CN105858779A - Method for recycling metal from low-concentration heavy metal ion wastewater - Google Patents
Method for recycling metal from low-concentration heavy metal ion wastewater Download PDFInfo
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- CN105858779A CN105858779A CN201610237623.XA CN201610237623A CN105858779A CN 105858779 A CN105858779 A CN 105858779A CN 201610237623 A CN201610237623 A CN 201610237623A CN 105858779 A CN105858779 A CN 105858779A
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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
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Abstract
The invention discloses a method for recycling metal from low-concentration heavy metal ion wastewater. The method for recycling metal from low-concentration heavy metal ion wastewater comprises the steps that activated carbon with the good adsorption performance and the mass transfer performance on heavy metal ions is selected as an adsorbent, a proper amount of water is added into the low-concentration heavy metal ion wastewater, and after a period time of adsorption, the content of heavy metal ions in wastewater is decreased to reach the national standard emission standard and then the wastewater is directly drained or recycled; after a certain amount of wastewater is treated by the activated carbon, the activated carbon reaches adsorption saturation, the adsorption saturation activated carbon is directly transferred into an electrolytic cell containing a supporting electrolyte, electrolysis is performed under the proper cell voltage and current density, metal is reduced and separated out at a cathode, and different metals can be obtained by controlling different electrolytic conditions, so that an enterprise truly achieves green production and circular economy.
Description
Technical field
The present invention relates to environmental protection and resources circulation reutilization technology field, be specifically related to a kind of by low concentration weight
The method reclaiming metal in metal ion waste water.
Background technology
Along with expanding economy, substantial amounts of industrial wastewater and sanitary sewage are directly discharged into rivers,lakes and seas, cause
The pollution of water resource.Unlike organic pollution, heavy metal contaminants cannot in ecological environment
Degraded, mutually can only convert with different shape between various environmental key-elements.Heavy metal is particularly easy to plant
It is enriched with in animal body, and by the health of the food chain harm mankind, people's heavy metal the most in recent years
Pollute and particularly pay close attention to.
Waste water containing heavy metal is mainly derived from mining, machining, non-ferrous metal metallurgy, gives up
Used batteries garbage disposal, Electroplate Factory's draining, printed circuit board (PCB) produce draining and pesticide, medicine, paint,
The waste water of the production process discharges such as pigment.With the heavy metal of water discharge, even if concentration is relatively low, it is also possible to logical
Cross biological concentration and cause serious harm.In these heavy metals, some is the trace that vital movement is required
Element, such as zinc, copper, manganese, but people and animal and plant then can be caused damage by excess intake.Such as grind
Studying carefully discovery, use copper-containing wastewater irrigated farmland, copper is accumulated in soil and crops, and crops can be caused special
Be not Oryza sativa L. and barley growth bad, and grain seed can be polluted.Copper is very big to hydrobiological toxicity,
The most once copper staining was occurred to cause aquatile acute poisoning event；In seashore and Gulf Region,
The most once copper staining was occurred to cause Carnis ostreae to turn green event.Copper is had significantly aquatile by particularly shellfish
Enrichment, people is the copper of excess intake by edible crops and aquatile, can cause digestive system
Discomfort, cause stomachache, vomiting；The copper of excess also can be accumulated in blood, liver, kidney and brain, makes
Becoming hemolytic hemolytic anemia, Liver and kidney downright bad and off one's dot, serious meeting causes death.Except a few metals element
Outward, most heavy metal is not the most the element required for life entity, and in life entity, enrichment can produce sternly
The harm of weight.Such as lead can be put aside in human body and animal tissue, and major toxicity effect is anemia, god
Through dysfunction and injury of kidney, vulnerable crowd has child, old man, immunocompromised crowd, You Er great
Brain is easily caused mental retardation by the infringement of lead.Survey data shows, China is ploughed by heavy metal pollution
Area has reached 20,000,000 hectares.Heavy metal in soil pollutant come from irrigation water greatly,
Therefore first repairing ploughs should start with from the heavy metal contaminants reduced water body.Various countries are for ground at present
In table water, the content of various pollutant has clear and definite standard, therefore to preserve the ecological environment, various contains
The industrial wastewater of heavy metal all has to pass through strict process and could discharge.
Most enterprises requirement based on environmental protection at present, mainly considers when processing the waste water containing heavy metal
Being emission compliance, waste water processes and only puts into, and does not has any economic benefit, causes the most unavoidably
The malpractice of effluent is stolen by enterprise.It is true that the heavy metal in waste water is harmful for environmental ecology,
But then, various metals are again non-renewable useful resources.If able to processing containing heavy metal
Waste water time reclaim useful metal, then while Environmental Inputs, the metal of recovery again can again by
Utilize and produce economic benefit, the most both can protect environment, achieve again the cycling and reutilization of resource,
It is to kill two birds with one stone.
Processing the waste water most common method containing heavy metal at present is chemical precipitation method.For some spent acidic
Water typically adds hydroxide, regulation pH value to alkalescence, and the hydroxide making heavy metal generate indissoluble sinks
Form sediment.This method technique is simple, relative inexpensiveness, but after processing, water body pH is higher, needs into one
Step neutralisation treatment, and precipitation process is likely to be formed different kinds of ions co-precipitation thing and complex, the most not
Being suitable for processing low concentration and the heavy metal wastewater thereby of easy complexation, the sedimentation effect for amphoteric metal is the best.
