CN104944636B - A kind of nonferrous metal mine acid waste water administering method - Google Patents
A kind of nonferrous metal mine acid waste water administering method Download PDFInfo
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Abstract
The invention discloses a kind of nonferrous metal mine acid waste water administering method, the method is broadly divided into oxidation processes, film process, displacement reaction and four step of neutralisation treatment, oxidation of divalent iron ion is become ferric ion when processing initially with oxidant or aeration mode by acid waste water, then heavy iron reaction is carried out, reacted clear liquid enters film processing system and carries out separating concentration, concentrate enters line replacement reaction treatment, valuable metal is reclaimed, the reacted clear liquid of displacement proceeds to neutralisation treatment unit and is neutralized precipitation.The present invention according to nonferrous metal mine acid waste water pH low, containing the feature such as various heavy, oxidation processes, heavy iron process, film process, displacement reaction, coagulating sedimentation and neutralisation treatment technology are combined together, substep collaboration in order is processed to nonferrous metal mine acid waste water, have the advantages that high treating effect, treatment effeciency height, system run all right, can valuable resource in recycle-water, be easy to commercial Application, the waste water after process can return to the technological process of production and use as recycled water or qualified discharge.
Description
Technical field
The present invention relates to resource and environment field, more particularly to a kind of nonferrous metal mine acid waste water administering method.
Background technology
Most of nonferrous metal mines belong to polymetallic ore, and ore contains the valuable elements such as copper, lead, zinc, gold, silver, molybdenum, this
, mainly based on secondary sulphide ore, these mineral are in recovery process, common due to empty gas and water and bacterium for a little metallic elements
Effect, forms sulfuric acid, many kinds of metal ions in metal sulfate, and dissolution ore, so as to formed containing copper, iron, zinc, manganese,
The acid waste water of arsenic etc..It is particularly some metal mines and only has flotation operation, electroless and dump leaching operation, add position residing for mine
Setting in high altitude localities such as Qinghai-Tibet Platean, the Yunnan-Guizhou Plateau, the ecosystem is fragile, is more likely formed containing a large amount of sulfate ions
Acid waste water, and then cause the geological disasters such as mud-rock flow, landslide.
After acid wastewater in mine enters environment, the pH value of water body can be made to change, the natural cushioning effect of water body is destroyed,
The growth of microorganism is eliminated or suppress, the self-purification of water is hindered, cause water body the phenomenons such as smelly, discoloration, and acid water meeting occur
The structures such as heavy corrosion pipeline, water pump, cement and other plant equipment, the health for giving people, life and production are brought huge
Threat.At present, mainly there are chemical precipitation method, ion-exchange, electrolysis, UF membrane to the method that acid wastewater in mine is processed
Method etc..Chemical precipitation method equipment is simple, technology maturation, but reaction produces the quantity of slag greatly, easily causes secondary pollution, and moisture percentage in sewage sludge
Height, easily causes the waste of water resource.The heavy-metal acid waste water of ion-exchange suitable treatment low concentration, treatment effect are preferable,
But exchanger resin regeneration used is frequently, and operating cost is higher.Electrolysis is applied to wastewater treatment to be had that equipment is simple, takes up an area
Little, easy to operate, the advantages of effectively reclaim valuable metal, but power consumption is big, and limiting it the shortcomings of wastewater treatment capacity is little obtains
Range of application.Membrane separation process is suitable for processing low-concentration heavy metal acid waste water, produces the enough circulating and recoverings of water energy, but condensed water need into
One step is processed.From the above, above-mentioned various processing methods are both advantageous and disadvantageous, limit the application of the method to a certain extent, because
This, how to study a kind of process for treating acidic waste water of pratical and feasible, economical rationality be current nonferrous metal mine face work as
Business is anxious.
Content of the invention
The purpose of the present invention is aiming at the problems referred to above of existing processing method presence, and provides a kind of technological process letter
High, the stable nonferrous metal mine acid waste water administering method of list, high treating effect, treatment effeciency.
