CN105858779B - A method of by recycling metal in low-concentration heavy metal ions waste water - Google Patents
A method of by recycling metal in low-concentration heavy metal ions waste water Download PDFInfo
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- CN105858779B CN105858779B CN201610237623.XA CN201610237623A CN105858779B CN 105858779 B CN105858779 B CN 105858779B CN 201610237623 A CN201610237623 A CN 201610237623A CN 105858779 B CN105858779 B CN 105858779B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses a kind of methods by recycling metal in low-concentration heavy metal ions waste water, a kind of method by recycling metal in low-concentration heavy metal ions waste water, select there is the active carbon of good adsorption properties and mass-transfer performance to make adsorbent heavy metal ion, it is added in the waste water containing low-concentration heavy metal ions according to dosage appropriate, after a certain period of time, the heavy metal ion content in waste water is reduced to direct emission or reuse after national standard discharge standard for absorption；Active carbon reaches adsorption saturation after handling a certain amount of waste water, directly the active carbon of adsorption saturation is transferred in the electrolytic cell containing supporting electrolyte, it is electrolysed under tank voltage appropriate and current density, metal is precipitated in cathodic reduction, different metals can be obtained by controlling different electrolytic conditions, enterprise is set really to realize green production, circular economy.
Description
Technical field
The present invention relates to environmental protection and resources circulation reutilization technology fields, and in particular to one kind is by low-concentration heavy metal ions
The method of metal is recycled in waste water.
Background technique
With the development of economy, a large amount of industrial wastewater and sanitary sewage are directly discharged into rivers,lakes and seas, cause water resource
Pollution.Unlike organic pollutant, heavy metal contaminants can not degrade in ecological environment, can only want in various environment
It is mutually converted between element with different shape.Heavy metal is particularly easy to be enriched in plant and animal body, and endangers people by food chain
The health of class, therefore people especially pay close attention to heavy metal pollution in recent years.
Waste water containing heavy metal is mainly derived from mining, machining, non-ferrous metal metallurgy, old and useless battery rubbish
Processing, electroplate factory's draining, printed circuit board produce the useless of the production processes such as draining and pesticide, medicine, paint, pigment discharge
Water.With the heavy metal that water discharges, even if concentration is lower, it is also possible to cause serious harm by biological concentration.In these huge sum of moneys
In category, some are microelements necessary to vital movement, as zinc, copper, manganese, but excess intake can then cause people and animal and plant
Damage.Such as studies have found that, with copper-containing wastewater irrigated farmland, copper is accumulated in soil and crops, will cause crops spy
It is not that rice and barley growth are bad, and can pollute grain seed.Copper is very big to the toxicity of aquatile, at home and abroad all once sends out
Pig copper pollution causes aquatile acute poisoning event；In seashore and Gulf Region, Cu-W ore deposit also once occurred, oyster meat is caused to become
Green event.Aquatile especially shellfish has apparent enrichment to copper, and people passes through edible crops and aquatile
The copper of excess intake will cause the discomfort of digestive system, cause abdominal pain, vomiting；Excessive copper can also be accumulated in blood, liver,
In kidney and brain, hemolytic hemolytic anemia, liver renal necrosis and off one's dot etc. are caused, it is serious to will cause death.In addition to a few metals element,
Most of heavy metal is not element required for life entity, and enrichment can generate serious harm in life entity.Such as lead
It can be put aside in human body and animal tissue, major toxicity effect is anemia, nervous function imbalance and injury of kidney, vulnerable people
Group has children, old man, immunocompromised crowd, and child's brain is be easy to cause feeblemindedness by the damage of lead.Survey data shows, I
State by heavy metal pollution cultivated area up to 20,000,000 hectares.Heavy metal in soil pollutant greatly comes from filling
Water is irrigate, therefore to repair arable land to start with from the heavy metal contaminants reduced in water body first.Various countries are in surface water at present
The content of various pollutants has specific standard, therefore in order to preserve the ecological environment, and the various industrial wastewaters containing heavy metal are all
Having to pass through stringent processing could discharge.
Requirement of the most enterprises based on environmental protection at present, when handling the waste water containing heavy metal primary concern is that discharge reaches
Mark, wastewater treatment is only put into, and without any economic benefit, therefore some enterprises is inevitably caused to steal the illegal row of effluent
For.In fact, the heavy metal in waste water be for environmental ecology it is harmful, but then, various metals are non-renewable again
Useful resources.If useful metal can be recycled when handling the waste water containing heavy metal, while Environmental Inputs,
The metal of recycling can be utilized again again and generate economic benefit, not only can protect environment in this way, but also realize the circulation of resource
It recycles, is to kill two birds with one stone.
