CN102887559B - Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater - Google Patents
Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater Download PDFInfo
- Publication number
- CN102887559B CN102887559B CN201110205614.XA CN201110205614A CN102887559B CN 102887559 B CN102887559 B CN 102887559B CN 201110205614 A CN201110205614 A CN 201110205614A CN 102887559 B CN102887559 B CN 102887559B
- Authority
- CN
- China
- Prior art keywords
- water
- hexavalent chromium
- cathode compartment
- biological adsorption
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to an electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater by using the integrated reactor. A proton exchange membrane is used for separating a container as a main body of the integrated reactor into a cathode chamber and an anode chamber, wherein a cathode and a stirring paddle connected with a stirring motor are arranged in the cathode chamber, an anode is arranged in the anode chamber, the cathode and the anode are respectively connected with a DC (direct current) power supply outside the container, and a modified brown seaweed biological adsorbent is loaded in the cathode chamber. The integrated reactor is formed by adopting the technical scheme. The hexavalent chromium-containing wastewater is treated through an electrochemical reduction process and a biosorption process which are simultaneously completed in the same reactor, wherein the cathode and the anode which are used in the electrochemical reduction process are respectively immersed into the cathode chamber and the anode chamber, and the cathode chamber and the anode chamber are separated by adopting the proton exchange membrane. According to the invention, hexavalent chromium and total chromium can be synchronously removed effectively.
Description
Technical field
The invention belongs to the Application Areas of water technology, particularly a kind of based on electrochemical reduction, auxiliary biological adsorption processing contains the integrated reactor of hexavalent chromium wastewater, and utilizes this integrated reactor to contain the treatment process of hexavalent chromium wastewater.
Background technology
Chromic salts is a kind of important inorganic chemicals industry product, is widely used in the aspects such as plating, tanning, printing and dyeing, medicine, alloy manufacture, wood preservation, gasoline purification.In chromium salt production and application process, produce a large amount of chromate waste waters, to environment structure serious threat.Chromium in waste water mainly exists with sexavalence (Cr (VI)) and two kinds of forms of trivalent (Cr (III)), wherein, chromic toxicity is very high, human body and other organism are had to carcinogenic and mutagenic effect, Long Term Contact sexavalent chrome can bring out esophagus cancer and lung cancer, causes stomachache, diarrhoea, dizziness, vomiting and hemorrhage etc.Many countries all classify sexavalent chrome as High risk population, have formulated strict environmental standard.China's sewage drainage standard stipulates that in existing production line, the highest permission emission concentration of sexavalent chrome is 0.5mg/L, and new production line is 0.1mg/L.Exploitation is the focus of environmental area research for effective treatment process of hexavalent chromium wastewater always.
Processing to hexavalent chromium wastewater both at home and abroad, mainly adopts chemical reduction-precipitator method, micro-electrolysis method, ion exchange method, active carbon adsorption, liquid membrane separation method and reverse osmosis method at present.These methods respectively have superiority, but also all exist obvious deficiency.Chemical reduction-precipitator method produce a large amount of chromium residues, easily cause secondary pollution, and are only applicable to high-concentration chromium-containing wastewater; Micro-electrolysis method sediment weight is large, and iron filings easily lump, and affects treatment system operation; Ion exchange method technical requirements is high, and one-time investment is large, and floor space is large, and the problem of resin oxidation need to solve; Regeneration of activated carbon complicated operation in active carbon adsorption, renovation process, technical process etc. need further to improve; Liquid membrane separation method processing cost is higher, and Technology is also immature; Reverse osmosis method investment is large, and working cost is high, and the film life-span is short.Biological adsorption is a kind of heavy metal containing wastewater treatment new technology of rising in recent years, compares with traditional method, has expense cheap, and sorbent material wide material sources, without advantages such as follow-up sludge treatment.Brown alga is a kind of modal biological adsorption agent, and its source is abundant, easily acquisition, and various heavy (as Cu, Cd, Zn, Ni, Pd etc.) is all had to good absorption property.Much research also reports that brown alga can be used as the biological adsorption agent except Cr (VI), but also generally find a problem simultaneously, be that Cr (VI) adsorption rate on brown alga sorbent material is very slow, reach the chronic of adsorption equilibrium, conventionally need 48～72 hours, the even longer time, greatly limited the biological adsorption agent of this high-quality cheapness in the use aspect hexavalent chromium wastewater processing.The present invention is by electrochemical reduction and the effective combination of biological adsorption, built the auxiliary biological adsorption technique of a kind of electrochemical reduction, solved the low problem of adsorption efficiency in independent use brown alga technique, given full play to the advantage of biosorption technology, in efficient removal Cr (VI), also can effectively remove total Cr.
