CN107352636A - It is a kind of to reclaim the apparatus and method for handling garden mud and sewage simultaneously for plating industrial district heavy metal in waste water - Google Patents
It is a kind of to reclaim the apparatus and method for handling garden mud and sewage simultaneously for plating industrial district heavy metal in waste water Download PDFInfo
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- CN107352636A CN107352636A CN201710727163.3A CN201710727163A CN107352636A CN 107352636 A CN107352636 A CN 107352636A CN 201710727163 A CN201710727163 A CN 201710727163A CN 107352636 A CN107352636 A CN 107352636A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
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Abstract
It is a kind of to reclaim the apparatus and method for handling garden mud and sewage simultaneously for plating industrial district heavy metal in waste water, it is related to heavy metal recovery while the method for handling mud and sewage, and the method that it will solve existing microbiological fuel cell processing electroplating wastewater is difficult to the technical problem for reclaiming heavy metal.The present apparatus includes the first biological anode chamber, biological-cathode room, settling zone, chemical cathode room and the second biological anode chamber being arranged in order；Also include outside storage electrical equipment or electrical appliance；Each room is respectively provided with graphite brush electrode, stomata and apopore；Has function bacterium on graphite brush electrode in addition to chemical cathode room, electrode connects into closed-loop path by storing electrical equipment or electrical appliance.Method：Sludge is placed on the first biological anode chamber and second biological anode chamber's inner sealing, and negative electrode culture medium is added in biological-cathode room, electroplating wastewater is added in chemical cathode room, and clear water is added to settling zone；Biological-cathode room is aerated and changes negative electrode culture medium, sludge and electroplating wastewater on time, completion processing.
Description
Technical field
The present invention relates to the method that heavy metal recovery handles mud and sewage simultaneously, belong to bioelectrochemistry field, be specially
One kind realizes plating industrial district heavy metal out of electroplating wastewater recovery, while realizes the recycling of sludge and stabilize and synchronously produce
The method of electricity.
Background technology
Because electroplating industry pollution yield is big, for environmental protection, it is easy to manage, electroplating enterprise is concentrated in each province and city, shape
Unify operational management into plating industrial district.Electroplate Factory in the process of running caused a large amount of wastewater source in pre-electroplating treatment,
Coating rinses, post-processes, wash away mill floor, coating bath seepage or operational administrative it is improper caused by run, drip, leak various grooves
Liquid and there are chromium, cadmium, lead, copper, nickel, zinc with water etc., contained Heavy Metals.If being thrown into environment, heavy metal ion can pass through drink
With the enrichment of water and food chain, the mankind are produced with more extensive and more serious harm.
Waste water is classified according to the type of plating, can be generally divided into chromate waste water, nickel-containing waste water, copper-containing wastewater,
Zinc-containing water, cadmium wastewater etc..Contained heavy metal species will see the article and quantity of processing, generally plating in waste water from plating plant
Waste water is based on chromium.Heavy metal containing wastewater treatment the most frequently used method in plating industrial district has chemical reduction method, electrolysis and film
Method.The chemical drugs dosage that wherein chemical reduction method adds is huge, causes lasting investment amount big and secondary caused by added regent
Pollution.Electrolysis is switched on power consumption height, the inadequate economical and effective of this method.Embrane method energy expenditure is more, and easily fouling membrane etc. occurs
Problem.Structure double-chamber microbiological fuel cell can accelerate the degraded of organic matter in sludge, while realize negative electrode heavy metal ion
Reduction, currently with microbiological fuel cell processing electroplating wastewater turn into research focus.Publication No. CN104386826A
Chinese patent disclose processing and the monitoring method of a kind of chromate waste water based on microbiological fuel cell.The reactor is double
Chamber microbiological fuel cell, in the anode compartment using anaerobic sludge and sodium acetate solution as matrix, negative electrode adds catholyte and started.Electricity
Anode uses the anolyte of anaerobic instead after pressure is stable, and negative electrode uses electroplating wastewater of chromium instead.The method is simply by Cr6+It is reduced to Cr3+,
The effect of continued synchronization recovery metal can not be reached.And operational effect is general, each heavy metal species are present in electroplating wastewater
In the case of, metal waste liqouor trouble.
The content of the invention
The present invention is to solve the method for existing microbiological fuel cell processing electroplating wastewater to be difficult to reclaim heavy metal
Technical problem, and a kind of plating industrial district heavy metal in waste water that is used for is provided and reclaims while handles the device of garden mud and sewage
And method.