The another kind of sedimentation method are to add sulfide, and this method (7-9) can generate under the conditions of relatively low pH,
Without follow-up neutralization, but sulfide precipitation agent the most easily generates hydrogen sulfide gas, produces secondary
Pollute.In addition sulfide precipitation granule is less, is easily formed colloid, can cause certain to precipitation and filtration
Adverse effect, therefore toward contact need to add flocculant etc. help heavy.After chemical precipitation method processes heavy metal wastewater thereby,
Precipitate (mud) content of beary metal generated is the highest, it is impossible to directly abandon, and is typically necessary further
Process, on the one hand can reclaim metal, on the other hand also for the secondary pollution reduced soil.Contain
The precipitating sludge of heavy metal uses strong acid drip washing mostly, makes heavy metal be dissolved in strong acid solution, collects leacheate
After neutralize again, concentrate, last reduction treatment obtains useful metal.Obvious this process is containing heavy metal
The chemical agents such as waster water process needs to consume substantial amounts of highly basic, strong acid, sulfide, particularly process low dense
During degree effluent containing heavy metal ions, the consumption of chemical reagent is the highest, and processing cost increases.The most this
Method can produce during processing the waste water containing heavy metal a large amount of containing sodium ion, calcium ion, chloride ion,
The brine wastes such as acid ion, are not therefore preferable environment-friendly treating process.For containing a low concentration huge sum of money
Belong to the processing method of waste water, be absorption method it is now recognized that relatively effective.I.e. add a certain amount of in waste water
Adsorbent, metal ion can be adsorbed by adsorbent and make the concentration of metal ion in water body reduce.Inhale
Attached dose with waste water certain time after, adsorbent reaches saturated extent of adsorption, now adsorbent lost efficacy, need
Reapply after the adsorbent more to renew or again regeneration.The adsorbent reaching saturated extent of adsorption can not be direct
Abandon, in order to avoid causing secondary pollution.Common processing method is similar with the sedimentation method, use strong acid soak or
Drip washing, by digestion of metallic ion, then restores recovery metal.Adsorbent after strong acid treatment also obtains
A certain degree of regeneration, can partly substitute new adsorbent to reduce cost.The most conventional adsorbent
Active charcoal, modified zeolite, bentonite etc., wherein adsorption effect of activated carbon in water is relatively good, but relative price
Higher, regeneration cost is bigger.Although the method that above two processes heavy metal ion-containing waste water can be basic
Realize the requirement of qualified discharge, but all can not directly reclaim metal, need the mud after processing or absorption
Agent uses chemical agent to process further, and technological process is long, and cost is high, and metal recovery rate 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 process in recent years is paid close attention to by people.This method
Being to utilize oxidoreduction ultimate principle, making the heavy metal ion electroreduction in waste water is metal.Processed
Without adding other chemical reagent in journey, also will not produce precipitating sludge, but it is big to there is energy consumption, cost
Height, the shortcomings such as electrode easily pollutes, and electrolytic process side reaction is many, therefore the method is only suitable for processing Organic substance
System little Deng impurity content, that concentration of metal ions is high (generally higher than 10g/L), for containing low dense
The waste water of degree heavy metal ion cannot go out, in cathodic deposition, the metal that purity is higher, simultaneously because there is liberation of hydrogen
The substantial amounts of side reactions such as analysis oxygen, cause electrolytic efficiency extremely low, and energy consumption is greatly improved, and the most this method is also
It is difficult to be widely popularized.
Summary of the invention
The present invention seeks to: provide a kind of by the method reclaiming metal in low-concentration heavy metal ions waste water,
The problem that can solve enterprise wastewater qualified discharge, can reclaim again useful metals resources simultaneously, bring through
Ji benefit.
The technical scheme is that
A kind of by the method reclaiming metal in low-concentration heavy metal ions waste water, the method includes walking as follows
Rapid:
(1) absorption: select the activated carbon that adsorption of metal ions capacity is big is made adsorbent, join containing weight
In the waste water of metal ion, stand, make metal ion fully be adsorbed by activated carbon；
(2) solid-liquid separation: by the liquid after absorption and Activated carbon separation, then repeats step (1) and step
Suddenly (2) process is several times, until described activated carbon adsorption is saturated；
(3) metal recovery: activated carbon saturated for absorption is moved into electrolysis bath, adds electrolyte solution electrolysis,
Metal is gone out in cathodic deposition.
Further, the activated carbon to adsorption of metal ions capacity is big that selects described in step (1) is made
Adsorbent, joins in the waste water containing heavy metal ion, stands, makes metal ion abundant by activated carbon
Absorption is particularly as follows: select adsorption capacity in the solution that single heavy metal mass of ion concentration is 1g/L big
In the activated carbon of 50mg/g as adsorbent, a lower end is then selected to control the appearance of outlet with piston
Device, as adsorption column, adds 20g activated carbon in described adsorption column, cuts out the work of described adsorption column lower end
Plug, adds the solution that 1L～2L concentration of metal ions is 10mg/L～1g/L, and room temperature stands 1h～5h.
Further, by the liquid after absorption and Activated carbon separation described in step (2), step is repeated
(1) and step (2) process several times, until activated carbon adsorption is saturated particularly as follows: by described adsorption column
Lower end piston is opened, and liquid flows out, and solid activated carbon is adsorbed column bottom filter screen and is retained in described adsorption column
In, closure piston, repeat the above steps (1) and step (2) are several times until activated carbon reaches absorption
Saturated.