Waste water most common method of the processing containing heavy metal is chemical precipitation method at present.Some acid waste waters are generally added
Enter hydroxide, adjusts pH value to alkalinity, heavy metal is made to generate the hydroxide precipitating of indissoluble.This method and process is simple, at
This relative moderate, but handle after water body pH it is higher, need further neutralisation treatment, and be likely to form in precipitation process it is a variety of from
Sub- co-precipitate and complex compound, therefore the heavy metal wastewater thereby for being not suitable for processing low concentration and being easily complexed, for the heavy of amphoteric metal
Shallow lake effect is also bad.Another precipitation method are that sulfide is added, and this method (7-9) can generate under the conditions of lower pH,
Without subsequent neutralization, but sulfide precipitation agent hydrogen sulfide gas easily generated in acid condition, generate secondary pollution.Furthermore vulcanize
Object precipitating particle is smaller, easily formation colloid, can cause certain adverse effect to precipitating and filtering, therefore wadding need to be added toward contact
It is heavy that solidifying agent etc. helps.After chemical precipitation method handles heavy metal wastewater thereby, sediment (sludge) content of beary metal of generation is very high, Bu Nengzhi
Discarding is connect, is typically necessary and is further processed, on the one hand can recycle metal, on the other hand also for reduction to the two of soil
Secondary pollution.Precipitating sludge containing heavy metal mostly uses strong acid to elute greatly, and heavy metal is made to be dissolved in strong acid solution, collects after leacheate again
It neutralizes, concentration, last reduction treatment obtains useful metal.Obviously this waster water process of the processing containing heavy metal needs to consume big
Highly basic, the strong acid of amount, the chemical agents such as sulfide, the consumption of chemical reagent when especially handling low-concentration heavy metal ions waste water
Measure relatively higher, processing cost increase.Furthermore this method can be generated largely during handling the waste water containing heavy metal containing sodium
The brine wastes such as ion, calcium ion, chloride ion, acid ion, therefore be not ideal environment-friendly treating process.For containing low dense
The processing method for spending heavy metal wastewater thereby, it is now recognized that relatively effective is absorption method.A certain amount of absorption is added in waste water
Agent, metal ion can be adsorbed by adsorbent and reduce the concentration of metal ion in water body.Adsorbent is certain with waste water
After time, adsorbent reaches saturated extent of adsorption, and adsorbent fails at this time, needs replacing new adsorbent or answers again after regenerating again
With.The adsorbent for reaching saturated extent of adsorption cannot be abandoned directly, in order to avoid cause secondary pollution.Common processing method and the precipitation method
It is similar, it is impregnated or is eluted using strong acid, by digestion of metallic ion, then restore recycling metal.Adsorbent after strong acid treatment
Also a degree of regeneration is obtained, new adsorbent can be substituted partially to reduce cost.Currently used adsorbent is active
Charcoal, modified zeolite, bentonite etc., wherein adsorption effect of activated carbon in water is relatively good, but relative price is higher, and regeneration cost is larger.On
Although the method for stating two kinds of processing heavy metal ion-containing waste waters can realize the requirement of qualified discharge substantially, all cannot directly return
Metal is received, needs to be further processed treated sludge or adsorbent using chemical agent, process flow is long, at high cost, gold
Belonging to the rate of recovery reduces, therefore industrial and be not been widely used for metal recovery.
The research of the heavy metal ion-containing waste water of electrochemical process processing in recent years is paid close attention to by people.This method is to utilize oxygen
Change reduction basic principle, makes the heavy metal ion electroreduction metal in waste water.Without adding other chemistry in treatment process
Reagent will not generate precipitating sludge, but in the presence of energy consumption is high, at high cost, electrode is easy to pollute, and electrolytic process side reaction is mostly equal to be lacked
Point, therefore this method is only suitable for handling that the impurity contents such as organic matter are seldom, body of concentration of metal ions high (generally higher than 10g/L)
System, can not deposit the higher metal of purity in cathode for the waste water containing low-concentration heavy metal ions, simultaneously because analysing
Hydrogen analyses a large amount of side reactions such as oxygen, causes electrolytic efficiency extremely low, energy consumption greatly improves, therefore this method is also difficult to push away extensively
Extensively.
Summary of the invention
Object of the present invention is to：A kind of method by recycling metal in low-concentration heavy metal ions waste water is provided, both can solve
The problem of enterprise wastewater qualified discharge, and useful metal resource can be recycled simultaneously, bring economic benefit.
The technical scheme is that：
A method of by recycling metal in low-concentration heavy metal ions waste water, this method comprises the following steps：
(1) it adsorbs：It selects the active carbon big to adsorption of metal ions capacity to make adsorbent, is added to containing heavy metal ion
Waste water in, stand, adsorb metal ion sufficiently by active carbon；
(2) it is separated by solid-liquid separation：By the liquid and Activated carbon separation after absorption, then repeatedly step (1) and step (2) if process
Dry time, until the activated carbon adsorption is saturated；
(3) metal recovery：The active carbon of adsorption saturation is moved into electrolytic cell, electrolyte solution electrolysis is added, it is heavy in cathode
Product goes out metal.
Further, the active carbon big to adsorption of metal ions capacity of selection described in step (1) makees adsorbent, is added
Into the waste water containing heavy metal ion, stands, adsorb metal ion sufficiently by active carbon to be specially：Selection is in a single huge sum of money
Belong to active carbon of the adsorption capacity greater than 50mg/g in the solution that mass of ion concentration is 1g/L and then selects one as adsorbent
20g active carbon is added in the adsorption column, closes the absorption as adsorption column for container of the lower end with piston control outlet
The piston of column lower end is added the solution that 1L~2L concentration of metal ions is 10mg/L~1g/L, is stored at room temperature 1h~5h.
Further, the liquid and Activated carbon separation after absorption are repeated into step (1) and step (2) described in step (2)
Process several times, until activated carbon adsorption saturation be specially：Adsorption column lower end piston is opened, liquid outflow, solid is living
Property charcoal is adsorbed column bottom strainer and is retained in the adsorption column, and closure piston, repeats the above steps (1) and step (2) is several
It is secondary until active carbon reach adsorption saturation.