The plating industrial district heavy metal in waste water that is used for of the present invention reclaims the device bag for handling garden mud and sewage simultaneously
Include the biological anode chamber 1 of first be arranged in order, biological-cathode room 2, settling zone 3,4 and second biological anode chamber 5 of chemical cathode room；
Also include two outside storage electrical equipment or electrical appliance 6；
Separated between first biological anode chamber 1 and biological-cathode room 2 with PEM, biological-cathode room 2 and settling zone 3
Between separated with anion-exchange membrane, separated between settling zone 3 and chemical cathode room 4 with cation-exchange membrane, chemical cathode room 4
Separated between the second biological anode chamber 5 with PEM；
The top of first biological anode chamber 1 is provided with a Room stomata 1-1, is internally provided with a Room graphite brush electrode 1-2, under
Portion is provided with a Room apopore 1-3, and a Room reference electrode 1-4, a Room graphite brush electrode are additionally provided with the first biological anode chamber 1
Has electro-chemical activity bacterium on 1-2；Biological anode chamber 1 is used to add sludge；Reference electrode 1-4 is used to reflect and characterize in pole room
The activity of electro-chemical activity bacterium；
The top of biological-cathode room 2 is provided with two Room stomata 2-1, is internally provided with two Room graphite brush electrode 2-2, bottom is set
Two Room apopore 2-3 are equipped with, aerator 2-4 is additionally provided with biological-cathode room 2 and doses appropriate graphite particle 2-5；Two Room
Adhere to aerated biological activated bacterium on graphite brush electrode 2-2 and graphite particle 2-5, be used to add negative electrode culture in biological-cathode room 2
Base；
The top of settling zone 3 is provided with three Room stomata 3-1, and bottom is provided with three Room apopore 3-2；It is used in settling zone 3
Clear water is placed to collect heavy metal and its precipitation；
The top of chemical cathode room 4 is provided with four Room stomata 4-1, is internally provided with four Room graphite brush electrode 4-2, bottom is set
It is equipped with four Room apopore 4-3；Chemical cathode room 4 is used to add electroplating wastewater；
The top of second biological anode chamber 5 is provided with five Room stomata 5-1, is internally provided with five Room graphite brush electrode 5-2, under
Portion is provided with five Room apopore 5-3；Five Room reference electrode 5-4, five Room graphite brush electrodes are additionally provided with second biological anode chamber 5
Has electro-chemical activity bacterium on 5-2；Second biological anode chamber 5 is used to add sludge；Reference electrode 5-4 is used to reflect and characterize pole
The activity of indoor electro-chemical activity bacterium；
One Room apopore 1-3 and five Room apopore 5-3 pipeline connections；
One Room graphite brush electrode 1-2 and two Room graphite brush electrode 2-2 is connected into through outside storage electrical equipment or electrical appliance 6 with wire
Closed-loop path, four Room graphite brush electrode 4-2 and five Room graphite brush electrode 5-2 are connected by outside storage electrical equipment or electrical appliance 6 with wire
Form closed-loop path；Or by a Room graphite brush electrode 1-2 is in parallel with five Room graphite brush electrode 5-2, two Room graphite brush electrode 2-2
In parallel with four Room graphite brush electrode 4-2, cathode anode is connected into and closed back by outside storage electrical equipment or electrical appliance 6 with wire again
Road.
Above-mentioned device is used for the recovery of plating industrial district heavy metal in waste water while handles the side of garden mud and sewage
Method, carry out according to the following steps：
First, sludge is placed in the first biological 1 and second biological anode chamber 5 of anode chamber, the first biological anode chamber 1 of closing
The stomata 5-1 of the one biological anode chambers 5 of Room stomata 1-1 and second；Negative electrode culture medium is added in biological-cathode room 2, will be electroplated
Waste water is added in chemical cathode room 4, and clear water is added to settling zone 3；
2nd, the first biological anode chamber 1, biological-cathode room 2, the temperature of 4 and second biological anode chamber 5 of chemical cathode room are kept
For 20~40 DEG C, the aerator 2-4 in biological-cathode room 2 is opened, is handled, changes half negative electrode culture medium within every 2~5 days,
Primary sludge is changed within every 5~10 days, changes within every 2~5 days an electroplating wastewater, completes the place of plating industrial district sludge and electroplating wastewater
Reason.
Separated in the present invention between two biological anode chambers and cathode chamber using PEM, this structure is advantageous to anode
Indoor proton is quickly transmitted to both sides cathode chamber；Anode chamber's closing anaerobic, the anaerobic sludge containing multiple types organic matter in it
Simple dissolved organic matter is formed through Hydrolysis Acidification under anaerobic, simple organic is attached to graphite brush electrode
Electro-chemical activity bacterium on (1-2,5-2) is utilized, and electronics is produced in metabolic process and is conducted through electrode to biological-cathode room 2
Graphite brush electrode 4-2 in graphite brush electrode 2-2 and chemical cathode room 4；Electronics is plated water reuse in chemical cathode room 4
Chemical reaction is participated in, reduction reaction occurs with proton and metal ion；Electronics is in biological-cathode room 2 by aerated biological activated bacterium
Using with H+Water is generated with oxygen reaction.Cathode chamber and the black lead brush of anode chamber are connected by storing electrical equipment or electrical appliance 6 with copper conductor
Connect, so as to which caused electric energy be used.Therefore, the chemical cathode 4 being connected in five Room reaction units with anode has reduction
The effect of metal ion in electroplating wastewater, and the biological-cathode 2 being connected with anode has generation OH-Effect, OH-It can be used for
Precipitate metal ion.The anion-exchange membrane and cation-exchange membrane of the both sides of settling zone 3 only allow respectively anion and sun from
Son is by so as to have the function that to collect and precipitate metal and its hydroxide.
The invention has the advantages that：1., can because the anion-exchange membrane between biological-cathode room 2 and the Room of settling zone 3 is present
To prevent the Room of settling zone 3, the heavy metal ion in chemical cathode room 4 from entering biological-cathode room 2 to destroy not tolerating the life of heavy metal
Thing negative electrode, and OH can be allowed-By so as to adjust the pH of settling zone 3 using biological-cathode room 2；Due to settling zone 3 and change
The presence of the cation-exchange membrane between cathode chamber 4 is learned, the OH of the Room of settling zone 3 can be prevented-Given birth to ahead of time into chemical cathode room 4
Into heavy metal precipitation, heavy metal collection is influenceed, and heavy metal ion can be allowed chemically the cross-film of cathode chamber 4 enters settling zone
3 generation hydroxide precipitations, carry out the enrichment and accumulation of heavy metal recovery.2. ensuring sufficiently large contact area and certain
After hydraulic detention time, reactor can industrialize completely, carry out configuration expansion, realize continuous stream, in optimum operating condition most
The heavy metal in electroplating wastewater is continuously reclaimed under conditions of good rate of reduction.3. aerobic pole room has stronger stabilization compared with anaerobism pole room
Property and antijamming capability, the electricity production of 4 and second biological anode chamber 5 of chemical cathode room reducible heavy metal concentration in by waste water
Influence, the first biological anode chamber 1 and biological-cathode room 2 runs and produced electricity stable so that the electric energy output of reactor is relatively stable.