The present invention according to nonferrous metal mine acid waste water pH value low, containing heavy metal, sulfate concentration high the features such as, first
Using oxidation reaction and precipitation reaction by the iron ion removing in waste water, then acid waste water is carried out from membrane processing method dense
Contracting, pure water qualified discharge is returned in technological process, and concentrate enters line replacement reaction, reclaims the valuable moneys such as Cu in waste water ion
Source, replaces reacted supernatant and is neutralized process.
The present invention is comprised the following steps：
(1), oxidation reaction：Acid waste water, will be with also by the way of adding oxidant or being passed through air aeration oxidation
The oxidation of divalent iron ion of originality metal ion becomes the ferric ion of oxidative metal ion, if in waste water reducing metal from
Sub- content is less, can directly carry out next step reaction；
(2) iron that, sinks reacts：Waste water after oxidation reaction by adding alkaline reagent, by pH value adjust to 3.5～4.0 it
Between, the reaction time is at least 20min, ferric ion is transformed into iron hydroxide and is precipitated down completely, or adds phosphate control
Between 1.5～2.5, the reaction time is at least 30min to pH value of waste water processed, and ferric ion is transformed under ferric phosphate precipitation
Go, coagulated agent can be added during reaction and promotes precipitation, if nothing ferric ion in waste water, can be directly entered film process step.
(3) separation of solid and liquid：The sediment of heavy iron reaction passes through concentrator, sedimentation basin, filter, the separation of solid and liquid of centrifuge
Mode carries out separation of solid and liquid, and the clear liquid after separating enters film process step, and the solid after separating is purified further, prepares iron
Product salt.
(4) film process：Clear liquid after separation of solid and liquid carries out hyperfiltration treatment first, at counter-infiltration or NF membrane
Reason system carries out film process, in the pure water of output and qualified discharge or returns technological process after process, and the concentrate of output carries out
Next step is processed；
(5) displacement reaction：The concentrate of film process output is useless by adding reduced iron powder, iron filings or nanometer iron powder, displacement
Copper ion or other heavy metal ion in liquid, displacement reaction time are at least 20min.
(6) separation of solid and liquid：Reacted slag-water slurry is replaced by sedimentation basin, filter, the separation of solid and liquid of centrifuge
Mode carries out separation of solid and liquid, and the solid that separates prepares metal product by purifying further, during the clear liquid after separating is entered
And process step；
(7) neutralisation treatment：Clear liquid after separation of solid and liquid adjusts pH value in carry out between 7～9 by adding alkaline reagent
And process, the neutralisation treatment reaction time is at least 30min, and then adding coagulated agent carries out coagulating sedimentation；
(8) separation of solid and liquid：Slag-water slurry after neutralisation treatment is by concentrator, sedimentation basin, filter, the consolidating of centrifuge
Liquid separate mode carries out separation of solid and liquid, and neutralization slag is delivered to slag field and is stored up or returned to heavy iron reactions steps and neutralisation treatment
Step, standard emission of clear is returned in technological process.
In step (1), oxidant is the oxidant such as hydrogen peroxide, bleaching powder, sodium hypochlorite or ozone.
In step (2), alkaline reagent is quick lime, white lime, calcium carbonate, sodium carbonate or NaOH, phosphate
For sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or ammonium phosphate, coagulant is inorganic salt coagulant or high-molecular coagulant adopting.
In step (4), ultrafiltration, counter-infiltration or nanofiltration processing system are one or more levels processing means, milipore filter, anti-
Permeable membrane or NF membrane adopt acidproof, resistant to pollution film.
In step (7), alkaline reagent is quick lime, white lime, calcium carbonate, sodium carbonate or NaOH, coagulant
For inorganic salt coagulant or high-molecular coagulant adopting.
Beneficial effects of the present invention：
The present invention according to nonferrous metal mine acid waste water pH low, containing the feature such as various heavy, by oxidation processes, the iron that sinks
Process, film process, displacement reaction, coagulating sedimentation and neutralisation treatment technology are combined together, and substep collaboration is to non-ferrous metal in order
Acid wastewater in mine is processed, with valuable money in high treating effect, treatment effeciency height, system run all right, energy recycle-water
Source, the advantages of be easy to commercial Application, the waste water after process can return to the technological process of production and use as recycled water or qualified discharge.