Further, the active carbon of adsorption saturation is moved into electrolytic cell described in step (3), electrolyte solution electricity is added
Solution, depositing metal in cathode is specially：Using two electrode system of anode and cathode, two electrode spacings are 2cm~5cm, two
It is inserted into a piece of polymer battery separator respectively at electrode on the inside of electrode, the active carbon of the adsorption saturation is placed in two polymerizations
Between object battery diaphragm, it is molten that sulfuric acid, sodium sulphate or sodium nitrate that concentration is 0.1mol/L~0.5mol/L are added in a cell
The electrolytic cell is placed on magnetic stirring apparatus by liquid, and control bath voltage is 2.0V~8.0V, and electrolysis time is 1h~40h,
Metal deposit directly recycles metal in cathode after electrolysis on cathode.
Further, the anode is graphite electrode, and the cathode is copper plate electrode, stainless steel substrates electrode or graphite electrode
In any one.
Further, the rotor speed on the magnetic stirring apparatus is 100~1000r/min.
A kind of method by recycling metal in low-concentration heavy metal ions waste water of the present invention, selects for heavy metal
There is ion the active carbon of good adsorption properties and mass-transfer performance to make adsorbent, be added to according to dosage appropriate containing low concentration
In the waste water of heavy metal ion, adsorb after a certain period of time, after the heavy metal ion content in waste water is reduced to national standard discharge standard
Direct emission or reuse；Active carbon reaches adsorption saturation after handling a certain amount of waste water, directly turns the active carbon of adsorption saturation
It moving in the electrolytic cell containing supporting electrolyte, is electrolysed under tank voltage appropriate and current density, metal is precipitated in cathodic reduction,
Different metals can be obtained by controlling different electrolytic conditions.Its advantages of is：
1. the present invention had not only reached environment protection emission requirement when realizing processing low-concentration heavy metal ions waste water, but also recycled
The target of high added value metal.The method of the present invention is particularly suitable for electroplating wastewater, and wastewater from battery production, printed circuit board processing are useless
The processing of water and noble metal processing waste water.Not only there is social benefit for enterprise, while also having an economic benefit, it is really real
Green production, circular economy are showed.
2. integrated use activated carbon adsorption of the present invention and electrochemical reduction method have good inhale using to heavy metal ion
The active carbon of attached performance adsorbs enriched in metals ion from low-concentration heavy metal ions solution, then has using active carbon certain
The characteristics of electric conductivity, is conducive under the action of electric field, adsorbs by the way that a certain amount of supporting electrolyte is added to enhance solution conductivity
Metal ion in active carbon is desorbed and to cathodic migration, is finally deposited as the higher metal of purity in cathodic reduction.With biography
Electrochemical process of uniting recycles metal phase ratio, does not need that waste water is concentrated, can directly handle low-concentration heavy metal ions solution,
The content of heavy metal ions in wastewater can be reduced, the requirement of waste water environment protection emission can be reached and directly recycles metal, is realized
Resource reutilization, energy consumption is lower, and the cost for recycling metal reduces.
3. the present invention is higher by the metal purity recycled in waste water, can directly recycle.In reclaiming metals
Meanwhile active carbon is also regenerated, regeneration rate reaches 85% or more, can continue cycling through use, reduce cost for wastewater treatment.
Specific embodiment
The present invention provides a kind of method by recycling metal in low-concentration heavy metal ions waste water, includes the following steps：
(1) it adsorbs：It selects the active carbon big to adsorption of metal ions capacity to make adsorbent, is added to containing heavy metal ion
Waste water in, stand, adsorb metal ion sufficiently by active carbon；
(2) it is separated by solid-liquid separation：By the liquid and Activated carbon separation after absorption, then repeatedly step (1) and step (2) if process
Dry time, until the activated carbon adsorption is saturated；
(3) metal recovery：The active carbon of adsorption saturation is moved into electrolytic cell, electrolyte solution electrolysis is added, it is heavy in cathode
Product goes out metal.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment
The present invention is described in further detail.
A method of by recycling metal in low-concentration heavy metal ions waste water, including：
Step (1)：Absorption：It selects the active carbon big to adsorption of metal ions capacity to make adsorbent, is added to containing a huge sum of money
In the waste water for belonging to ion, stands, adsorb metal ion sufficiently by active carbon；
In one embodiment, which specific as follows can execute：Select single heavy metal mass of ion concentration for
In the solution of 1g/L then active carbon of the adsorption capacity greater than 50mg/g selects a lower end to control with piston as adsorbent
20g active carbon is added in the adsorption column, closes the piston of the adsorption column lower end, adds as adsorption column for the container of outlet
Enter the solution that 1L~2L concentration of metal ions is 10mg/L~1g/L, is stored at room temperature 1h~5h.
Step (2)：It is separated by solid-liquid separation：By the liquid and Activated carbon separation after absorption, then repeatedly step (1) and step (2)
Process several times, until the activated carbon adsorption be saturated；
In one embodiment, which specific as follows can execute：Adsorption column lower end piston is opened, liquid flow
Out, solid activated carbon is adsorbed column bottom strainer and is retained in the adsorption column, closure piston.It repeats the above steps (1) and walks
Suddenly (2) are several times until active carbon reaches adsorption saturation, generally according to heavy metal ions in wastewater concentration to be processed and activity
Charcoal repeats the adsorption capacity of different heavy metal ion 2~50 times.