No matter 4. heavy metal-containing electroplating effluent condition (aerobic, anaerobism) though concentration (middle concentration, high concentration or ultrahigh concentration) no matter purity
(whether having other metal ion disturbances) may be degraded, and be different from common biological treatment, high concentration heavy metal ion
Reactor degradation effect will not be reduced, degradation rate can be accelerated to a certain extent on the contrary.5. the present invention can be by Cr6+It is reduced to Cr3 +, and with Cr (OH)3Form settling zone 3 precipitate collect；Can be by Cu2+It is reduced to Cu2O, or regulation pH make it with Cu (OH)2Shape
State precipitates in settling zone 3 collects；Can be by Ni2+It is reduced to Ni, Zn2+It is reduced to Zn, Cd2+Cd is reduced to, but due to Ni, Zn and Cd
Oxidation-reduction potential be negative value (Ni2+/Ni0, SHE is -0.230V；Zn2+/Zn0, SHE is -0.763V；Cd2+/Cd0, SHE for-
0.403V), reduction effect is slightly poor compared with Cr and Cu；Or the pH value of adjustable settling zone 3 makes Ni2+、Zn2+、Cd2+Respectively with Ni
(OH)2、Zn(OH)2、Cd(OH)2Form precipitates in settling zone 3 collects (Ni (OH)2Produce and precipitate in pH=7, Zn (OH)2
Produce and precipitate during pH=8~10, Cd (OH)2Produce and precipitate in pH=11).6. the method for the present invention can be not additional
Efficiently the heavy metal in electroplating wastewater is reclaimed in reduction in the case of medicament；Compared to Treatment of Industrial Park of Plating zone electroplating waste water conventional process
Method also can largely reduce sludge quantity caused by preprocessing process before biological treatment stage, so as to reduce dangerous waste disposal expense
With.7. the heavy metal purity that the present invention reclaims is higher, cost increase Electroplate Factory benefit can be saved.
The present invention also has certain while ensureing good to crome metal recovering effect to copper, zinc, nickel, cadmium plasma
Removal effect.
Brief description of the drawings
The plating industrial district heavy metal in waste water that is used for that Fig. 1 is the present invention reclaims while handles the dress of garden mud and sewage
Put structural representation；Wherein 1 it is the first biological anode chamber, 2 is biological cathode chamber, 3 is settling zone, 4 is chemical cathode room, 5 is
Second biological anode chamber, 6 be outside storage electrical equipment or electrical appliance；1-1 is a Room stomata, and 1-2 is a Room graphite brush electrode, and 1-3 is
One Room apopore, 1-4 are a Room reference electrode；2-1 is two Room stomatas, and 2-2 is two Room graphite brush electrodes, and 2-3 is two Room water outlets
Hole, 2-4 are aerator, and 2-5 is graphite particle；3-1 is three Room stomatas, and 3-2 is three Room apopores；4-1 is four Room stomatas, 4-
2 be four Room graphite brush electrodes, and 4-3 is four Room apopores；5-1 is five Room stomatas, and 5-2 is five Room graphite brush electrodes, and the Room of 5-3 five goes out
Water hole, 5-4 are five Room reference electrodes；
Embodiment
Embodiment one：The plating industrial district heavy metal in waste water that is used for of present embodiment reclaims while handles garden
The device of area's mud and sewage includes the first biological anode chamber 1, biological-cathode room 2, settling zone 3, the chemical cathode room 4 being arranged in order
With the second biological anode chamber 5；Also include two outside storage electrical equipment or electrical appliance 6；First biological anode chamber 1 and biological-cathode room 2
Between separated with PEM, separated between biological-cathode room 2 and settling zone 3 with anion-exchange membrane, settling zone 3 with chemistry
Separated between cathode chamber 4 with cation-exchange membrane, with PEM point between 4 and second biological anode chamber 5 of chemical cathode room
Every；The top of first biological anode chamber 1 is provided with a Room stomata 1-1, is internally provided with a Room graphite brush electrode 1-2, bottom is set
A Room apopore 1-3 is equipped with, a Room reference electrode 1-4, a Room graphite brush electrode 1-2 are additionally provided with the first biological anode chamber 1
It is upper to have electro-chemical activity bacterium；Biological anode chamber 1 is used to add sludge；Reference electrode 1-4 is used to reflect and characterize pole indoor electric
The activity of chemism bacterium；The top of biological-cathode room 2 is provided with two Room stomata 2-1, is internally provided with two Room graphite brush electrodes
2-2, bottom are provided with two Room apopore 2-3, are additionally provided with aerator 2-4 in biological-cathode room 2 and dose appropriate graphite
Grain 2-5；Adhere to aerated biological activated bacterium on two Room graphite brush electrode 2-2 and graphite particle 2-5, biological-cathode room 2 is used to add
Negative electrode culture medium；The top of settling zone 3 is provided with three Room stomata 3-1, and bottom is provided with three Room apopore 3-2；Used in settling zone 3
Precipitated in placing clear water with collecting heavy metal and its hydroxide；The top of chemical cathode room 4 is provided with four Room stomata 4-1, interior
Portion is provided with four Room graphite brush electrode 4-2, and bottom is provided with four Room apopore 4-3；Chemical cathode room 4, which is used to add to electroplate, gives up
Water；The top of second biological anode chamber 5 is provided with five Room stomata 5-1, is internally provided with five Room graphite brush electrode 5-2, bottom is set
It is equipped with five Room apopore 5-3；Five Room reference electrode 5-4, five Room graphite brush electrode 5-2 are additionally provided with second biological anode chamber 5
It is upper to have electro-chemical activity bacterium；It is used to add sludge in second biological anode chamber 5；Reference electrode 5-4 is used to reflect and characterize pole
The activity of indoor electro-chemical activity bacterium；One Room apopore 1-3 and five Room apopore 5-3 pipeline connections；One Room graphite brush electrode
1-2 and two Room graphite brush electrode 2-2 connects into closed-loop path, four Room black lead brush electricity through outside storage electrical equipment or electrical appliance 6 with wire
Pole 4-2 and five Room graphite brush electrode 5-2 even forms closed-loop path by outside storage electrical equipment or electrical appliance 6 with wire；Or by one
Room graphite brush electrode 1-2 is in parallel with five Room graphite brush electrode 5-2, two Room graphite brush electrode 2-2 and four Room graphite brush electrode 4-2 simultaneously
Connection, cathode anode connect into closed-loop path with wire by outside storage electrical equipment or electrical appliance 6 again.