Description of the drawings
Fig. 1 is the process chart of the present invention.
Specific embodiment
Referring to the drawings shown in 1, the present invention is comprised the following steps：
(1), oxidation reaction：Acid waste water, will be with also by the way of adding oxidant or being passed through air aeration oxidation
The oxidation of divalent iron ion of originality metal ion becomes the ferric ion of oxidative metal ion, if in waste water reducing metal from
Sub- content is less, can directly carry out next step reaction；
(2) iron that, sinks reacts：Waste water after oxidation reaction by adding alkaline reagent, by pH value adjust to 3.5～4.0 it
Between, the reaction time is at least 20min, ferric ion is transformed into iron hydroxide and is precipitated down completely, or adds phosphate control
Between 1.5～2.5, the reaction time is at least 30min to pH value of waste water processed, and ferric ion is transformed under ferric phosphate precipitation
Go, coagulated agent can be added during reaction and promotes precipitation, if nothing ferric ion in waste water, can be directly entered film process step.
(3) separation of solid and liquid：The sediment of heavy iron reaction passes through concentrator, sedimentation basin, filter, the separation of solid and liquid of centrifuge
Mode carries out separation of solid and liquid, and the clear liquid after separating enters film process step, and the solid after separating is purified further, prepares iron
Product salt.
(4) film process：Clear liquid after separation of solid and liquid carries out hyperfiltration treatment first, at counter-infiltration or NF membrane
Reason system carries out film process, in the pure water of output and qualified discharge or returns technological process after process, and the concentrate of output carries out
Next step is processed；
(5) displacement reaction：The concentrate of film process output is useless by adding reduced iron powder, iron filings or nanometer iron powder, displacement
Copper ion or other heavy metal ion in liquid, displacement reaction time are at least as 20min.
(6) separation of solid and liquid：Reacted slag-water slurry is replaced by sedimentation basin, filter, the separation of solid and liquid of centrifuge
Mode carries out separation of solid and liquid, and the solid that separates prepares metal product by purifying further, during the clear liquid after separating is entered
And process step；
(7) neutralisation treatment：Clear liquid after separation of solid and liquid adjusts pH value in carry out between 7～9 by adding alkaline reagent
And process, the neutralisation treatment reaction time is at least 30min, and then adding coagulated agent carries out coagulating sedimentation；
(8) separation of solid and liquid：Slag-water slurry after neutralisation treatment is by concentrator, sedimentation basin, filter, the consolidating of centrifuge
Liquid separate mode carries out separation of solid and liquid, and neutralization slag is delivered to slag field and is stored up or returned to heavy iron reactions steps and neutralisation treatment
Step, standard emission of clear is returned in technological process.
In step (1), oxidant is the oxidant such as hydrogen peroxide, bleaching powder, sodium hypochlorite or ozone.
In step (2), alkaline reagent is quick lime, white lime, calcium carbonate, sodium carbonate or NaOH, phosphate
For sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or ammonium phosphate, coagulant is inorganic salt coagulant or high-molecular coagulant adopting.
In step (4), ultrafiltration, counter-infiltration or nanofiltration processing system are one or more levels processing means, milipore filter, anti-
Permeable membrane or NF membrane adopt acidproof, resistant to pollution film.
In step (7), alkaline reagent is quick lime, white lime, calcium carbonate, sodium carbonate or NaOH, coagulant
For inorganic salt coagulant or high-molecular coagulant adopting.