Step (3)：Metal recovery：The active carbon of adsorption saturation is moved into electrolytic cell, electrolyte solution electrolysis is added, in yin
Pole deposits metal.
In one embodiment, which specific as follows can execute：Using two electrode system of yin-yang, the anode is stone
Electrode ink, the cathode are any one in copper plate electrode, stainless steel substrates electrode or graphite electrode, and two electrode spacings are 2cm
~5cm is inserted into a piece of polymer battery separator at electrode on the inside of two electrodes, by the active carbon of the adsorption saturation respectively
It is placed between two polymer battery separators, sulfuric acid, the sodium sulphate that concentration is 0.1mol/L~0.5mol/L is added in a cell
Or sodium nitrate solution, the electrolytic cell is placed on magnetic stirring apparatus, the rotor speed on the magnetic stirring apparatus be 100~
1000r/min is not contacted directly with electrode generation in the solution for being suspended in active carbon between two polymer battery separators.Control
Tank voltage processed is 2.0V~8.0V, electrolysis time 1h~40h, and metal deposit directly returns after electrolysis in cathode on cathode
Receive metal.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, further below with reference to embodiment
Illustrate technical solution of the present invention.But the present invention is not limited to listed embodiments, should also be included in of the presently claimed invention
Other any well known changes in interest field.
Firstly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
In addition, the low-concentration heavy metal ions waste water said in the present invention refers to that single heavy metal mass of ion concentration is less than
The solution of 1g/L.
Embodiment one
By taking copper-containing wastewater as an example
Take the homemade rice husk matrix activated carbon of 20g that adsorption column is added, the active carbon is in the solution that copper ion concentration is 1g/L
Cupric ion adsorption is about 150mg/g.Adsorption column lower end piston is closed, it is 500mg/ that 1L copper ion concentration is added in adsorption column
The simulated wastewater of L, is stored at room temperature 2h.Adsorption column lower end piston is opened, liquid is released, detects the concentration of copper ion in efflux
Less than 1mg/L, reach discharge standard.Adsorption column lower end piston is closed, repeats above-mentioned adsorption process three times.Copper in discharge water every time
Ion concentration is respectively less than 1mg/L.20g active carbon can continuous processing 4L copper ion concentration be 500mg/L waste water, active carbon at this time
Close to adsorption saturation, next step reclaiming metals copper can be carried out.Graphite electrode is inserted into the electrolytic cell of 7 × 7 × 10cm
As anode, 4 × 3cm copper sheet is cathode, and two electrode spacing 4cm are being inserted into polymer battery separator at two electrode plates, will
The active carbon of above-mentioned adsorption saturation is placed between two polymer battery separators.The sulfuric acid solution of 300mL0.1mol/L is added, opens
Magnetic stirring apparatus, control rotor speed are 200r/min, and active carbon is suspended in the solution between two polymer battery separators simultaneously
It is not contacted directly with electrode generation, connects DC power supply, tank voltage 3.5V, electrolysis time 12h recycle copper 1.8g, every recycling
About 3.7 degree of 1kg copper loss electricity.Regenerating active carbon rate after electrolysis can be reused up to 90%.Handling 1m3 copper ion concentration is
The waste water of 500mg/L need to use the active carbon of 5kg the present embodiment, and copper ion concentration is less than 1mg/L in processed waste water, can be recycled
450g copper, 1.67 degree of power consumption.
Comparative example one
By taking copper-containing wastewater as an example
The features of the present invention is further illustrated below by comparing with existing wastewater treatment method.Assuming that using tradition
Electrochemical process processing present example described in copper ion concentration be 500mg/L simulated wastewater, and recycle metallic copper, if
Electroreduction is directly carried out, since copper ion concentration is low, electrolysis side reaction is more, and current efficiency is extremely low, is difficult to collect on cathode
To metallic copper, therefore waste water needs first to be concentrated about 10 times, i.e. processing 1m3 waste water need to be concentrated into 100L.However every evaporation lL water is big
About 1 degree of power consumption is only concentrated waste water and just needs additionally to consume about 900 degree of electricity, the significantly larger than energy consumption of electrolytic reduction process itself, because
This is economically and infeasible.Assuming that first adsorbing copper ion using active carbon, copper ion then is parsed with acid solution, is finally electrolysed again
The method for obtaining metallic copper is restored, equally using active carbon used in the present embodiment, 20g active carbon continuous processing 4L copper ion is dense
Degree is the waste water of 500mg/L, and the active carbon of adsorption saturation is then transferred to parsing slot, and it is 1mol/L's that 200mL concentration, which is added,
Hydrochloric acid solution impregnates 1h, is separated by solid-liquid separation, and active carbon repeats above-mentioned resolving 3 times, collects all desorbed solutions, copper ion parsing
Rate 85%-90%, copper ion concentration is about 2.2g/L in desorbed solution.Desorbed solution is concentrated into 300mL and is adjusted to pH=4-5,
It is electrolysed 12h in tank voltage 3.0V-3.5V, recycles copper 1.7g.The waste water that processing 1m3 copper ion concentration is 500mg/L need to use 5kg
The active carbon of the present embodiment, needs to consume the alkali of about 16.7L concentrated hydrochloric acid and neutralization when copper ion parses, electrolytic process is every
About 3.4 degree of 1kg copper loss electricity of recycling.But since desorbed solution needs appropriate concentration, about 125 degree of power consumption before electroreduction, it is much higher than
Electrolytic process energy consumption, therefore COMPREHENSIVE CALCULATING this method handles waste water and recycles the cost of metallic copper much higher than the present embodiment method.