Further, described in step (3), activated carbon saturated for absorption is moved into electrolysis bath, add electricity
Electrolyte solution is electrolysed, and goes out metal in cathodic deposition particularly as follows: use anode and negative electrode two electrode system, and two
Electrode spacing is 2cm～5cm, inserts a piece of polymer battery respectively inside two electrodes at electrode
Barrier film, is placed in activated carbon saturated for described absorption between two polymer battery separators, adds in a cell
Entering concentration is the sulphuric acid of 0.1mol/L～0.5mol/L, sodium sulfate or sodium nitrate solution, by described electrolysis bath
Being placed on magnetic stirring apparatus, controlling bath voltage is 2.0V～8.0V, and electrolysis time is 1h～40h,
Metal deposit is on negative electrode, and electrolysis directly reclaims metal at negative electrode after terminating.
Further, described anode is graphite electrode, and described negative electrode is copper plate electrode, stainless steel substrates electrode
Or any one in graphite electrode.
Further, the rotor speed on described magnetic stirring apparatus is 100～1000r/min.
Of the present invention a kind of by the method reclaiming metal in low-concentration heavy metal ions waste water, it is right to select
The activated carbon in heavy metal ion with good adsorption properties and mass-transfer performance makees adsorbent, according to suitable
Dosage joins in the waste water containing low-concentration heavy metal ions, after absorption certain time, and the weight in waste water
Metal ion content is reduced to directly discharge or reuse after GB discharge standard；After processing a certain amount of waste water
Activated carbon reaches to adsorb saturated, is directly transferred to the electrolysis containing supporting electrolyte by adsorbing saturated activated carbon
In groove, being electrolysed under suitable tank voltage and electric current density, metal separates out in cathodic reduction, controls difference
Electrolytic condition can obtain different metals.Its advantage is:
1. when present invention achieves process low-concentration heavy metal ions waste water, both reached environment protection emission requirement,
Reclaim the most again the target of high added value metal.The inventive method is particularly suited for electroplating wastewater, and battery is raw
Produce waste water, printed circuit board (PCB) processing waste water and the process of noble metal processing waste water.For enterprise not only
There is social benefit, also have an economic benefit simultaneously, be truly realized green production, recycling economy.
Integrated use activated carbon adsorption the most of the present invention and electrochemical reduction method, utilize heavy metal ion
There is activated carbon adsorption and enrichment metal ion from low-concentration heavy metal ions solution of good adsorption properties,
Then activated carbon is utilized to have the feature of certain electric conductivity, by adding a certain amount of supporting electrolyte to strengthen
Solution conductivity, is conducive under the effect of electric field, and the metal ion being adsorbed in activated carbon is desorbed and to the moon
Pole migrates, and is finally deposited as, in cathodic reduction, the metal that purity is higher.Metal is reclaimed with Conventional electrochemical method
Compare, it is not necessary to waste water is concentrated, can directly process low-concentration heavy metal ions solution, can drop
The content of low heavy metal ions in wastewater, can reach the requirement of waste water environment protection emission, can directly reclaim again
Metal, it is achieved resource reutilization, its energy consumption is lower, and the cost reclaiming metal reduces.
3. the present invention is higher by the metal purity reclaimed in waste water, can directly recycle.In electrolysis
While reclaiming metal, activated carbon is also regenerated, and regeneration rate reaches more than 85%, can continue cycling through
Use, reduce cost for wastewater treatment.
Detailed description of the invention
The present invention provides a kind of by the method reclaiming metal in low-concentration heavy metal ions waste water, including following
Step:
(1) absorption: select the activated carbon that adsorption of metal ions capacity is big is made adsorbent, join containing weight
In the waste water of metal ion, stand, make metal ion fully be adsorbed by activated carbon；
(2) solid-liquid separation: by the liquid after absorption and Activated carbon separation, then repeats step (1) and step
Suddenly (2) process is several times, until described activated carbon adsorption is saturated；
(3) metal recovery: activated carbon saturated for absorption is moved into electrolysis bath, adds electrolyte solution electrolysis,
Metal is gone out in cathodic deposition.
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with specifically
The present invention is further detailed explanation for embodiment.
A kind of by the method reclaiming metal in low-concentration heavy metal ions waste water, including:
Step (1): absorption: select the activated carbon that adsorption of metal ions capacity is big is made adsorbent, add
Enter in the waste water containing heavy metal ion, stand, make metal ion fully be adsorbed by activated carbon；
In one embodiment, this step can specific as follows perform: selects in single heavy metal ion matter
Measure the adsorption capacity activated carbon more than 50mg/g in the solution that concentration is 1g/L, as adsorbent, then to select
Select a lower end with piston control outlet container as adsorption column, in described adsorption column add 20g
Activated carbon, closes the piston of described adsorption column lower end, adds 1L～2L concentration of metal ions and is
The solution of 10mg/L～1g/L, room temperature stands 1h～5h.
Step (2): solid-liquid separation: by the liquid after absorption and Activated carbon separation, then repeat step
(1) and step (2) process several times, until described activated carbon adsorption is saturated；
In one embodiment, this step can specific as follows perform: is beaten by described adsorption column lower end piston
Opening, liquid flows out, and solid activated carbon is adsorbed column bottom filter screen and is retained in described adsorption column, closes and lives
Plug.Repeat the above steps (1) and step (2) are several times until activated carbon reaches to adsorb saturated, typically
According to pending heavy metal ions in wastewater concentration and activated carbon, the absorption of different heavy metal ion is held
Amount repeats 2～50 times.
Step (3): metal recovery: activated carbon saturated for absorption is moved into electrolysis bath, adds electrolyte
Solution is electrolysed, and goes out metal in cathodic deposition.