Embodiment two：Present embodiment is unlike embodiment one：First biological anode chamber 1 is length
Cube or cylinder；Biological-cathode room 2 is cuboid or cylinder；Chemical cathode room 4 is cuboid or cylinder；Second biology
Anode chamber is cuboid or cylinder；It is other identical with embodiment one.
Cuboid pole room compound with regular structure, prepare simply, be easy to neatly arrange in groups by batch；The advantages of cylinder pole room, exists
In dead zone range caused by the corner of pole room can be reduced, make strength of fluid in pole room uniform.The configuration of settling zone 3 is adapted to conveniently i.e.
Can.
Embodiment three：Present embodiment is unlike embodiment one or two in the first biological anode chamber
1st, biological-cathode room 2, settling zone 3, the bottom of 4 and/or second biological anode chamber 5 of chemical cathode room be provided with magnetic stirring apparatus or
Indoors plus agitator；It is other identical with embodiment one or two.
Strengthen each chamber interior liquid mixing by agitator, microbial activity caused by mitigating topical substance accumulation presses down
System.
Embodiment four：In the first biology sun unlike one of present embodiment and embodiment one to three
Pole room 1, biological-cathode room 2, settling zone 3, the outside of 4 and/or second biological anode chamber 5 of chemical cathode room set attemperator,
Wherein attemperator is water-bath or heat-preservation cotton；It is other identical with one of embodiment one to three.
Can according to the temperature control needs of system (Main Basiss with aerated biological activated bacterium and electro-chemical activity bacteria growing most
Preference temperature adjusts), using the heat insulation effect of heat-insulation layer, it is easy to carry out temperature control to system, microorganism is in optimum
Under temperature conditionss.
Embodiment five：Device described in embodiment one is used for plating industrial district heavy metal in waste water
The method that recovery handles garden mud and sewage simultaneously, is carried out according to the following steps：
First, the sludge of plating industrial district sewage treatment plant is placed on the first biological 1 and second biological anode chamber 5 of anode chamber
It is interior, close the stomata 5-1 of the biological anode chambers 5 of Room stomata 1-1 and second of the first biological anode chamber 1；Negative electrode culture medium is added
Enter into biological-cathode room 2, electroplating wastewater is added in chemical cathode room 4, clear water is added to settling zone 3；
2nd, the first biological anode chamber 1, biological-cathode room 2, the temperature of 4 and second biological anode chamber 5 of chemical cathode room are kept
For 20~40 DEG C, the aerator 2-4 in biological-cathode room 2 is opened, is handled, changes half negative electrode culture medium within every 2~5 days,
Primary sludge is changed within every 5~10 days, changes within every 2~5 days an electroplating wastewater, completes the place of plating industrial district sludge and electroplating wastewater
Reason.
Embodiment six：Present embodiment and the galvanizer unlike embodiment five described in step 1
The sludge of industry garden sewage treatment plant is domestic sludge, industrial sludge either domestic sludge and industrial sludge mixture.It is other
It is identical with embodiment five.
Embodiment seven：Present embodiment contains in the electroplating wastewater unlike embodiment five or six
Cr6+、Cu2+、Ni2+、Zn2+And/or Cd2+.It is other identical with embodiment five or six.
Embodiment eight：Weight in electroplating wastewater unlike one of present embodiment and embodiment five to seven
The concentration of metal ion is 50~1000mg/L.It is other identical with one of embodiment five to seven.
Heavy metal concentration is unlimited in heavy metal-containing electroplating effluent in the present invention, but the high concentration heavy metal of present embodiment from
The electricity production of the electroplating wastewater of son and metal recovery effect are more preferable.
Embodiment nine：Contain Cr unlike one of present embodiment and embodiment five to eight6+Plating is useless
Water pretreatment process is as follows：To Cr6+It is 1~2 that the electroplating wastewater that concentration is 50mg/L~300mg/L, which adds sulfuric acid regulation pH value,
Stirred after adding enough hydrogen peroxide, complexing agent is abolished so as to aoxidize, complete pretreatment.Other and embodiment five
It is identical to one of eight.