Embodiment two
By taking copper-containing wastewater as an example
Take the homemade rice husk matrix activated carbon of 20g that adsorption column is added, the active carbon is in the solution that copper ion concentration is 1g/L
Cupric ion adsorption is about 200mg/g.Adsorption column lower end piston is closed, it is useless that the simulation that 1L copper ion concentration is 100mg/L is added
Water is stored at room temperature 3h.Adsorption column lower end piston is opened, liquid is released, the concentration for detecting copper ion in efflux is less than 1mg/
L reaches discharge standard.Adsorption column lower end piston is closed, is repeated above-mentioned adsorption process 7 times.Copper ion concentration in discharge water every time
Respectively less than 1mg/L.20g active carbon can continuous processing 8L copper ion concentration be 100mg/L waste water, at this time active carbon close to absorption
Saturation, can carry out next step reclaiming metals copper.Graphite electrode is inserted into the electrolytic cell of 7 × 7 × 10cm as anode,
4 × 3cm copper sheet is cathode, and two electrode spacing 4cm are being inserted into polymer battery separator, by above-mentioned absorption at two electrode plates
The active carbon of saturation is placed between two polymer battery separators.The metabisulfite solution of 200mL0.2mol/L is added in a cell,
Magnetic stirring apparatus is opened, control rotor speed is 500r/min, connects DC power supply, and control tank voltage is 3.0V, electrolysis time
6h, recycle copper 730mg, every about 3.4 degree of recycling 1kg copper loss electricity.Regenerating active carbon rate after electrolysis can repeat benefit up to 90%
With.The active carbon of 2.5kg the present embodiment, copper in processed waste water need to be used by handling the waste water that 1m3 copper ion concentration is 100mg/L
Ion concentration be less than 1mg/L, can be recycled 95g copper, 0.3 degree of power consumption.
Comparative example two
By taking copper-containing wastewater as an example
If handling the copper-containing wastewater of the present embodiment 100mg/L using existing electrochemical process and recycling metallic copper, waste water
50 times need to be concentrated, i.e. processing 1m3 waste water need to be concentrated into 20L, about 980 degree of power consumption, higher compared with 1 energy consumption of embodiment.If using living
Property charcoal first adsorb again with acid solution parse copper ion, the method that last electroreduction obtains metallic copper, equally use the present embodiment
Active carbon used, 20g active carbon continuous processing 8L copper ion concentration is the waste water of 100mg/L, then by the work of adsorption saturation
Property charcoal be transferred to parsing slot, the hydrochloric acid solution that 200mL concentration is 1mol/L is added, impregnates 4h, is separated by solid-liquid separation, on active carbon repeats
It states resolving 2 times, collects all desorbed solutions, copper ion resolution factor about 90%, copper ion concentration is about 1.2g/L in desorbed solution.
Desorbed solution is concentrated into 120mL and adjusts pH=4-5.It is electrolysed 5h in tank voltage 3.0V, recycles copper 700mg, every recycling 1kg copper electricity
About 3.3 degree of power consumption of solution.The active carbon of 2.5kg the present embodiment need to be used by handling the waste water that 1m3 copper ion concentration is 100mg/L, separately
The alkali for needing to consume about 6.25L concentrated hydrochloric acid and neutralization when outer copper ion parses, can be recycled 87.5g copper, power consumption about 0.29
Degree.But since desorbed solution also needs appropriate concentration, about 60 degree of power consumption before electroreduction, it is much higher than electrolytic process energy consumption.Therefore comprehensive
Total cost calculated this method processing waste water and recycle metallic copper is much higher than the present embodiment method.
Embodiment three
By taking lead waste water as an example
Take the homemade active fruit shell carbon of 20g that adsorption column, active carbon lead in the solution that plumbum ion concentration is 1g/L is added
Ionic adsorption amount is about that 150mg/g closes adsorption column lower end piston, and the solution that 1L plumbum ion concentration is 50mg/L is added, and room temperature is quiet
Set 3h.Adsorption column lower end piston is opened, liquid is released, the concentration for detecting lead ion in efflux is less than 1mg/L, reaches discharge
Standard.Adsorption column lower end piston is closed, is repeated above-mentioned adsorption process 4 times.Plumbum ion concentration is respectively less than 1mg/ in discharge water every time
L.20g active carbon can continuous processing 5L plumbum ion concentration be 50mg/L waste water, active carbon stops inhaling close to adsorption saturation at this time
It is attached.In the electrolytic cell of 7 × 7 × 10cm be inserted into graphite electrode be used as anode, 4 × 3cm copper sheet be cathode, two electrode spacing 4cm,
It is being inserted into polymer battery separator at two electrode plates, the active carbon of above-mentioned adsorption saturation is placed in two polymer battery separators
Between.The sodium nitrate solution of 200mL0.5mol/L is added in a cell, opens magnetic stirring apparatus, control rotor speed is
500r/min, active carbon, which is suspended in the solution between two polymer battery separators, not to be contacted directly with electrode generation, is connected
DC power supply, tank voltage 2V, electrolysis time 1h, recycle lead 0.23g, every about 1.56 degree of recycling 1kg lead loss electricity.Work after electrolysis
Property charcoal regeneration rate can be reused up to 90% or more.The waste water that processing 1m3 plumbum ion concentration is 50mg/L need to use 4kg sheet
The active carbon of embodiment, plumbum ion concentration is less than 1mg/L in processed waste water, can be recycled 46g lead, and 0.07 degree of power consumption.