In one embodiment, this step can specific as follows perform: uses negative and positive two electrode system, institute
Stating anode is graphite electrode, and described negative electrode is appointing in copper plate electrode, stainless steel substrates electrode or graphite electrode
Meaning one, two electrode spacings are 2cm～5cm, insert a piece of inside two electrodes at electrode respectively
Polymer battery separator, is placed in activated carbon saturated for described absorption between two polymer battery separators,
Adding concentration in electrolysis bath is the sulphuric acid of 0.1mol/L～0.5mol/L, sodium sulfate or sodium nitrate solution, will
Described electrolysis bath is placed on magnetic stirring apparatus, the rotor speed on described magnetic stirring apparatus be 100～
1000r/min, makes activated carbon be suspended in the solution between two polymer battery separators and does not send out with electrode
Raw directly contact.Control flume voltage is 2.0V～8.0V, and electrolysis time 1h～40h, metal deposit is at the moon
Extremely going up, electrolysis directly reclaims metal at negative electrode after terminating.
Understandable, below in conjunction with enforcement for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
Example further illustrates technical scheme.But the invention is not restricted to listed embodiment, also should
It is included in other any known changes in interest field of the presently claimed invention.
First, " embodiment " or " embodiment " referred to herein refers to may be included in the present invention extremely
Special characteristic, structure or characteristic in a few implementation.Different in this manual local appearance
" in one embodiment " not refer both to same embodiment, be not single or selective and it
The embodiment that his embodiment is mutually exclusive.
It addition, the low-concentration heavy metal ions waste water said in the present invention refers to single heavy metal mass of ion
The concentration solution less than 1g/L.
Embodiment one
As a example by copper-containing wastewater
Taking 20g homemade rice husk matrix activated carbon and add adsorption column, this activated carbon is 1g/L at copper ion concentration
Solution in cupric ion adsorption be about 150mg/g.Close adsorption column lower end piston, add in adsorption column
Entering the simulated wastewater that 1L copper ion concentration is 500mg/L, room temperature stands 2h.By adsorption column lower end piston
Opening, release liquid, in detection effluent, the concentration of copper ion is less than 1mg/L, reaches discharge standard.
Close adsorption column lower end piston, repeat above-mentioned adsorption process three times.In discharge water, copper ion concentration is equal every time
Less than 1mg/L.20g activated carbon can continuous processing 4L copper ion concentration be the waste water of 500mg/L, this
Time activated carbon close to absorption saturated, next step reclaiming metals copper can be carried out.At 7 × 7 × 10cm
Electrolysis bath in insert graphite electrode as anode, 4 × 3cm copper sheet is negative electrode, two electrode spacings 4cm,
At insertion polymerization thing battery diaphragm at two battery lead plates, activated carbon saturated for above-mentioned absorption is placed in two and gathers
Between compound battery diaphragm.Add the sulfuric acid solution of 300mL0.1mol/L, open magnetic stirring apparatus,
Control rotor speed is 200r/min, and activated carbon is suspended in the solution between two polymer battery separators also
Not occurring directly to contact with electrode, connect DC source, tank voltage is 3.5V, electrolysis time 12h, returns
Receive copper 1.8g, often reclaim 1kg copper loss electricity about 3.7 degree.Regenerating active carbon rate after electrolysis reaches 90%, can
With recycling.Process the waste water that 1m3 copper ion concentration is 500mg/L and need to use 5kg the present embodiment
Activated carbon, in processed waste water copper ion concentration be less than 1mg/L, recyclable 450g copper, power consumption 1.67
Degree.
Comparative example one
As a example by copper-containing wastewater
The feature of the present invention is further illustrated below by comparing with existing method of wastewater treatment.Assume
Traditional electrochemical process is used to process the simulation that copper ion concentration is 500mg/L described in present example
Waste water, and reclaim metallic copper, if directly carrying out electroreduction, owing to copper ion concentration is low, electrolysis pair
Reaction is many, and current efficiency is extremely low, is difficult to collect metallic copper on negative electrode, and therefore waste water needs first to concentrate
About 10 times, i.e. process 1m3 waste water and need to be concentrated into 100L.But often evaporation lL water about power consumption 1 degree,
Only concentrate waste water to be accomplished by additionally consuming about 900 degree of electricity, the significantly larger than energy of electrolytic reduction process itself
Consumption, the most economically and infeasible.Assume to use activated carbon elder generation absorbing copper ion, then use acid solution solution
Analysis copper ion, the method that electroreduction obtains metallic copper the most again, use the work used by the present embodiment equally
Property charcoal, 20g activated carbon continuous processing 4L copper ion concentration is the waste water of 500mg/L, then will absorption
Saturated activated carbon is transferred to resolve groove, and adding 200mL concentration is the hydrochloric acid solution of 1mol/L, soaks
1h, solid-liquid separation, activated carbon repeats above-mentioned resolving 3 times, collects all desorbed solutions, copper ion solution
Analysis rate 85%-90%, in desorbed solution, copper ion concentration is about 2.2g/L.Desorbed solution is concentrated into 300mL
And regulate to pH=4-5, it is electrolysed 12h at tank voltage 3.0V-3.5V, reclaims copper 1.7g.Process 1m3 copper
Ion concentration is the activated carbon that the waste water of 500mg/L need to use 5kg the present embodiment, when copper ion resolves
Needs consume about 16.7L concentrated hydrochloric acid, and the alkali neutralized, and electrolytic process often reclaims 1kg copper loss electricity about
3.4 degree.But owing to desorbed solution needs appropriateness concentration before electroreduction, about power consumption 125 degree, is far above
Electrolytic process energy consumption, therefore COMPREHENSIVE CALCULATING the method processes waste water and reclaims the cost of metallic copper far above this
Embodiment method.