Because of a large amount of complexing agents meeting bind metal ion added in electroplating process, it is dense to reduce metal ion in electroplating wastewater
Degree, so needing to cement out each metal ion species before electroplating wastewater processing.Present embodiment utilizes Cr under acid condition6+It is strong
Oxidisability and the oxidisability of hydrogen peroxide abolish complexing, and each metal ion species are cemented out and are easy to participate in reacting.
With following verification experimental verification beneficial effects of the present invention：
Experiment 1：The plating industrial district heavy metal in waste water that is used for of this experiment reclaims while handles garden mud and sewage
Method, carry out according to the following steps：
First, preparation：
(1) take 2L anaerobic sludges to seal, 2-3 days are preserved at a temperature of 4~15 DEG C to tame；
(2) material as graphite brush electrode is conductive carbon fibre, is first rinsed with water, then uses 1mol/L HCl respectively
2h is respectively soaked with 1mol/L NaOH solutions, to remove the impurity of electrode material surface, finally soaks 5h with deionized water, it is standby；
(3) PEM, cation-exchange membrane, anion-exchange membrane first use the H of mass fraction 30% before use2O2
Boil 30min, then soak 2h successively with 1mol/L HCl and 1mol/L NaOH solutions respectively, with go membrane removal surface contaminant and
Impurity, 5h finally is soaked with deionized water, it is standby；
(4) Cr in electroplating wastewater6+Concentration is 100mg/L, and electroplating wastewater adds sulphur acid for adjusting pH to be 2, adds enough dioxygens
Stirred after water, complexing agent is abolished so as to aoxidize, complete pretreatment；
2nd, reaction unit is built：
The present apparatus is by the be arranged in order first biological anode chamber 1, biological-cathode room 2, settling zone 3, chemical cathode room 4 and
Two biological anode chambers 5 form；Also two outside storage electrical equipment 6；Proton is used between first biological anode chamber 1 and biological-cathode room 2
Exchange membrane separates, and is separated between biological-cathode room 2 and settling zone 3 with anion-exchange membrane, settling zone 3 and chemical cathode room 4 it
Between separated with cation-exchange membrane, chemical cathode room is separated between 4 and second biological anode chamber 5 with PEM；First life
The top of thing anode chamber 1 is provided with a Room stomata 1-1, is internally provided with a Room graphite brush electrode 1-2, bottom is provided with a Room and gone out
Water hole 1-3, a Room reference electrode 1-4 is additionally provided with the first biological anode chamber 1, and reference electrode 1-4 is used to reflect and characterize pole
The activity of indoor electro-chemical activity bacterium；The top of biological-cathode room 2 is provided with two Room stomata 2-1, is internally provided with two Room graphite
Brush electrode 2-2, bottom are provided with two Room apopore 2-3, and aerator 2-4 is additionally provided with biological-cathode room 2 and is dosed appropriate
Graphite particle 2-5；The top of settling zone 3 is provided with three Room stomata 3-1, and bottom is provided with three Room apopore 3-2；Chemical cathode room
4 top is provided with four Room stomata 4-1, is internally provided with four Room graphite brush electrode 4-2, and bottom is provided with four Room apopore 4-3；
The top of second biological anode chamber 5 is provided with five Room stomata 5-1, is internally provided with five Room graphite brush electrode 5-2, bottom is provided with
Five Room apopore 5-3；Be additionally provided with five Room reference electrode 5-4 in second biological anode chamber 5, reference electrode 5-4 be used to reflect and
Characterize the activity of electro-chemical activity bacterium in pole room；One Room apopore 1-3 and five Room apopore 5-3 pipeline connections；One Room graphite
Brush electrode 1-2 and two Room graphite brush electrode 2-2 connects into closed-loop path, four Room stones through outside storage electrical equipment or electrical appliance 6 with wire
Black brush electrode 4-2 and five Room graphite brush electrode 5-2 even forms closed-loop path by outside storage electrical equipment or electrical appliance 6 with wire；Ginseng
It is commonly connected to than electrode with the anode and negative electrode of reactor in voltage collector, for monitoring electrochemistry production capacity situation；
3rd, start：
The sludge that step 1 has been tamed is added in the first biological 1 and second biological anode chamber 5 of anode chamber, sealing；In life
Negative electrode culture medium and a small amount of garden soil are added in thing cathode chamber 2 and chemical cathode room 4 as inoculation soil, is added into settling zone 3
Clear water；Aeration head is also placed in chemical cathode room 4, is aerated in biological-cathode room 2 and chemical cathode room 4, starts to cultivate；Often
The negative electrode culture medium changed for 2 days in half biological-cathode room 2 and chemical cathode room 4, change within every 5 days a first biological He of anode chamber 1
Sludge in second biological anode chamber 5, after two weeks, cell voltage potential reaches maximum and continual and steady one day, now a Room black lead brush electricity
Have electro-chemical activity bacterium on pole 1-2 and five Room graphite brush electrode 5-2, two Room graphite brush electrode 2-2 with it is attached on graphite particle 2-5
Aerated biological activated bacterium, adheres to aerated biological activated bacterium on four Room graphite brush electrodes；Start successfully；
Wherein negative electrode Medium Proportion is as follows：
| NH4Cl | K2HPO4 | MgSO4 | KCl | KH2PO4 | Fe2(SO4)3 | Dusty yeast | Trace element |
| 1.0g/L | 1.2g/L | 0.5g/L | 0.5g/L | 0.14g/L | 0.01g/L | 0.02g/L | 10mL/L |
Trace element solution matches：
| Nitrilotriacetic acid | MgSO4 | MnSO4·H2O | NaCl | CuSO4·5H2O | KAl(SO4)2 |
| 1.7g/L | 1.6g/L | 0.37g/L | 1.5g/L | 0.01g/L | 0.02g/L |
| H3BO3 | FeSO4·7H2O | CaCl2·2H2O | CoCl2·6H2O | ZnSO4·7H2O | Na2MoO4 |
| 0.01g/L | 0.1g/L | 0.1g/L | 0.1g/L | 0.1g/L | 0.01g/L |
4th, carry out the recovery of plating industrial district heavy metal in waste water and handle garden mud and sewage simultaneously：
First, sludge is placed in the first biological 1 and second biological anode chamber 5 of anode chamber, the first biological anode chamber 1 of closing
The stomata 5-1 of the one biological anode chambers 5 of Room stomata 1-1 and second；Negative electrode culture medium is added in biological-cathode room 2, will changed
The aeration head learned in cathode chamber 4 is taken out, and the graphite brush electrode in chemical cathode room 4 was replaced with the step of no bacterium adheres to one
The black lead brush managed, by Cr6+Concentration is that 100mg/L electroplating wastewater is added in chemical cathode room 4, is added clearly to settling zone 3
Water；
2nd, the first biological anode chamber 1, biological-cathode room 2, the temperature of 4 and second biological anode chamber 5 of chemical cathode room are kept
For 30 DEG C, the aerator 2-4 in biological-cathode room 2 is opened, is handled, changes within every 2 days half negative electrode culture medium, changed within every 5 days
Primary sludge, an electroplating wastewater is changed within every 2 days, complete the processing of plating industrial district sludge and electroplating wastewater.