Comparative example three
By taking lead waste water as an example
If handling the lead waste water of the present embodiment 50mg/L using existing electrochemical process and recycling metallic lead, waste water is needed
20 times of concentration, i.e. processing 1m3 waste water need to be concentrated into 50L, about 950 degree of power consumption, be much higher than electrolysis energy consumption.If using active carbon elder generation
Absorption is parsed with acid solution again, the method that last electroreduction obtains metallic lead, equally uses active carbon used in the present embodiment,
20g active carbon continuous processing 5L plumbum ion concentration is the waste water of 50mg/L, and the active carbon of adsorption saturation is then transferred to parsing
Slot is added the nitric acid solution that 200mL concentration is 1mol/L, impregnates 2h, is separated by solid-liquid separation, and active carbon repeats above-mentioned resolving 2 times,
Collect all desorbed solutions, lead ion resolution factor about 88%, plumbum ion concentration is about 0.36g/L in desorbed solution, adds alkali neutralization to pH
=5, and it is concentrated into 150mL.Tank voltage 2.0V be electrolysed 1h, recycle lead 0.18g, every about 1.6 degree of recycling 1kg lead loss electricity.Processing
The waste water that 1m3 plumbum ion concentration is 50mg/L need to use the active carbon of 4kg the present embodiment, and 36g lead, power consumption about 0.06 can be recycled
Degree.But since desorbed solution also needs appropriate concentration, about 90 degree of power consumption before electroreduction, it is much higher than electrolytic process energy consumption.In addition lead
Need to consume the alkali of about 7.7L concentrated nitric acid and neutralization when ion parses, therefore COMPREHENSIVE CALCULATING this method handles waste water and returns
The cost for receiving metallic lead is much higher than the present embodiment method, and the metallic lead recycled in identical wastewater treatment capacity is also less than this implementation
Example.
Example IV
By taking nickel-containing waste water as an example
Take the homemade rice husk matrix activated carbon of 20g that adsorption column is added, the active carbon is in the solution that nickel ion concentration is 1g/L
Nickel ion adsorbance is about 2000mg/g.Adsorption column lower end piston is closed, it is useless that the simulation that 1L nickel ion concentration is 100mg/L is added
Water is stored at room temperature 4h.Adsorption column lower end piston is opened, liquid is released, the concentration for detecting nickel ion in efflux is less than 1mg/
L reaches discharge standard.Adsorption column lower end piston is closed, is repeated above-mentioned adsorption process 49 times.Nickel ion concentration in discharge water every time
Respectively less than 1mg/L.20g active carbon can continuous processing 50L nickel ion concentration be 100mg/L waste water, at this time active carbon close to inhale
Attached saturation is transferred to reclaiming metals nickel in electrolytic cell.Graphite electrode is inserted into the electrolytic cell of 7 × 7 × 10cm as anode,
4 × 3cm copper sheet is cathode, and two electrode spacing 4cm are being inserted into polymer battery separator, by above-mentioned absorption at two electrode plates
The active carbon of saturation is placed between two polymer battery separators.The sodium sulphate that 200mL 0.3mol/L is added in a cell is molten
Liquid opens magnetic stirring apparatus, and control rotor speed is 500r/min, connects DC power supply, control tank voltage is 3.5V, when electrolysis
Between 21.5h, recycle nickel 4.75g, every about 3.8 degree of the power consumption of recycling 1kg nickel.Regenerating active carbon rate after electrolysis, can up to 90% or more
With recycling.The active carbon of 0.4kg the present embodiment need to be used by handling the waste water that 1m3 nickel ion concentration is 100mg/L, after processing
Nickel ion concentration is less than 1mg/L in waste water, and 95g nickel, about 0.36 degree of power consumption can be recycled.
Comparative example four
By taking nickel-containing waste water as an example
If handling the nickel-containing waste water of the present embodiment 100mg/L using existing electrochemical process and recycling metallic nickel, waste water
20 times need to be concentrated, i.e., processing 1m3 waste water need to be concentrated into 50L, about 950 degree of power consumption, be much higher than electrolysis energy consumption.If using active carbon
It first adsorbs and is parsed again with acid solution, the method that last electroreduction obtains metallic nickel, equally using activity used in the present embodiment
Charcoal, 20g active carbon continuous processing 50L nickel ion concentration are the waste water of 100mg/L, are then transferred to the active carbon of adsorption saturation
Slot is parsed, the sulfuric acid solution that 200mL concentration is 1mol/L is added, impregnates 2h, is separated by solid-liquid separation, active carbon repeats above-mentioned resolving
2 times, collect all desorbed solutions, nickel ion resolution factor about 90%, nickel ion concentration is about 7.5g/L in desorbed solution, adds alkali neutralization extremely
PH=5.Tank voltage 3.5V be electrolysed 18h, recycle nickel 4.0g, every about 3.8 degree of the power consumption of recycling 1kg nickel.Handle 1m3 nickel ion concentration
For 100mg/L waste water need to use 0.4kg the present embodiment active carbon, can be recycled 80.0g nickel, about 0.3 degree of power consumption.In addition nickel from
Need to consume the alkali of the about 0.4L concentrated sulfuric acid and neutralization when subsolution is analysed, therefore COMPREHENSIVE CALCULATING this method handles waste water and recycles
The cost of metallic nickel is still higher than the present embodiment method, and the metallic nickel recycled in identical wastewater treatment capacity is also less than the present embodiment.