Embodiment two
As a example by copper-containing wastewater
Taking 20g homemade rice husk matrix activated carbon and add adsorption column, this activated carbon is 1g/L at copper ion concentration
Solution in cupric ion adsorption be about 200mg/g.Close adsorption column lower end piston, add 1L copper from
Sub-concentration is the simulated wastewater of 100mg/L, and room temperature stands 3h.Adsorption column lower end piston is opened, puts
Going out liquid, in detection effluent, the concentration of copper ion is less than 1mg/L, reaches discharge standard.Close absorption
Post lower end piston, repeats above-mentioned adsorption process 7 times.In discharge water, copper ion concentration is respectively less than every time
1mg/L.20g activated carbon can continuous processing 8L copper ion concentration be the waste water of 100mg/L, now lives
Property charcoal close to absorption saturated, next step reclaiming metals copper can be carried out.Electricity at 7 × 7 × 10cm
In solution groove, insertion graphite electrode is as anode, and 4 × 3cm copper sheet is negative electrode, two electrode spacings 4cm,
Insertion polymerization thing battery diaphragm at two battery lead plates, is placed in two polymerizations by activated carbon saturated for above-mentioned absorption
Between thing battery diaphragm.Add the metabisulfite solution of 200mL0.2mol/L in a cell, open magnetic
Power agitator, control rotor speed is 500r/min, connects DC source, and control flume voltage is 3.0V,
Electrolysis time 6h, reclaims copper 730mg, often reclaims 1kg copper loss electricity about 3.4 degree.Activated carbon after electrolysis
Regeneration rate reaches 90%, can reuse.Process the waste water that 1m3 copper ion concentration is 100mg/L to need
Using the activated carbon of 2.5kg the present embodiment, in processed waste water, copper ion concentration is less than 1mg/L, recyclable
95g copper, power consumption 0.3 degree.
Comparative example two
As a example by copper-containing wastewater
If using existing electrochemical process process the copper-containing wastewater of the present embodiment 100mg/L and reclaim gold
Belonging to copper, waste water need to concentrate 50 times, i.e. processes 1m3 waste water and need to be concentrated into 20L, power consumption about 980 degree,
Relatively embodiment 1 energy consumption is higher.If using activated carbon first to adsorb resolve copper ion with acid solution again, finally
Electroreduction obtains the method for metallic copper, uses the activated carbon used by the present embodiment, 20g activated carbon equally
Continuous processing 8L copper ion concentration is the waste water of 100mg/L, then by activated carbon transfer saturated for absorption
To resolving groove, adding 200mL concentration is the hydrochloric acid solution of 1mol/L, immersion 4h, solid-liquid separation,
Activated carbon repeats above-mentioned resolving 2 times, collects all desorbed solutions, copper ion resolution factor about 90%, solves
In analysis liquid, copper ion concentration is about 1.2g/L.Desorbed solution is concentrated into 120mL and regulates pH=4-5.
It is electrolysed 5h at tank voltage 3.0V, reclaims copper 700mg, often reclaim 1kg cupric electrolysis power consumption about 3.3 degree.Place
Manage the waste water that 1m3 copper ion concentration is 100mg/L and need to use the activated carbon of 2.5kg the present embodiment, separately
Need to consume about 6.25L concentrated hydrochloric acid, and the alkali neutralized, recyclable 87.5g when outer copper ion resolves
Copper, power consumption about 0.29 degree.But owing to desorbed solution also needs appropriateness concentration, about power consumption 60 before electroreduction
Degree, far above electrolytic process energy consumption.Therefore COMPREHENSIVE CALCULATING the method processes waste water and reclaims the one-tenth of metallic copper
This is far above the present embodiment method.
Embodiment three
As a example by lead waste water
Taking the homemade active fruit shell carbon of 20g and add adsorption column, this activated carbon is 1g/L at plumbum ion concentration
Solution in lead ion adsorbance be about 150mg/g and close adsorption column lower end piston, add 1L lead ion
Concentration is the solution of 50mg/L, and room temperature stands 3h.Adsorption column lower end piston is opened, releases liquid,
In detection effluent, the concentration of lead ion is less than 1mg/L, reaches discharge standard.Close adsorption column lower end to live
Plug, repeats above-mentioned adsorption process 4 times.In discharge water, plumbum ion concentration is respectively less than 1mg/L every time.20g
Activated carbon can continuous processing 5L plumbum ion concentration be the waste water of 50mg/L, and now activated carbon is close to absorption
Saturated, stop absorption.In the electrolysis bath of 7 × 7 × 10cm, insertion graphite electrode is as anode, 4 ×
3cm copper sheet is negative electrode, two electrode spacings 4cm, at insertion polymerization thing battery diaphragm at two battery lead plates,
Activated carbon saturated for above-mentioned absorption is placed between two polymer battery separators.Add in a cell
The sodium nitrate solution of 200mL0.5mol/L, opens magnetic stirring apparatus, and control rotor speed is 500r/min,
Activated carbon is suspended in the solution between two polymer battery separators and does not occurs directly to contact with electrode, connects
Logical DC source, tank voltage is 2V, electrolysis time 1h, reclaims lead 0.23g, often reclaims 1kg lead loss electricity
About 1.56 degree.Regenerating active carbon rate after electrolysis reaches more than 90%, can reuse.Process 1m3
Plumbum ion concentration is the activated carbon that the waste water of 50mg/L need to use 4kg the present embodiment, in processed waste water
Plumbum ion concentration is less than 1mg/L, recyclable 46g lead, power consumption 0.07 degree.