Result of implementation shows：
In Cr6+In terms of recovering effect, this experiment degraded contains Cr6+100mg/L electroplating wastewater water distribution degraded peak velocity reaches
To 27.2mg/Lh, Cr will be contained in 48h6+100mg/L electroplating wastewater is degraded to containing Cr6+16.24mg/L degradation rate
83.76%.Cr (OH) is collected into settling zone simultaneously3Flocculent deposit, total chromium concn value is determined without outer adding medicine by ICP
In the case of, Cr6+Precipitate recovery rate be 71%；NaOH regulations pH, Cr are added in settling zone 36+The rate of recovery reaches 82%.More
After changing the electroplating wastewater in chemical cathode room 4, settling zone precipitation capacity increase, the metal target of recovery realizes enrichment.Course of reaction
In, system battery potential is stable in more than 0.80V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 2 day time, anode slime TCOD degrades by 16799mgO2/ L is changed into 15620mgO2/ L, sludge degradation rate 7%.Say
Bright this method has the function that certain sludge stabilizing.Test data proves that the present apparatus can be with continuous service, from electroplating industry
Heavy metal is reclaimed in the waste water of garden to handle garden mud and sewage simultaneously and produce electricity.
Experiment 2：This experiment is from testing a Room graphite brush electrode 1-2 and five Room stones in the device of step 2 unlike 1
Black brush electrode 5-2 is in parallel, two Room graphite brush electrode 2-2 and four Room graphite brush electrode 4-2 are in parallel, and cathode anode is passed through with wire again
Outside storage electrical equipment or electrical appliance 6 connect into closed-loop path.It is other identical with experiment 1.
This experiment is in Cr6+In terms of recovering effect, this experiment degraded contains Cr6+100mg/L electroplating wastewater water distribution degraded peak value
Speed reaches 35.2mg/Lh, will contain Cr in 48h6+100mg/L electroplating wastewater is degraded to containing Cr6+0.36mg/L, degradation rate
99.64%.Cr (OH) is collected into settling zone simultaneously3Flocculent deposit, total chromium concn value is determined in the case of without outer adding medicine,
Cr6+Precipitate recovery rate be 78%；NaOH regulations pH, Cr are added in settling zone 36+The rate of recovery reaches 97%.It is cloudy to change chemistry
After electroplating wastewater in pole room 4, settling zone precipitation capacity increase, the metal target of recovery realizes enrichment.In course of reaction, system electricity
Pond potential is stable in more than 0.83V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 2 day time, anode slime TCOD degrades by 15833mgO2/ L is changed into 14240mgO2/ L, sludge degradation rate 10%.
Such stability being provided with beneficial to intensifier electricity production, improve the reduction efficiency of device heavy metal ion.Because in weight
When metal concentration reduces, the indoor electronic proton of second plate room 5 accumulation, electricity production bacterium activity reduces, but this connected mode makes electronics
Biological-cathode room 2 is delivered to, the inhibitory action of excess electrons accumulation can be alleviated to a certain extent, maintains to produce in second plate room 5
The activity of electric bacterium, the heavy metal rate of reduction of chemical cathode 4 is kept to a certain extent.
Experiment 3：Electroplating wastewater in step 4 is containing Cu unlike experiment 1 by this experiment2+Concentration is 100mg/L's
Waste water.It is other identical with experiment 1.
This experiment is in Cu2+In terms of recovering effect, Cu will be contained in 24h2+100mg/L electroplating wastewater is degraded to containing Cu2+
0.48mg/L, degradation rate 99.52%.Cu (OH) is collected into settling zone simultaneously2Precipitation, in the case of without outer adding medicine, Cu2+
Precipitate recovery rate be 73%.NaOH regulation pH value, Cu are added in settling zone 32+The rate of recovery reaches 94%.Change chemical cathode
After electroplating wastewater in room 4, settling zone precipitation capacity increase, the metal target of recovery realizes enrichment.In course of reaction, system battery
Potential is stable in more than 0.75V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 1 day time, anode slime TCOD degrades by 14333mgO2/ L is changed into 13610mgO2/ L, sludge degradation rate 5%.