Summary of the invention
One of the object of the invention is to provide a kind ofly processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
Two of object of the present invention is to provide the treatment process of utilizing the integrated reactor of object one to contain hexavalent chromium wastewater.
The present invention adopts appropriate means to carry out modification to brown alga sorbent material, further optimizes its absorption property; Preparation active high, the life-span long, moderate electrode materials; Electrochemical action is incorporated in biological adsorption process, design is processed the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction, optimize operating parameter, utilize electrochemical reduction that sexavalent chrome is converted into trivalent chromium quickly and efficiently, the advantage of the brown alga of simultaneously giving full play to modification to trivalent chromium efficient adsorption, synchronous sexavalent chrome and the trivalent chromium effectively removed, to reach fast, to remove efficiently, easily and safely the object of Cr in waste water (VI) and total Cr.
Method of the present invention is by electrochemical reduction and the effective combination of biological adsorption, utilize electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical that sexavalent chrome is converted into trivalent chromium efficiently, give full play to the brown alga biological adsorption agent of modification to fast, the capacious advantage of trivalent chromium cation-adsorption speed, synchronous sexavalent chrome and the total chromium effectively removed simultaneously.The invention solves independent use brown alga and process the low problem of adsorption efficiency in hexavalent chromium wastewater technique, given full play of the advantage of this emerging technology of biological adsorption.The present invention has designed the auxiliary biological adsorption integrated reactor of electrochemical reduction, and electro-reduction process and biological adsorption process are synchronously completed, and simplifies technique, cost-saving.Technique of the present invention is simple, and facility compact is easy and simple to handle, obvious processing effect.
The integrated reactor of processing containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction of the present invention comprises: brown alga biological adsorption agent, proton exchange membrane, stirring rake, agitator motor and the direct supply of negative electrode, anode, modification;
Proton exchange membrane described in one is divided into cathode compartment and anolyte compartment's two portions using the container of the integrated reactor main body as described, negative electrode described in being wherein provided with in cathode compartment and the described stirring rake that the agitator motor with described is connected are provided with described anode in anolyte compartment; Described negative electrode and described anode are connected with the described direct supply outside described container by electric wire respectively;
On the wall of container of the bottom of described cathode compartment, be provided with water outlet, on the wall of container on this water outlet top, be provided with water-in, on the wall of container of the bottom of described anolyte compartment, be provided with water outlet, on the wall of container on this water outlet top, be provided with water-in;
In described cathode compartment, be mounted with the brown alga biological adsorption agent of described modification.
At described water outlet and described water inlet, valve is installed.
Described negative electrode is on titanium (Ti) board substrate, to deposit a kind of noble metal film negative electrode being selected from palladium, gold, rhodium, ruthenium precious metal.
Described noble metal film negative electrode is to adopt electrochemical deposition method to be prepared, as first, to after 200 orders, 400 orders, 800 object sand paper are polished respectively for surface of titanium (Ti) board substrate, titanium (Ti) plate is immersed in the NaOH aqueous solution that concentration is 10mol/L in 90 ℃ of heating oil removing in 2 hours; Then water is immersed in the H that concentration is 2mol/L after rinsing
2sO
4in the aqueous solution, in 60 ℃ of heating 2 hours, taking-up was immersed in the HCl aqueous solution (V (HCl): V (H after cleaning
2o)=1: 3), boil 1 hour; Take out and after water is rinsed well, to put into precious metal (being selected from a kind of of palladium, gold, rhodium, ruthenium precious metal) plating solution and carry out electrodeposit reaction.The preparation of described precious metal plating solution is that the solubility lead compound of the precious metal of metering is dissolved in hydrochloric acid soln, and compound concentration is 0.5～2mmol/L (in precious metal).Described electrodeposit reaction is that continuous current is controlled, and current density is-0.5～-4mA/cm
2, depositing time is 10～40 minutes.
Described anode is selected from a kind of in the inactive, conductive material such as platinum, ruthenium oxide, iridium oxide, plumbous oxide.