Embodiment five
By taking the simulation electroplating wastewater of the hybrid ionic containing copper and mickel as an example
It takes 4 active carbon of 20g embodiment that adsorption column is added, closes adsorption column lower end piston, 1L nickel ion containing 50mg/L is added
Electroplating wastewater is simulated with the hybrid ionic of 20mg/L copper ion, is stored at room temperature 4h.Adsorption column lower end piston is opened, liquid is released
Body detects the concentration of nickel ion and copper ion in efflux and is respectively less than 1mg/L, reaches discharge standard.It is living to close adsorption column lower end
Plug repeats above-mentioned adsorption process 19 times.The concentration of nickel ion and copper ion is respectively less than 1mg/L in discharge water every time.20g active carbon
Can continuous processing 20L nickel ion containing 50mg/L and 20mg/L copper ion simulation electroplating wastewater, active carbon is full close to absorption at this time
Be transferred to reclaiming metals in electrolytic cell.Graphite electrode is inserted into the electrolytic cell of 7 × 7 × 10cm as anode, 4 × 3cm
Copper sheet is cathode, and two electrode spacing 4cm are being inserted into polymer battery separator, by above-mentioned adsorption saturation at two electrode plates
Active carbon is placed between two polymer battery separators.The metabisulfite solution of 200mL 0.3mol/L is added in a cell, opens
Magnetic stirring apparatus, control rotor speed are 800r/min, connect DC power supply, and control tank voltage is 5V, and electrolysis 1.2h is recyclable
Copper 318mg, temporary close power supply replace a piece of cathode.It opens DC power supply to continue to be electrolysed, cathode in initial 0.5h electrolytic process
Deposition is cupro-nickel mixture, continues to be electrolysed the recyclable nickel 900mg of 4h.Regenerating active carbon rate after electrolysis, can up to 90% or more
With recycling.The active carbon of 1kg the present embodiment need to be used by handling the above-mentioned hybrid ionic waste water of 1m3, in processed waste water copper from
Son and nickel ion concentration are respectively less than 1mg/L, and the higher metallic copper 15.9g of purity can be recycled, and nickel 45.0g and 9.0g nickel, copper are mixed
Close object, altogether about 0.4 degree of power consumption.
Comparative example five
By taking the simulation electroplating wastewater of the hybrid ionic containing copper and mickel as an example
If handling the mixing of the present embodiment nickel ion containing 50mg/L and 20mg/L copper ion using existing electrochemical process
Waste water simultaneously recycles metal copper and mickel, and waste water need to be concentrated 50 times or more, i.e. processing 1m3 waste water need to be concentrated into 20L hereinafter, power consumption is more than
980 degree, it is much higher than electrolysis energy consumption.It is parsed again with acid solution if first adsorbed using active carbon, last electroreduction obtains metal
Method, equally using active carbon used in the present embodiment, then the 20g active carbon continuous processing 20L hybrid ionic waste water will
The active carbon of adsorption saturation is transferred to parsing slot, and the sulfuric acid solution that 200mL concentration is 1mol/L is added, impregnates 3h, is separated by solid-liquid separation,
Active carbon repeats above-mentioned resolving 2 times, collects all desorbed solutions, copper ion resolution factor about 82%, nickel ion resolution factor is about
90%, copper ion concentration is about 0.54g/L in desorbed solution, and nickel ion concentration is about 1.5g/L, adds alkali neutralization to pH=5 and is concentrated
To 300mL.It is electrolysed 1.2h in tank voltage 5V, recycles copper 290mg.Temporary close power supply replaces a piece of cathode.Open DC power supply
Continue to be electrolysed, what cathode deposited in initial 0.5h electrolytic process is cupro-nickel mixture, continues to be electrolysed the recyclable nickel 850mg of 4h.Place
The active carbon of 1kg the present embodiment, copper ion and nickel ion concentration in processed waste water need to be used by managing the above-mentioned hybrid ionic waste water of 1m3
The higher metallic copper 14.5g of purity can be recycled in respectively less than 1mg/L, and nickel 42.5g and 5.9g nickel, copper mixture, total power consumption is about
0.4 degree.But since desorbed solution also needs appropriate concentration, about 15 degree of power consumption before electroreduction, it is much higher than electrolytic process energy consumption.In addition
Need to consume the alkali of the about 0.4L concentrated sulfuric acid and neutralization when copper, nickel ion parsing, therefore COMPREHENSIVE CALCULATING this method handles waste water
And the cost for recycling metal copper and mickel is still higher than the present embodiment method, the metal copper and mickel recycled in identical wastewater treatment capacity
Less than the present embodiment.In conclusion the invention discloses a kind of method by recycling metal in low-concentration heavy metal ions waste water,
The heavy metal ion in the activated carbon adsorption solution that there are good adsorption properties for heavy metal ion is selected, by the weight of low concentration
Metal ion is enriched in active carbon, is then dispersed the active carbon of adsorption saturation in the electrolytic cell of two electrode systems, suitable
When tank voltage and current density under, the metal ion that is adsorbed in active carbon is parsed and is moved under the action of electric field to cathode