Experiment 4：Electroplating wastewater in step 4 is containing Ni unlike experiment 1 by this experiment2+Concentration is 200mg/L's
Waste water.It is other identical with experiment 1.
This experiment is in Ni2+In terms of recovering effect, Ni will be contained in 48h2+200mg/L electroplating wastewater is degraded to containing Ni2+
45.61mg/L degradation rate 77.20%.Ni (OH) is collected into settling zone simultaneously2Precipitation, in the case of without outer adding medicine, Ni2 +Precipitate recovery rate be 38%；NaOH regulations pH, Ni are added in settling zone 32+The rate of recovery reaches 91%.Change chemical cathode
After electroplating wastewater in room 4, settling zone precipitation capacity increase, the metal target of recovery realizes enrichment.In course of reaction, system battery
Potential is stable in more than 0.70V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 2 day time, anode slime TCOD degrades by 15618mgO2/ L is changed into 14063mgO2/ L, sludge degradation rate 10%.
Experiment 5：Electroplating wastewater in step 4 is containing Zn unlike experiment 1 by this experiment2+Concentration is 1000mg/L
Waste water.It is other identical with experiment 1.
This experiment is in Zn2+In terms of recovering effect, Zn will be contained in 48h2+1000mg/L electroplating wastewater is degraded to containing Zn2+
690.5mg/L degradation rate 30.95%.Microprecipitation, in the case of without outer adding medicine, Zn are found in settling zone2+Precipitation return
Yield is 6%；NaOH regulations pH to 10, Zn is added in settling zone 32+The rate of recovery reaches 93%.Change in chemical cathode room 4
After electroplating wastewater, settling zone precipitation capacity increase, the metal target of recovery realizes enrichment.In course of reaction, system battery potential is steady
It is scheduled on more than 0.70V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 2 day time, anode slime TCOD degrades by 14988mgO2/ L is changed into 12902mgO2/ L, sludge degradation rate 14%.
Experiment 6：Electroplating wastewater in step 4 is containing Cd unlike experiment 1 by this experiment2+Concentration is 100mg/L's
Waste water.It is other identical with experiment 1.
This experiment is in Cd2+In terms of recovering effect, Cd will be contained in 48h2+100mg/L electroplating wastewater is degraded to containing Cd2+
40.36mg/L degradation rate 59.64%.Microprecipitation, in the case of without outer adding medicine, Cd are found in settling zone2+Precipitation return
Yield is 8%；NaOH regulations pH, Cd are added in settling zone 32+The rate of recovery reaches 96%.Change the plating in chemical cathode room 4
After waste water, settling zone precipitation capacity increase, the metal target of recovery realizes enrichment.In course of reaction, system battery potential stabilization exists
More than 0.70V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 2 day time, anode slime TCOD degrades by 14266mgO2/ L is changed into 13120mgO2/ L, sludge degradation rate 8%.
Experiment 7：Electroplating wastewater in step 4 is containing Cr unlike experiment 1 by this experiment6+And Zn2+Two kinds of metals
The waste water of ion, their concentration are respectively 100mg/L and 200mg/L.It is other identical with experiment 1.
This experiment will contain Cr in terms of metal recovery effect in 48h6+100mg/L electroplating wastewater is degraded to containing Cr6+
14.33mg/L degradation rate 85.67%.Flocculent deposit is collected into settling zone (is identified as Cr (OH) simultaneously3), without additional
In the case of medicament, Cr6+Precipitate recovery rate be 73%；Zn will be contained in 48h2+200mg/L electroplating wastewater is degraded to containing Zn2+
164.74mg/L, degradation rate 17.63%, reclaimed almost without precipitation；NaOH regulations pH to 7, Cr is added in settling zone 36+Recovery
Rate reaches 83%；After filtering out precipitation, continue to adjust pH to 10, Zn in settling zone 32+The rate of recovery reaches 93%.In course of reaction, it is
Cell voltage potential of uniting is stable in more than 0.75V.
The reacted total mud COD of two anode chambers sludge hybrid measurement is taken, the relevant parameter pair of earth of positive pole when starting with reaction
Than analysis, in 2 day time, anode slime TCOD degrades by 16333mgO2/ L is changed into 14533mgO2/ L, sludge degradation rate 11%.