The material of described proton exchange membrane can be the polymkeric substance of fluorine alkene sulfonic acid.In the present invention proton exchange membrane be used for (1) separate negative and positive two Room, the oxidizing atmosphere of Bu Rang anolyte compartment affects the reduction reaction of cathode compartment; (2) H
+can freely pass through from proton exchange membrane, between two Room, exchange, play electric action; (3) sexavalent chrome negatively charged ion can not enter anolyte compartment by proton exchange membrane.
The treatment process of utilizing above-mentioned integrated reactor to contain hexavalent chromium wastewater of the present invention, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, and negative and positive the two poles of the earth separate with proton exchange membrane between chamber; Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.01～0.1mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The brown alga of modification is put in cathode compartment by the top (top of cathode compartment is uncovered) of cathode compartment according to certain solid-to-liquid ratio (preferably dosage is 1～5g/L), stirred, make the brown alga of described modification keep suspended state; Sexavalent chrome (Cr (VI)) reduces by electrochemistry direct-reduction and atomic hydrogen indirect electrochemical at cathode compartment, changes into quickly and efficiently trivalent chromium (Cr (III)); Cr (III) heavy metal ion generating fully contacts in solution with the brown alga of described modification, and Cr (III) is removed by efficient adsorption; Under effective combination of cathodic reduction and biological adsorption, under both actings in conjunction, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 0.5～2V, and the handled Initial pH containing hexavalent chromium wastewater is 2～3.
Although the brown alga biological adsorption agent of the modification described in the present invention is slow to the removal speed of Cr (VI) negatively charged ion, very rapid to the cationic absorption of Cr (III), just can reach adsorption equilibrium in 2～4 hours.The present invention's design is incorporated into electrochemical action in biological adsorption process, utilize electrochemical reduction that Cr (VI) is converted into Cr (III) quickly and efficiently, the advantage of the brown alga of the modification described in simultaneously giving full play to Cr (III) efficient adsorption, synchronous Cr (VI) and the Cr (III) of effectively removing.The present invention compares with other method of reducing, and electrochemical reducing has without adding medicament, environmental friendliness, and selectivity is high, simple to operate, is easy to the multiple advantages such as automatization, and the method is combined with the biosorption technology of Cheap highly effective, with the obvious advantage.
The brown alga of described modification is that brown alga is dried, grinding is sieved, then the algae grain obtaining after sieving (preferable particle size is 200～1000 μ m) is impregnated into (time of general dipping is 10～40 hours) in the formalin that mass concentration is 1～5g/L, solid-to-liquid ratio is 5～20g algae grain/1L water.
Described brown alga (brown algae) is nonactive organism, be the abundant typical algae kinds of reserves, as be selected from one or more in sargassun (Sargassum), entoilage algae (Dictyotales), black top algae (Sphacelariales), sea-tangle (Laminariales), black wrack (Fucales), bladder wrack (Ascophyllum), kelp (Ecklonia hornem), wakame (Undaria pinnatifida) etc.
Feature of the present invention:
1. the brown alga sorbent material source adopting is abundant, cheap.
2. adopt electrochemical reduction mode, reductive agent is electronics and atomic hydrogen, clean harmless, environmental friendliness; Reductive agent produces online, uses online, without adding a large amount of reduction medicaments, has avoided going out water generates secondary pollution.
3. prepared titanium-based noble metal membrane electrode reduction of hexavalent chromium activity is high, and speed of response is fast, and the life-span is long, moderate cost.
4. the present invention effectively combines electrochemical reduction and biological adsorption, electro-reduction process and biological adsorption process synchronously complete in same reactor, be built into electrochemical reduction auxiliary biological adsorption integrated reactor and processing method, utilize electrochemical reduction to realize Cr (VI) to the Efficient Conversion of Cr (III), thereby give full play of the advantage of brown alga absorption Cr (III), synchronous Cr (VI) and the Cr (III) of effectively removing.
5. method of the present invention is simple, and equipment volume is little, easy to install, easily is automated.
Accompanying drawing explanation
Fig. 1. the schematic diagram of integrated reactor of the present invention.
Reference numeral:
1. integrated reactor main body 2. negative electrode 3. anodes
4. brown alga biological adsorption agent 5. proton exchange membrane 6. stirring rakes of modification
7. agitator motor 8. direct supply 9,11. water-in 10,12. water outlets
Embodiment
Refer to Fig. 1, the integrated reactor of processing containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction comprises: the brown alga biological adsorption agent 4 of negative electrode 2, anode 3, modification, proton exchange membrane 5, stirring rake 6, agitator motor 7 and direct supply 8.