It moves, final metal ion is deposited as the higher metal of purity in cathodic reduction.This processing low-concentration heavy metal ions waste water
Method can not only reduce heavy metal ions in wastewater content to reach environment protection emission requirement, but also can directly be recovered in cathode
With metal, while active carbon is also regenerated, and can be reused for adsorbing, be reduced cost for wastewater treatment.The method of the present invention can be located
The waste water that concentration of heavy metal ion is 10mg/L~1g/L is managed, recycles about 3.0 degree~4.0 degree of power consumption of 1kg copper；Recycle 1kg nickel about
3.5 degree~4.5 degree of power consumption；About 1.5 degree~2.5 degree of power consumption of 1kg lead of recycling.In practical applications, many industrial wastewaters contain not
An only metal ion species, method provided by the invention can make the different metal being adsorbed on active carbon by controlling electrolytic condition
Ion order restoring on cathode deposits, and obtains the higher different metal of purity respectively.The method of the present invention be particularly suitable for plating,
The processing of the industrial wastewaters such as printed circuit board production, battery production, cannot when solving processing low-concentration heavy metal ions waste water
Useful metal is directly recycled, and handles the problems such as waste water process be easy to cause secondary pollution and high expensive, keeps enterprise real
Realize green production, circular economy.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (3)
1. a kind of method by recycling metal in low-concentration heavy metal ions waste water, which is characterized in that this method includes following step
Suddenly：
(1) it adsorbs：Select the work for being greater than 50mg/g for adsorption capacity in the solution of 1g/L in single heavy metal mass of ion concentration
Property charcoal as adsorbent, then select a lower end with the container of piston control outlet as adsorption column, in the adsorption column
Middle addition 20g active carbon, closes the piston of the adsorption column lower end, and addition 1L~2L concentration of metal ions is 10mg/L~1g/L
Solution, be stored at room temperature 1h~5h；
(2) it is separated by solid-liquid separation：Adsorption column lower end piston is opened, liquid outflow, solid activated carbon is adsorbed column bottom strainer
It is retained in the adsorption column, closure piston, repeats the above steps (1) and step (2) is several times until active carbon reaches absorption
Saturation；
(3) metal recovery：Using two electrode system of anode and cathode, two electrode spacings are 2cm~5cm, are leaned on the inside of two electrodes
It is inserted into a piece of polymer battery separator respectively at nearly electrode, the active carbon of the adsorption saturation is placed in two polymer battery separators
Between, sulfuric acid, sodium sulphate or the sodium nitrate solution that concentration is 0.1mol/L~0.5mol/L are added in a cell, by the electricity
Solution slot is placed on magnetic stirring apparatus, and control bath voltage is 2.0V~8.0V, and electrolysis time is 1h~40h, and metal deposit exists
On cathode, metal is directly recycled in cathode after electrolysis.
2. the method according to claim 1 by recycling metal in low-concentration heavy metal ions waste water, which is characterized in that institute
Stating anode is graphite electrode, and the cathode is any one in copper plate electrode, stainless steel substrates electrode or graphite electrode.
3. the method according to claim 1 by recycling metal in low-concentration heavy metal ions waste water, which is characterized in that institute
Stating the rotor speed on magnetic stirring apparatus is 100~1000r/min.
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| CN106757150A (en) * | 2016-11-16 | 2017-05-31 | 天津碧水源膜材料有限公司 | A kind of method that copper in contained waste liquid is reclaimed using absorption and electro-deposition group technology |
| CN107129079A (en) * | 2017-05-31 | 2017-09-05 | 厦门紫金矿冶技术有限公司 | A kind of method for handling low concentration cupric cyanide wastewater |
| TWI678334B (en) * | 2018-03-30 | 2019-12-01 | 義守大學 | Recovery device and method for recovering valuable metals from activated carbon |
| CN110862180A (en) * | 2018-08-28 | 2020-03-06 | 淄博泰典新材料有限公司 | Method and device for treating and recycling high-acid mercury-containing wastewater |
| CN109231337B (en) * | 2018-10-09 | 2024-04-05 | 四川农业大学 | Portable adsorption treatment device and treatment method for farmland low-concentration heavy metal-containing sewage |
| CN110921754B (en) * | 2019-11-25 | 2022-01-25 | 山东深信节能环保科技有限公司 | Resource treatment method for low-concentration heavy metal ion wastewater |
| CN111233240A (en) * | 2020-03-02 | 2020-06-05 | 天津辰创环境工程科技有限责任公司 | Treatment device and treatment method for liquid hazardous waste pretreatment |
| CN112403028A (en) * | 2020-08-13 | 2021-02-26 | 郴州雄风环保科技有限公司 | Method for purifying lead electrolyte by using columnar activated carbon |
| CN112079526A (en) * | 2020-09-03 | 2020-12-15 | 常德鑫芙蓉环保有限公司 | Mine heavy metal wastewater remediation treatment method |
| CN112342572B (en) * | 2020-09-21 | 2022-02-15 | 万华化学集团股份有限公司 | Method for recycling low-concentration platinum in organic waste liquid |
| CN114349232B (en) * | 2022-01-24 | 2023-04-18 | 生态环境部华南环境科学研究所 | High-concentration electroplating wastewater adsorption treatment tank and use method thereof |
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