Claims (8)
1. a kind of reclaim the device for handling garden mud and sewage simultaneously for plating industrial district heavy metal in waste water, its feature exists
In the first biological anode chamber (1), biological-cathode room (2), settling zone (3), chemical cathode room (4) that the device includes being arranged in order
With the second biological anode chamber (5)；Also include two outside storage electrical equipment or electrical appliance (6)；First biological anode chamber (1) is cloudy with biology
Pole room is separated between (2) with PEM, is separated between biological-cathode room (2) and settling zone (3) with anion-exchange membrane, is sunk
Separated between shallow lake area (3) and chemical cathode room (4) with cation-exchange membrane, chemical cathode room (4) and the second biological anode chamber (5)
Between separated with PEM；The top of first biological anode chamber (1) is provided with a Room stomata (1-1), is internally provided with one
Room graphite brush electrode (1-2), bottom are provided with a Room apopore 1-3, a Room reference are additionally provided with the first biological anode chamber (1)
Electrode (1-4), has electro-chemical activity bacterium on a Room graphite brush electrode (1-2)；Reference electrode 1-4 is used to reflect and characterize pole room
The activity of interior electro-chemical activity bacterium；The top of biological-cathode room (2) is provided with two Room stomatas (2-1), is internally provided with two Room stones
Black brush electrode (2-2), bottom are provided with two Room apopores (2-3), aerator (2-4) are additionally provided with biological-cathode room (2)
And dose appropriate graphite particle (2-5)；Two Room graphite brush electrodes (2-2) on carbon granules 2-5 with adhering to aerated biological activated bacterium；Precipitation
The top in area (3) is provided with three Room stomatas (3-1), and bottom is provided with three Room apopores (3-2)；The top of chemical cathode room (4)
Four Room stomatas (4-1) are provided with, are internally provided with four Room graphite brush electrodes (4-2), bottom is provided with four Room apopores (4-3)；
The top of second biological anode chamber (5) is provided with five Room stomatas (5-1), is internally provided with five Room graphite brush electrodes (5-2), bottom
It is provided with five Room apopores (5-3)；Five Room reference electrode 5-4, five Room black lead brush electricity are additionally provided with second biological anode chamber (5)
Has electro-chemical activity bacterium on pole (5-2)；Reference electrode (5-4) is used for the work for reflecting and characterizing electro-chemical activity bacterium in pole room
Property；One Room apopore (1-3) uses pipeline connection with five Room apopores (5-3)；One Room graphite brush electrode (1-2) and two Room black lead brush
Electrode (2-2) connects into closed-loop path, four Room graphite brush electrode 4-2 and five Room through outside storage electrical equipment or electrical appliance (6) with wire
Graphite brush electrode (5-2) even forms closed-loop path by outside storage electrical equipment or electrical appliance (6) with wire；Or by a Room black lead brush
Electrode (1-2) is in parallel with five Room graphite brush electrode (5-2), two Room graphite brush electrodes (2-2) and four Room graphite brush electrode 4-2 simultaneously
Connection, cathode anode connect into closed-loop path with wire by outside storage electrical equipment or electrical appliance (6) again.
2. a kind of plating industrial district heavy metal in waste water that is used for according to claim 1 reclaims while handles garden sludge
The device of sewage, it is characterised in that the first biological anode chamber (1) is cuboid or cylinder；Biological-cathode room (2) is cuboid
Or cylinder；Chemical cathode room (4) is cuboid or cylinder；Second biological anode chamber (5) is cuboid or cylinder.
3. a kind of plating industrial district heavy metal in waste water that is used for according to claim 1 or 2 reclaims while handles garden
The device of mud and sewage, it is characterised in that the first biological anode chamber (1), biological-cathode room (2), settling zone (3), chemical cathode room
(4) and/or the bottom of the second biological anode chamber (5) is provided with magnetic stirring apparatus or indoors plus agitator.
4. a kind of plating industrial district heavy metal in waste water that is used for according to claim 1 or 2 reclaims while handles garden
The device of mud and sewage, it is characterised in that in the first biological anode chamber (1), biological-cathode room (2), settling zone (3), chemical cathode
Room (4) and/or the outside of the second biological anode chamber (5) set attemperator, and wherein attemperator is water-bath or heat-preservation cotton.
5. carry out the recovery of plating industrial district heavy metal in waste water using the device described in claim 1 handles garden sludge simultaneously
The method of sewage, it is characterised in that this method is carried out according to the following steps：
First, the sludge of plating industrial district sewage treatment plant is placed on the first biological anode chamber (1) and the second biological anode chamber (5)
It is interior, close a Room stomata (1-1) of the first biological anode chamber (1) and the stomata 5-1 of the second biological anode chamber (5)；Negative electrode is trained
Foster base is added in biological-cathode room (2), and electroplating wastewater is added in chemical cathode room (4), is added to settling zone (3) clear
Water；
2nd, the first biological anode chamber (1), biological-cathode room (2), chemical cathode room (4) and the second biological anode chamber (5) are kept
Temperature is 20~40 DEG C, opens the aerator 2-4 in biological-cathode room (2), is handled, and changes within every 2~5 days the training of half negative electrode
Base is supported, changes within every 5~10 days primary sludge, changes within every 2~5 days an electroplating wastewater, plating industrial district sludge is completed and plating is useless
The processing of water.
6. heavy metal in waste water recovery in plating industrial district according to claim 5 handles the side of garden mud and sewage simultaneously
Method, it is characterised in that the sludge of the plating industrial district sewage treatment plant described in step 1 be domestic sludge, industrial sludge or
Person is domestic sludge and industrial sludge mixture.
7. the plating industrial district heavy metal in waste water recovery according to claim 5 or 6 handles garden mud and sewage simultaneously
Method, it is characterised in that contain Cr in described electroplating wastewater6+、Cu2+、Ni2+、Zn2+And/or Cd2+。
8. the plating industrial district heavy metal in waste water recovery according to claim 5 or 6 handles garden mud and sewage simultaneously
Method, it is characterised in that the concentration of heavy metal out of electroplating wastewater ion is 50~1000mg/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108832162A (en) * | 2018-06-19 | 2018-11-16 | 杭州电子科技大学 | The experimental system of discarded rice husk is handled using MFC |
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| US20120082868A1 (en) * | 2010-10-01 | 2012-04-05 | University Of Southern California | Floating Microbial Fuel Cells |
| CN102324542A (en) * | 2011-07-28 | 2012-01-18 | 西安交通大学 | Device for coprocessing heavy metal waste water and organic waste water and generating electric power |
| WO2015150610A1 (en) * | 2014-03-31 | 2015-10-08 | Abengoa Water, S.L. | Bioelectrochemical system and method for removing organic matter and nitrogen compounds from wastewater |
| CN105060504A (en) * | 2015-08-12 | 2015-11-18 | 北京化工大学 | Method for treating heavy metal wastewater through intermittent non-power-output, parallel connection of two MFCs and voltage increase |
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