Proton exchange membrane 5 described in one is divided into cathode compartment and anolyte compartment's two portions using the container of the integrated reactor main body 1 as described, negative electrode 2 described in being wherein provided with in cathode compartment and the described stirring rake 6 that the agitator motor 7 with described is connected are provided with described anode 3 in anolyte compartment; Described negative electrode 2 and described anode 3 are connected with the described direct supply 8 outside described container by electric wire respectively.
On the wall of container of the bottom of described cathode compartment, be provided with valvular water outlet 10 is installed, on the wall of container on this water outlet top, be provided with valvular water-in 9 is installed, on the wall of container of the bottom of described anolyte compartment, be provided with valvular water outlet 12 is installed, on the wall of container on this water outlet top, be provided with valvular water-in 11 is installed.
In described cathode compartment, be mounted with the brown alga biological adsorption agent 4 of described modification.
Described noble metal film negative electrode is to adopt electrochemical deposition method to be prepared, first to after 200 orders, 400 orders, 800 object sand paper are polished respectively for surface of titanium (Ti) board substrate, titanium (Ti) plate is immersed in the NaOH aqueous solution that concentration is 10mol/L in 90 ℃ of heating oil removing in 2 hours; Then water is immersed in the H that concentration is 2mol/L after rinsing
2sO
4in the aqueous solution, in 60 ℃ of heating 2 hours, taking-up was immersed in the HCl aqueous solution (V (HCl): V (H after cleaning
2o)=1: 3), boil 1 hour; Taking-up water is put into metallic palladium plating solution after rinsing well and is carried out electrodeposit reaction.The preparation of described metallic palladium plating solution is that the solubility lead compound of the metallic palladium of metering is dissolved in hydrochloric acid soln, and compound concentration is 1.0mmol/L (in metallic palladium).Described electrodeposit reaction is that continuous current is controlled, and current density is-2mA/cm
2, depositing time is 35 minutes.Make titanium base palladium metal foil membrane electrode as negative electrode, anode is selected ruthenium-oxide electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.01mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 3g/L according to solid-to-liquid ratio by the sargassun of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the sargassun of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the sargassun of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 1.5V, the handled initial pH containing hexavalent chromium wastewater is 2.0, sexavalent chrome starting point concentration is 50mg/L, after wastewater treatment 3 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 85.5%.
The sargassun (Sargassum) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: sargassun is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 200～500 μ m is impregnated in the formalin that mass concentration is 2g/L, dipping time is 24 hours, and solid-to-liquid ratio is 10g sargassun grain/1L water.
Employing embodiment 1 processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
The sargassun (Sargassum) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: sargassun is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 500～800 μ m is impregnated in the formalin that mass concentration is 5g/L, dipping time is 10 hours, and solid-to-liquid ratio is 15g sargassun grain/1L water.
The process for surface preparation of titanium (Ti) board substrate is with embodiment 1, and the titanium that pre-treatment is good (Ti) board substrate is immersed in the plating solution of metallic gold and carries out electrodeposit reaction.The preparation of the plating solution of described metallic gold is that the golden solubility lead compound of metering is dissolved in hydrochloric acid soln, and compound concentration is 0.5mmol/L (in gold).Described electrodeposit reaction is that continuous current is controlled, and current density is-2mA/cm
2, depositing time is 20 minutes.Make titanium fund membrane electrode as negative electrode, anode is selected iridium oxide electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.05mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 5g/L according to solid-to-liquid ratio by the sargassun of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the sargassun of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the sargassun of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 2.0V, the handled initial pH containing hexavalent chromium wastewater is 2.0, sexavalent chrome starting point concentration is 50mg/L, after wastewater treatment 3 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 93.7%.
Embodiment 3.
Employing embodiment 1 processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
The black wrack (Fucales) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: black wrack is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 500～800 μ m is impregnated in the formalin that mass concentration is 1g/L, dipping time is 40 hours, and solid-to-liquid ratio is 5g black wrack grain/1L water.