Comparative example three
As a example by lead waste water
If using existing electrochemical process process the lead waste water of the present embodiment 50mg/L and reclaim metal
Lead, waste water need to concentrate 20 times, i.e. processes 1m3 waste water and need to be concentrated into 50L, power consumption about 950 degree, far
Higher than electrolysis energy consumption.If using activated carbon first to adsorb to resolve with acid solution, last electroreduction obtains again
The method of metallic lead, uses the activated carbon used by the present embodiment, 20g activated carbon continuous processing 5L equally
Plumbum ion concentration is the waste water of 50mg/L, then is transferred to resolve groove by adsorbing saturated activated carbon, adds
Enter the salpeter solution that 200mL concentration is 1mol/L, soak 2h, solid-liquid separation, on activated carbon repeats
State resolving 2 times, collect all desorbed solutions, lead ion resolution factor about 88%, lead ion in desorbed solution
Concentration is about 0.36g/L, adds alkali and is neutralized to pH=5, and is concentrated into 150mL.It is electrolysed at tank voltage 2.0V
1h, reclaims lead 0.18g, often reclaims 1kg lead loss electricity about 1.6 degree.Processing 1m3 plumbum ion concentration is 50mg/L
Waste water need to use the activated carbon of 4kg the present embodiment, recyclable 36g lead, power consumption about 0.06 degree.But
Owing to desorbed solution also needs appropriateness concentration before electroreduction, about power consumption 90 degree, far above electrolytic process energy
Consumption.Additionally lead ion needs to consume about 7.7L concentrated nitric acid, and the alkali neutralized when resolving, and therefore combines
Add up to and calculate the method and process waste water and reclaim the cost of metallic lead far above the present embodiment method, identical useless
The metallic lead reclaimed during water treating capacity is also less than the present embodiment.
Embodiment four
As a example by nickel-containing waste water
Taking 20g homemade rice husk matrix activated carbon and add adsorption column, this activated carbon is 1g/L at nickel ion concentration
Solution in nickel ion adsorbance be about 2000mg/g.Close adsorption column lower end piston, add 1L nickel from
Sub-concentration is the simulated wastewater of 100mg/L, and room temperature stands 4h.Adsorption column lower end piston is opened, puts
Going out liquid, in detection effluent, the concentration of nickel ion is less than 1mg/L, reaches discharge standard.Close absorption
Post lower end piston, repeats above-mentioned adsorption process 49 times.In discharge water, nickel ion concentration is respectively less than every time
1mg/L.20g activated carbon can continuous processing 50L nickel ion concentration be the waste water of 100mg/L, now lives
Property charcoal close to absorption saturated, proceed to reclaiming metals nickel in electrolysis bath.Electrolysis at 7 × 7 × 10cm
In groove, insertion graphite electrode is as anode, and 4 × 3cm copper sheet is negative electrode, and two electrode spacings 4cm are being leaned on
At nearly two battery lead plates, insertion polymerization thing battery diaphragm, is placed in two polymer by activated carbon saturated for above-mentioned absorption
Between battery diaphragm.Add the metabisulfite solution of 200mL 0.3mol/L in a cell, open magnetic force
Agitator, control rotor speed is 500r/min, connects DC source, and control flume voltage is 3.5V, electricity
Solution time 21.5h, reclaims nickel 4.75g, often reclaims 1kg nickel power consumption about 3.8 degree.Activated carbon after electrolysis
Regeneration rate reaches more than 90%, can reuse.Processing 1m3 nickel ion concentration is the useless of 100mg/L
Water need to use the activated carbon of 0.4kg the present embodiment, and in processed waste water, nickel ion concentration is less than 1mg/L,
Recyclable 95g nickel, about power consumption 0.36 degree.
Comparative example four
As a example by nickel-containing waste water
If using existing electrochemical process process the nickel-containing waste water of the present embodiment 100mg/L and reclaim gold
Belonging to nickel, waste water need to concentrate 20 times, i.e. processes 1m3 waste water and need to be concentrated into 50L, power consumption about 950 degree,
Far above electrolysis energy consumption.If using activated carbon first to adsorb to resolve with acid solution, last electroreduction obtains again
To the method for metallic nickel, use the activated carbon used by the present embodiment, 20g activated carbon continuous processing 50L equally
Nickel ion concentration is the waste water of 100mg/L, then is transferred to resolve groove by adsorbing saturated activated carbon,
Adding 200mL concentration is the sulfuric acid solution of 1mol/L, soaks 2h, solid-liquid separation, and activated carbon repeats
Above-mentioned resolving 2 times, collects all desorbed solutions, nickel ion resolution factor about 90%, in desorbed solution nickel from
Sub-concentration is about 7.5g/L, adds alkali and is neutralized to pH=5.It is electrolysed 18h at tank voltage 3.5V, reclaims nickel 4.0g,
Often reclaim 1kg nickel power consumption about 3.8 degree.Process the waste water that 1m3 nickel ion concentration is 100mg/L need to make
With the activated carbon of 0.4kg the present embodiment, recyclable 80.0g nickel, power consumption about 0.3 degree.Additionally nickel ion
Need to consume about 0.4L concentrated sulphuric acid, and the alkali neutralized during parsing, therefore at COMPREHENSIVE CALCULATING the method
Reason waste water also reclaims the cost of metallic nickel and remains above the present embodiment method, reclaims when identical wastewater treatment capacity
Metallic nickel also less than the present embodiment.