Instantiation 1：
Certain nonferrous metal mine acid waste water, pH for 2.6, Cu for 263.51mg/L, Fe for 1235.47mg/L, Zn is
It is 2.12mg/L, SO that 4.52mg/L, Ni are 6.64mg/L, As4 2-For 15360.43mg/L, additionally weigh containing other micro
Metal ion.Take 5L waste water to be placed in tank diameter, stirring is opened, add 30% hydrogen peroxide solution 20mL, 30min is reacted, so
The milk of lime for adding mass concentration 10% afterwards adjusts pH value of waste water to 3.5, reacts 30min, then adds mass concentration 0.5 ‰
PAM reagent 5mL carry out coagulating sedimentation, filtered after the completion of reaction, then filtrate be passed into reverse osmosis membrane processing device
In, the pure water that produces after reverse-osmosis treated is placed in tank diameter and adds the milk of lime of mass concentration 10% and adjust pH value of waste water
To 8.0, the concentrate produced after reverse-osmosis treated is placed in displacement reaction tank diameter, adds reduced iron powder 3g stirring reaction
Filter after 120min, copper products will be prepared after filter residue pickling-washing, filtrate is placed in tank diameter, adds mass concentration 10%
Milk of lime adjusts pH value of waste water to 8.0, and reacting 30min, the PAM reagent 5mL for then adding mass concentration 0.5 ‰ carries out coagulation
Precipitation, is filtered after the completion of precipitation.After reverse-osmosis treated, after treatment, wastewater pH is 7 for the pure water of output and concentrate
Between～9, Cu ＜ 0.5mg/L, Fe are ＜ 0.3mg/L, Zn ＜ 0.5mg/L, Ni ＜ 0.5mg/L, As ＜ 0.1mg/L, SO4 2-For
＜ 250mg/L, after process, water quality can reach reuse or discharge standard.
Instantiation 2：
Certain nonferrous metal mine acid waste water, pH for 2.3, Cu for 263.51mg/L, Fe for 1235.47mg/L, Zn is
It is 2.12mg/L, SO that 4.52mg/L, Ni are 6.64mg/L, As4 2-For 15360.43mg/L, additionally weigh containing other micro
Metal ion.Take 5L waste water to be placed in aeration tank, aerating system is opened, 60min is reacted, then add plus mass concentration 20%
Sodium dihydrogen phosphate 100mL, reaction time 30min, then add mass concentration 0.5 ‰ PAM reagent 5mL carry out coagulation sink
Form sediment, filtered after the completion of reaction, filter residue prepares phosphoric acid iron product after phosphoric acid,diluted and washing purification, and filtrate is passed into counter-infiltration
In membrane treatment appts, the pure water that produces after reverse-osmosis treated be placed in tank diameter add the milk of lime of mass concentration 10% will be useless
Water pH value is adjusted to 8.0, and the concentrate produced after reverse-osmosis treated is placed in displacement reaction tank diameter, adds reduced iron powder 3g
Filter after stirring reaction time 120min, copper products will be prepared after filter residue pickling-washing, filtrate is placed in tank diameter, adds matter
The milk of lime of amount concentration 10% adjusts pH value of waste water to 8.0, reaction time 30min, then adds mass concentration 0.5 ‰
PAM reagent 5mL carries out coagulating sedimentation, is filtered after the completion of precipitation.The pure water of output and concentrate warp after reverse-osmosis treated
After crossing process, between 7～9, Cu ＜ 0.5mg/L, Fe are ＜ 0.3mg/L, Zn ＜ 0.5mg/L, Ni ＜ 0.5mg/L to wastewater pH,
As ＜ 0.1mg/L, after process, water quality can reach reuse or discharge standard.