The process for surface preparation of titanium (Ti) board substrate, with embodiment 1, is carried out electrodeposit reaction in the plating solution of the titanium that pre-treatment is good (Ti) board substrate immersion ruthenium metal.The preparation of the plating solution of described ruthenium metal is that the solubility lead compound of the ruthenium metal of metering is dissolved in hydrochloric acid soln, and compound concentration is 1.0mmol/L (in ruthenium metal).Described electrodeposit reaction is that continuous current is controlled, and current density is-2mA/cm
2, depositing time is 30 minutes.Make titanium base metal ruthenium film electrode as negative electrode, anode is selected lead dioxide electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.05mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 4g/L according to solid-to-liquid ratio by the black wrack of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the black wrack of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the black wrack of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 1.2V, the handled initial pH containing hexavalent chromium wastewater is 2.2, sexavalent chrome starting point concentration is 20mg/L, after wastewater treatment 2 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 95.2%.
Employing embodiment 1 processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
The black wrack (Fucales) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: black wrack is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 800～1000 μ m is impregnated in the formalin that mass concentration is 5g/L, dipping time is 24 hours, and solid-to-liquid ratio is 20g black wrack grain/1L water.
The process for surface preparation of titanium (Ti) board substrate, with embodiment 1, is carried out electrodeposit reaction in the plating solution of the titanium that pre-treatment is good (Ti) board substrate immersion rhodium metal.The preparation of the plating solution of described rhodium metal is that the solubility lead compound of the rhodium metal of metering is dissolved in hydrochloric acid soln, and compound concentration is 1.0mmol/L (in rhodium metal).Described electrodeposit reaction is that continuous current is controlled, and current density is-0.5mA/cm
2, depositing time is 40 minutes.Make titanium base rhodium metal membrane electrode as negative electrode, anode is selected platinum electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.05mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 5g/L according to solid-to-liquid ratio by the black wrack of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the black wrack of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the black wrack of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 1.5V, the handled initial pH containing hexavalent chromium wastewater is 2.0, sexavalent chrome starting point concentration is 100mg/L, after wastewater treatment 4.5 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 86.3%.
Embodiment 5.
Employing embodiment 1 processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
The black wrack (Fucales) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: black wrack is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 500～800 μ m is impregnated in the formalin that mass concentration is 2g/L, dipping time is 24 hours, and solid-to-liquid ratio is 10g black wrack grain/1L water.
The process for surface preparation of titanium (Ti) board substrate, with embodiment 1, is carried out electrodeposit reaction in the plating solution of the titanium that pre-treatment is good (Ti) board substrate immersion metallic palladium.The preparation of the plating solution of described metallic palladium is that the solubility lead compound of the metallic palladium of metering is dissolved in hydrochloric acid soln, and compound concentration is 1.0mmol/L (in metallic palladium).Described electrodeposit reaction is that continuous current is controlled, and current density is-4mA/cm
2, depositing time is 10 minutes.Make titanium base palladium metal foil membrane electrode as negative electrode, anode is selected ruthenium-oxide electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.05mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 5g/L according to solid-to-liquid ratio by the black wrack of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the black wrack of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the black wrack of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 1.5V, the handled initial pH containing hexavalent chromium wastewater is 2.0, sexavalent chrome starting point concentration is 35mg/L, trivalent chromium concentration is 15mg/L, after wastewater treatment 3 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 97.8%.
Employing embodiment 1 processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
The sargassun (Sargassum) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: sargassun is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 500～800 μ m is impregnated in the formalin that mass concentration is 2g/L, dipping time is 24 hours, and solid-to-liquid ratio is 10g sargassun grain/1L water.
The process for surface preparation of titanium (Ti) board substrate, with embodiment 1, is carried out electrodeposit reaction in the plating solution of the titanium that pre-treatment is good (Ti) board substrate immersion metallic palladium.The preparation of the plating solution of described metallic palladium is that the solubility lead compound of the metallic palladium of metering is dissolved in hydrochloric acid soln, and compound concentration is 1.0mmol/L (in metallic palladium).Described electrodeposit reaction is that continuous current is controlled, and current density is-2mA/cm
2, depositing time is 35 minutes.Make titanium base palladium metal foil membrane electrode as negative electrode, anode is selected ruthenium-oxide electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.05mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 1g/L according to solid-to-liquid ratio by the sargassun of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the sargassun of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the sargassun of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 0.5V, the handled initial pH containing hexavalent chromium wastewater is 2.0, sexavalent chrome starting point concentration is 10mg/L, after wastewater treatment 5 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 81.6%.
Employing embodiment 1 processes the integrated reactor containing hexavalent chromium wastewater based on the auxiliary biological adsorption of electrochemical reduction.