Embodiment five
As a example by the simulation electroplating wastewater containing copper and mickel hybrid ionic
Take 20g embodiment 4 activated carbon and add adsorption column, close adsorption column lower end piston, add 1L and contain
The hybrid ionic simulation electroplating wastewater of 50mg/L nickel ion and 20mg/L copper ion, room temperature stands 4h.
Being opened by adsorption column lower end piston, release liquid, in detection effluent, the concentration of nickel ion and copper ion is equal
Less than 1mg/L, reach discharge standard.Close adsorption column lower end piston, repeat above-mentioned adsorption process 19
Secondary.In discharge water, the concentration of nickel ion and copper ion is respectively less than 1mg/L every time.20g activated carbon can be continuous
Process 20L containing 50mg/L nickel ion and the simulation electroplating wastewater of 20mg/L copper ion, now activated carbon
Saturated close to absorption, proceed to reclaiming metals in electrolysis bath.The electrolysis bath of 7 × 7 × 10cm is inserted
Entering graphite electrode as anode, 4 × 3cm copper sheet is negative electrode, two electrode spacings 4cm, near two electricity
Insertion polymerization thing battery diaphragm at pole plate, activated carbon saturated for above-mentioned absorption is placed in two polymer batteries every
Between film.Add the metabisulfite solution of 200mL 0.3mol/L in a cell, open magnetic stirring apparatus,
Control rotor speed is 800r/min, connects DC source, and control flume voltage is 5V, and electrolysis 1.2h can return
Receive copper 318mg, temporary close power supply, change a piece of negative electrode.Open DC source and continue electrolysis, initially
In 0.5h electrolytic process, cathodic deposition is copper nickel mixture, continues electrolysis 4h recyclable nickel 900mg.
Regenerating active carbon rate after electrolysis reaches more than 90%, can reuse.Process the above-mentioned mixing of 1m3 from
Sub-waste water need to use the activated carbon of 1kg the present embodiment, and in processed waste water, copper ion and nickel ion concentration are equal
Less than 1mg/L, the metallic copper 15.9g that recyclable purity is higher, nickel 45.0g, and the mixing of 9.0g nickel, copper
Thing, power consumption about 0.4 degree altogether.
Comparative example five
As a example by the simulation electroplating wastewater containing copper and mickel hybrid ionic
If using existing electrochemical process to process the present embodiment containing 50mg/L nickel ion and 20mg/L copper
The composite waste of ion also reclaims metal copper and mickel, and waste water need to concentrate more than 50 times, i.e. processes 1m3 and gives up
Water need to be concentrated into below 20L, and power consumption is more than 980 degree, far above electrolysis energy consumption.If employing activated carbon
First adsorbing and resolve with acid solution, last electroreduction obtains the method for metal, uses the present embodiment equally
Activated carbon used, this hybrid ionic waste water of 20g activated carbon continuous processing 20L, then will adsorb saturated
Activated carbon be transferred to resolve groove, add 200mL concentration be the sulfuric acid solution of 1mol/L, soak 3h,
Solid-liquid separation, activated carbon repeats above-mentioned resolving 2 times, collects all desorbed solutions, copper ion resolution factor
About 82%, nickel ion resolution factor about 90%, in desorbed solution, copper ion concentration is about 0.54g/L, and nickel ion is dense
Degree is about 1.5g/L, adds alkali and is neutralized to pH=5 and is concentrated into 300mL.It is electrolysed 1.2h at tank voltage 5V,
Reclaim copper 290mg.Temporary close power supply, changes a piece of negative electrode.Open DC source and continue electrolysis,
In first 0.5h electrolytic process, cathodic deposition is copper nickel mixture, continues the electrolysis recyclable nickel of 4h
850mg.Process 1m3 above-mentioned hybrid ionic waste water and need to use the activated carbon of 1kg the present embodiment, after process
Cu in waste water ion and nickel ion concentration are respectively less than 1mg/L, the metallic copper 14.5g that recyclable purity is higher,
Nickel 42.5g, and 5.9g nickel, copper mixture, power consumption about 0.4 degree altogether.But owing to desorbed solution is in electrolysis
Also needing appropriateness concentration before reduction, about power consumption 15 degree, far above electrolytic process energy consumption.Additionally copper, nickel from
Need to consume about 0.4L concentrated sulphuric acid, and the alkali neutralized, therefore COMPREHENSIVE CALCULATING the method during subsolution analysis
Process waste water and reclaim the cost of metal copper and mickel and remain above the present embodiment method, in identical wastewater treatment capacity
The metal copper and mickel of Shi Huishou is also less than the present embodiment.In sum, the invention discloses one by low dense
The method reclaiming metal in degree effluent containing heavy metal ions, selects have good adsorption for heavy metal ion
Heavy metal ion in the activated carbon adsorption solution of energy, by the heavy metal ion enrichment of low concentration at activated carbon
In, then it is scattered in adsorbing saturated activated carbon in the electrolysis bath of two electrode systems, at suitable groove electricity
Under pressure and electric current density, the metal ion being adsorbed in activated carbon resolves and to negative electrode under the effect of electric field
Migrating, final metal ion is deposited as, in cathodic reduction, the metal that purity is higher.This process low concentration weight
The method of metal ion waste water both can reduce heavy metal ions in wastewater content and want to reach environment protection emission
Asking, directly can be recovered to useful metal at negative electrode again, activated carbon is also regenerated simultaneously, can again use
In absorption, reduce cost for wastewater treatment.The inventive method can process concentration of heavy metal ion
The waste water of 10mg/L～1g/L, reclaims the about power consumption 3.0 degree～4.0 degree of 1kg copper；Reclaim 1kg nickel about to consume
Electricity 3.5 degree～4.5 degree；Reclaim the about power consumption 1.5 degree～2.5 degree of 1kg lead.In actual applications, a lot
Industrial wastewater contains more than one metal ion, and the method that the present invention provides can be by controlling electrolytic condition
Make the different metal ion being adsorbed on activated carbon order restoring deposition on negative electrode, obtain purity relatively respectively
High different metal.The inventive method is particularly suited for plating, printed circuit board (PCB) production, battery production etc.