Claims (5)
1. a kind of nonferrous metal mine acid waste water administering method, as follows the step of the method：
(1) oxidation reaction：Acid waste water, will be with reproducibility gold by the way of adding oxidant or being passed through air aeration oxidation
The oxidation of divalent iron ion of category ion becomes the ferric ion of oxidative metal ion, if reducing metal ion concentration in waste water
Less, directly carry out next step reaction；
(2) iron that sinks reacts：PH value is adjusted and is reacted between 3.5～4.0 by adding alkaline reagent by the waste water after oxidation reaction
More than 20min, ferric ion is transformed into iron hydroxide and is precipitated down completely, or adds phosphate control pH value of waste water to exist
Between 1.5～2.5, more than 30min is reacted, ferric ion is transformed into ferric phosphate precipitation and is gone down, during reaction, add coagulation medicine
Agent promotes precipitation, if nothing ferric ion in waste water, is directly entered film process unit；
(3) separation of solid and liquid：The sediment of heavy iron reaction is carried out solid-liquid and is divided by concentrator or sedimentation basin or filter or centrifuge
From the clear liquid after separating enters film process unit, and the solid after separating is purified further, prepares molysite product；
(4) film process：Clear liquid after separation of solid and liquid carries out hyperfiltration treatment first, then into counter-infiltration or nanofiltration membrane treatment system
System carries out film process, in the pure water of output and qualified discharge or returns technological process after process, and the concentrate of output carries out next
Step is processed；
(5) displacement reaction：The concentrate of film process output is replaced in waste liquid by adding reduced iron powder, iron filings or nanometer iron powder
Copper ion or other heavy metal ion, the displacement reaction time be more than 20min；
(6) separation of solid and liquid：Replacing reacted slag-water slurry carries out separation of solid and liquid by sedimentation basin or filter or centrifuge,
The solid that separates prepares metal product by purifying further, and the clear liquid after separating enters neutralisation treatment step；
(7) neutralisation treatment：Clear liquid after separation of solid and liquid adjusts pH value to being neutralized place between 7～9 by adding alkaline reagent
Reason, more than neutralisation treatment reaction time 30min, then adding coagulated agent carries out coagulating sedimentation；
(8) separation of solid and liquid：Slag-water slurry after neutralisation treatment is carried out by concentrator or sedimentation basin or filter or centrifuge
Separation of solid and liquid, neutralization slag are delivered to slag field and are stored up or returned to heavy iron reactions steps and neutralisation treatment step, and clear liquid is up to standard
Discharge is returned in technological process.
2. a kind of nonferrous metal mine acid waste water administering method according to claim 1, it is characterised in that：The step
(1), in, oxidant is hydrogen peroxide, bleaching powder, sodium hypochlorite or ozone.
3. a kind of nonferrous metal mine acid waste water administering method according to claim 1, it is characterised in that：The step
(2) in, alkaline reagent is quick lime, white lime, calcium carbonate, sodium carbonate or NaOH, and phosphate is sodium phosphate, phosphoric acid hydrogen two
Sodium, sodium dihydrogen phosphate or ammonium phosphate, coagulant are inorganic salt coagulant or high-molecular coagulant adopting.
4. a kind of nonferrous metal mine acid waste water administering method according to claim 1, it is characterised in that：The step
(4), in, ultrafiltration, counter-infiltration or nanofiltration processing system are one or more levels processing means, and milipore filter, reverse osmosis membrane or NF membrane are adopted
With acidproof, resistant to pollution film.
5. a kind of nonferrous metal mine acid waste water administering method according to claim 1, it is characterised in that：The step
(7) in, alkaline reagent be quick lime, white lime, calcium carbonate, sodium carbonate or NaOH, coagulant be inorganic salt coagulant or
High-molecular coagulant adopting.
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| CN105502728B (en) * | 2015-11-25 | 2018-05-11 | 克拉玛依市三达新技术股份有限公司 | A kind of processing method for the high temperature highly salt containing organic waste water that oilfield sewage softening produces |
| CN105906168B (en) * | 2016-06-27 | 2019-06-14 | 安徽金联地矿科技有限公司 | A kind of mine wastewater recovery and treatment method |
| CN106517584A (en) * | 2016-11-29 | 2017-03-22 | 攀枝花市九鼎智远知识产权运营有限公司 | Mine acid wastewater treatment system and mine acid wastewater treatment method |
| CN107416959A (en) * | 2017-05-17 | 2017-12-01 | 同济大学 | A kind of method of chromium nickel in removal pickle liquor |
| CN111470649A (en) * | 2019-01-23 | 2020-07-31 | 上海旷宇环境科技有限公司 | Recovery treatment method of industrial acidic wastewater |
| CN110921809B (en) * | 2019-12-14 | 2022-08-05 | 吕广鑫 | High-efficient separator of iron ion in mine water sample |
| CN113501608A (en) * | 2021-07-05 | 2021-10-15 | 内蒙古金河环保科技股份有限公司 | Wastewater zero-discharge treatment system and process |
| CN114477602A (en) * | 2022-01-25 | 2022-05-13 | 安尔达技术(北京)有限责任公司 | Comprehensive utilization treatment method for heavy metal wastewater |
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