The sargassun (Sargassum) that the brown alga biological adsorption agent of described modification is modification, method of modifying is: sargassun is dried, grinding is sieved, then the algae grain that by the particle diameter obtaining after sieving is 200～500 μ m is impregnated in the formalin that mass concentration is 3g/L, dipping time is 30 hours, and solid-to-liquid ratio is 15g sargassun grain/1L water.
The process for surface preparation of titanium (Ti) board substrate, with embodiment 1, is carried out electrodeposit reaction in the plating solution of the titanium that pre-treatment is good (Ti) board substrate immersion metallic palladium.The preparation of the plating solution of described metallic palladium is that the solubility lead compound of the metallic palladium of metering is dissolved in hydrochloric acid soln, and compound concentration is 1.0mmol/L (in metallic palladium).Described electrodeposit reaction is that continuous current is controlled, and current density is-2mA/cm
2, depositing time is 35 minutes.Make titanium base palladium metal foil membrane electrode as negative electrode, anode is selected ruthenium-oxide electrode.
Utilize above-mentioned integrated reactor to contain the treatment process of hexavalent chromium wastewater, that electro-reduction process and biological adsorption process synchronously complete in same reactor, the negative electrode that electrochemical process is used and anode are immersed in respectively in cathode compartment and anolyte compartment, between chamber, negative and positive the two poles of the earth with proton exchange membrane separate (adopt du pont company (Nafion 117, Dupont); Adopt intermittent type wastewater treatment mode, chromyl waste water is pumped in above-mentioned cathode compartment by the water-in of cathode compartment, containing 0.05mol/L sodium sulfate (Na
2sO
4) water-in of electrolytical Shui You anolyte compartment is pumped in above-mentioned anolyte compartment; The dosage that is 3g/L according to solid-to-liquid ratio by the sargassun of modification is put in cathode compartment by the top of cathode compartment, stirs, and makes the sargassun of described modification keep suspended state; Sexavalent chrome (Cr (VI)) changes into trivalent chromium (Cr (III)) at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; Cr (III) heavy metal ion generating fully contacts in solution with the sargassun of described modification, and Cr (III) is removed by efficient adsorption; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water (Cr (VI)) and total chromium (Cr) obtain synchronous effectively removal; After reaction finishes, the chromate waste water after processing is flowed out by the water outlet of cathode compartment, contains sodium sulfate (Na
2sO
4) electrolytical water can continue to use, and reuses the water outlet of 5～10 Ci Houzaiyou anolyte compartments and emits, and pumped into the contains sodium sulfate (Na of new preparation by the water-in of anolyte compartment
2sO
4) electrolytical water.
When the processing that contains hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 1.5V, the handled initial pH containing hexavalent chromium wastewater is 3.0, sexavalent chrome starting point concentration is 10mg/L, after wastewater treatment 6 hours, hexavalent chromium concentration is down to below 0.1mg/L, and total Cr clearance can reach 98.8%.
Claims (7)
1. based on the auxiliary biological adsorption of electrochemical reduction, process the integrated reactor containing hexavalent chromium wastewater, comprising: brown alga biological adsorption agent, proton exchange membrane, stirring rake, agitator motor and the direct supply of negative electrode, anode, modification; It is characterized in that:
Proton exchange membrane described in one is divided into cathode compartment and anolyte compartment's two portions using the container of the integrated reactor main body as described, negative electrode described in being wherein provided with in cathode compartment and the described stirring rake that the agitator motor with described is connected are provided with described anode in anolyte compartment; Described negative electrode and described anode are connected with the described direct supply outside described container by electric wire respectively;
On the wall of container of the bottom of described cathode compartment, be provided with water outlet, on the wall of container on this water outlet top, be provided with water-in, on the wall of container of the bottom of described anolyte compartment, be provided with water outlet, on the wall of container on this water outlet top, be provided with water-in;
In described cathode compartment, be mounted with the brown alga biological adsorption agent of described modification;
Described negative electrode is on titanium board substrate, to deposit a kind of noble metal film negative electrode being selected from palladium, gold, rhodium, ruthenium precious metal;
The brown alga of described modification is that brown alga is dried, and grinding is sieved, and then the algae grain obtaining after sieving is impregnated in the formalin that mass concentration is 1～5g/L, and solid-to-liquid ratio is 5～20g algae grain/1L water.
2. according to claim 1ly based on the auxiliary biological adsorption of electrochemical reduction, process the integrated reactor containing hexavalent chromium wastewater, it is characterized in that: described water outlet and described water inlet are provided with valve.