The process of industrial wastewater, can not directly reclaim useful gold when solving process low-concentration heavy metal ions waste water
Belong to, and process waste water process and easily cause the problem such as secondary pollution and high expensive, make enterprise really real
Existing green produces, recycling economy.
It should be noted that above example only in order to technical scheme to be described and unrestricted, although
Being described in detail the present invention with reference to preferred embodiment, those of ordinary skill in the art should manage
Solve, technical scheme can be modified or equivalent, without deviating from the technology of the present invention
The spirit and scope of scheme, it all should be contained in the middle of scope of the presently claimed invention.
Claims (6)
1. one kind by the method reclaiming metal in low-concentration heavy metal ions waste water, it is characterised in that should
Method comprises the steps:
(1) absorption: select the activated carbon that adsorption of metal ions capacity is big is made adsorbent, join containing weight
In the waste water of metal ion, stand, make metal ion fully be adsorbed by activated carbon；
(2) solid-liquid separation: by the liquid after absorption and Activated carbon separation, then repeat step (1) and step (2)
Process several times, until described activated carbon adsorption is saturated；
(3) metal recovery: activated carbon saturated for absorption is moved into electrolysis bath, adds electrolyte solution electrolysis,
Metal is gone out in cathodic deposition.
The most according to claim 1 by the method reclaiming metal in low-concentration heavy metal ions waste water, its
It is characterised by: the activated carbon that adsorption of metal ions capacity is big is made adsorbent by the selection described in step (1),
Join in the waste water containing heavy metal ion, stand, make metal ion fully be adsorbed by activated carbon particularly as follows:
Select the adsorption capacity activity more than 50mg/g in the solution that single heavy metal mass of ion concentration is 1g/L
Charcoal, as adsorbent, then selects a lower end with the container of piston control outlet as adsorption column, in institute
State in adsorption column addition 20g activated carbon, close the piston of described adsorption column lower end, add 1L～2L metal from
Sub-concentration is the solution of 10mg/L～1g/L, and room temperature stands 1h～5h.
The most according to claim 2 by the method reclaiming metal in low-concentration heavy metal ions waste water, its
It is characterised by: by the liquid after absorption and Activated carbon separation described in step (2), repeat step one and step
Two processes several times, until activated carbon adsorption is saturated particularly as follows: opened by described adsorption column lower end piston, liquid
Body flows out, and solid activated carbon is adsorbed column bottom filter screen and is retained in described adsorption column, closure piston, repeats
Above-mentioned steps (1) and step (2) are several times until activated carbon reaches to adsorb saturated.
The most according to claim 3 by the method reclaiming metal in low-concentration heavy metal ions waste water, its
It is characterised by, described in step (3), activated carbon saturated for absorption is moved into electrolysis bath, add electrolyte solution
Electrolysis, goes out metal in cathodic deposition particularly as follows: use anode and negative electrode two electrode system, and two electrode spacings are
2cm～5cm, inserts a piece of polymer battery separator, by described suction inside two electrodes at electrode respectively
Attached saturated activated carbon is placed between two polymer battery separators, adds concentration in a cell and is
The sulphuric acid of 0.1mol/L～0.5mol/L, sodium sulfate or sodium nitrate solution, be placed in magnetic force by described electrolysis bath and stir
Mixing on device, controlling bath voltage is 2.0V～8.0V, and electrolysis time is 1h～40h, and metal deposit is at negative electrode
On, electrolysis directly reclaims metal at negative electrode after terminating.
The most according to claim 4 by the method reclaiming metal in low-concentration heavy metal ions waste water, its
Being characterised by, described anode is graphite electrode, and described negative electrode is copper plate electrode, stainless steel substrates electrode or graphite
Any one in electrode.
The most according to claim 4 by the method reclaiming metal in low-concentration heavy metal ions waste water, its
Being characterised by, the rotor speed on described 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 |
| CN109231337A (en) * | 2018-10-09 | 2019-01-18 | 四川农业大学 | Farmland low concentration contains the portable absorbing treatment device of heavy metal containing sewage and processing method |
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| 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 |
| CN110921754A (en) * | 2019-11-25 | 2020-03-27 | 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 |
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| 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 |
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| CN109231337A (en) * | 2018-10-09 | 2019-01-18 | 四川农业大学 | Farmland low concentration contains the portable absorbing treatment device of heavy metal containing sewage and processing method |
| 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 |
| CN110921754A (en) * | 2019-11-25 | 2020-03-27 | 山东深信节能环保科技有限公司 | Resource treatment method for low-concentration heavy metal ion wastewater |
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