |
| CN108217896A (en) * | 2018-01-24 | 2018-06-29 | 东莞市升佳净水材料有限公司 | A kind of polymerization alkali and preparation method thereof |
| 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 |
| CN108751533A (en) * | 2018-06-05 | 2018-11-06 | 苏州聚微环保科技有限公司 | A kind of processing method of the acidic rinse waste water suitable for process of metal working |
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| CN109336333A (en) * | 2018-11-14 | 2019-02-15 | 湖南冠颜料有限公司 | A kind of ferric oxide red colorant producing wastewater treatment |
| CN109399832A (en) * | 2018-11-27 | 2019-03-01 | 中国恩菲工程技术有限公司 | The processing method of acid heavy metal wastewater |
| CN110004296A (en) * | 2019-03-28 | 2019-07-12 | 长春黄金研究院有限公司 | A kind of gold concentrate roasting enterprise acid wastewater in mine synthetical recovery administering method |
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| CN114368851A (en) * | 2021-11-29 | 2022-04-19 | 矿冶科技集团有限公司 | Method and system for treating acidic heavy metal wastewater |
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| CN117923704A (en) * | 2024-01-18 | 2024-04-26 | 广东台泉科技股份有限公司 | Resource utilization method of shale oil high-salinity wastewater |
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| CN106745979A (en) * | 2016-12-15 | 2017-05-31 | 攀枝花钢城集团有限公司 | Strontium ferrite powder process for treating acidic waste water |
| CN106830432A (en) * | 2017-03-07 | 2017-06-13 | 中冶节能环保有限责任公司 | A kind of iron content high alkalinity mine water treatment technique high and system |
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