3. according to claim 1ly based on the auxiliary biological adsorption of electrochemical reduction, process the integrated reactor containing hexavalent chromium wastewater, it is characterized in that: described anode is selected from a kind of in platinum, ruthenium oxide, iridium oxide, plumbous oxide inactive, conductive material.
4. utilize and based on the auxiliary biological adsorption of electrochemical reduction, process a treatment process that contains hexavalent chromium wastewater containing the integrated reactor of hexavalent chromium wastewater described in claim 1～3 any one, the method is that electro-reduction process and biological adsorption process synchronously complete in same reactor; It is characterized in that: the water-in by chromyl waste water by cathode compartment is pumped in cathode compartment, the water-in that contains the Shui You anolyte compartment of 0.01～0.1mol/L sodium sulfate is pumped in anolyte compartment; The brown alga of modification is put in cathode compartment by the top of cathode compartment, stirred; Sexavalent chrome changes into trivalent chromium at cathode compartment by electrochemistry direct-reduction and the reduction of atomic hydrogen indirect electrochemical; The trivalent chromium heavy metal ion generating fully contacts in waste water with the brown alga of described modification, and trivalent chromium is adsorbed removal; Under the acting in conjunction of cathodic reduction and biological adsorption, the sexavalent chrome in waste water and total chromium are synchronously removed;
When carrying out the described processing containing hexavalent chromium wastewater, the voltage applying between negative electrode and positive electrode is 0.5～2V, and the Initial pH of handled chromyl waste water is 2～3.
5. method according to claim 4, is characterized in that: the brown alga of described modification and the solid-to-liquid ratio of waste water are 1～5g/L.
6. according to the method described in claim 4 or 5, it is characterized in that: the particle diameter of described algae grain is 200～1000 μ m.
7. method according to claim 6, is characterized in that: described brown alga is nonactive organism, is selected from one or more in sargassun, entoilage algae, black top algae, sea-tangle, black wrack, bladder wrack, kelp, wakame.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110205614.XA CN102887559B (en) | 2011-07-21 | 2011-07-21 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110205614.XA CN102887559B (en) | 2011-07-21 | 2011-07-21 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102887559A CN102887559A (en) | 2013-01-23 |
| CN102887559B true CN102887559B (en) | 2014-03-19 |
Family
ID=47531266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110205614.XA Active CN102887559B (en) | 2011-07-21 | 2011-07-21 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102887559B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150651B (en) * | 2014-08-15 | 2016-08-24 | 中国科学院生态环境研究中心 | A kind of electronation assisted electrochemical method removes chromic method in water |
| CN104710014B (en) * | 2015-03-23 | 2017-03-15 | 泰山医学院 | A kind of method using hexavalent chromium in modified yellow tang absorption water |
| CN104787860B (en) * | 2015-04-14 | 2016-09-14 | 哈尔滨工程大学 | One utilizes Metal semi-fuel cells to process chromic method in waste water |
| CN105692800B (en) * | 2016-03-22 | 2018-11-06 | 浙江清华长三角研究院 | A kind of wastewater treatment equipment and method |
| CN107188278A (en) * | 2017-07-18 | 2017-09-22 | 集美大学 | A kind of method of the nano-catalytic electrolytic experiment room containing hexavalent chromium wastewater |
| CN110563094B (en) * | 2019-09-17 | 2021-08-24 | 南昌航空大学 | Application of sulfonated carbon cloth electrode |
| CN112607969B (en) * | 2020-12-18 | 2023-10-31 | 湖北紫诺新材料科技股份有限公司 | Dye wastewater treatment process |
| CN112678922B (en) * | 2020-12-18 | 2023-07-18 | 宁夏新力新能源科技有限公司 | Electrochemical water treatment device and system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1212963A1 (en) * | 1983-04-06 | 1986-02-23 | Приборомеханическое Объединение "Курганприбор" | Method of removing trivalent chromium hydroxide from waste water |
| CN1556045A (en) * | 2004-01-02 | 2004-12-22 | 郑州大学 | Hexa valence chromium in industriel waste water electrolysis treatment method |
| MX2007013111A (en) * | 2007-10-19 | 2009-04-20 | Univ Guanajuato | Solar energy-assisted process for treating effluents polluted with hexavalent chromium. |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101059772B1 (en) * | 2009-03-31 | 2011-08-26 | 부산대학교 산학협력단 | Dechlorination Method Using Bioelectrochemical System |
-
2011
- 2011-07-21 CN CN201110205614.XA patent/CN102887559B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1212963A1 (en) * | 1983-04-06 | 1986-02-23 | Приборомеханическое Объединение "Курганприбор" | Method of removing trivalent chromium hydroxide from waste water |
| CN1556045A (en) * | 2004-01-02 | 2004-12-22 | 郑州大学 | Hexa valence chromium in industriel waste water electrolysis treatment method |
| MX2007013111A (en) * | 2007-10-19 | 2009-04-20 | Univ Guanajuato | Solar energy-assisted process for treating effluents polluted with hexavalent chromium. |
Non-Patent Citations (3)
| Title |
|---|
| 司靖 等.铁铜内电解－膨润土组合工艺处理含铬废水.《环境科学与管理》.2011,第36卷(第5期),第71-74页第2.1节-第2.4节及表1. * |
| 张海丽 等.电化学处理含铬废水及铬的回收研究.《功能材料》.2009,第增刊(40)卷第769-772页摘要、第2.2节-第4节及图1. |
| 电化学处理含铬废水及铬的回收研究;张海丽 等;《功能材料》;20091231;第增刊(40)卷;第769-772页摘要、第2.2节-第4节及图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102887559A (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102887559B (en) | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater | |
| Li et al. | Self-enhanced decomplexation of Cu-organic complexes and Cu recovery from wastewaters using an electrochemical membrane filtration system | |
| Zhang et al. | Exhaustive conversion of inorganic nitrogen to nitrogen gas based on a photoelectro-chlorine cycle reaction and a highly selective nitrogen gas generation cathode | |
| Wu et al. | Carbon-nanotube-doped Pd-Ni bimetallic three-dimensional electrode for electrocatalytic hydrodechlorination of 4-chlorophenol: Enhanced activity and stability | |
| Sirés et al. | Electrochemical advanced oxidation processes: today and tomorrow. A review | |
| CN103342405B (en) | Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate | |
| Chen et al. | Photoelectrocatalytic oxidation of metal-EDTA and recovery of metals by electrodeposition with a rotating cathode | |
| Rajoria et al. | Review on the treatment of electroplating industry wastewater by electrochemical methods | |
| Kim et al. | High-efficiency solar desalination accompanying electrocatalytic conversions of desalted chloride and captured carbon dioxide | |
| CN101538078A (en) | Micro-multiphase electro-Fenton oxidation-reduction reactor | |
| CN106673140B (en) | The method that removing chloride is removed in electrochemical reactor and electro-catalysis | |
| CN105601002B (en) | A kind of processing system and method for purification of organic waste water | |
| CN102101733A (en) | Method for treating electroplating comprehensive wastewater by scrap iron electrolysis and electrochemical technology | |
| Lu et al. | Cu, Ni and multi-walled carbon-nanotube-modified graphite felt electrode for nitrate electroreduction in water | |
| Tang et al. | Efficient denitrification and removal of natural organic matter, emerging pollutants simultaneously for RO concentrate based on photoelectrocatalytic radical reaction | |
| Hu et al. | Simultaneous phenol detoxification and dilute metal recovery in cyclone electrochemical reactor | |
| CN103641207B (en) | A kind of Zinc-containing electroplating waste water combined electrolysis groove treatment process | |
| Kuang et al. | A bipolar membrane-integrated electrochlorination process for highly efficient ammonium removal in mature landfill leachate: the importance of ClO• generation | |
| CN103641206B (en) | A kind of method applied the process of combined electrolysis groove and contain cadmium electroplating wastewater | |
| Ji et al. | Heterostructure Cu2O@ TiO2Nanotube Array Coated Titanium Anode for Efficient Photoelectrocatalytic Oxidation of As (III) in Aqueous Solution | |
| Kim et al. | A protocol for electrocatalyst stability evaluation: H2O2 electrosynthesis for industrial wastewater treatment | |
| CN109293100B (en) | Heavy metal sewage treatment method | |
| CN104925914B (en) | Photoelectric combination waste water of the processing containing heavy metal cyanide and the method for reclaiming heavy metal simultaneously | |
| CN106745536A (en) | The method that electrolysis electrocatalytic oxidation binding resin exchanges the dirty Organic substance in water of removing | |
| Kang et al. | Development of a scalable electrochemical filter for removing nitrate from recirculating aquaculture saltwater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |