CN102234145A - Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode - Google Patents
Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode Download PDFInfo
- Publication number
- CN102234145A CN102234145A CN 201010155321 CN201010155321A CN102234145A CN 102234145 A CN102234145 A CN 102234145A CN 201010155321 CN201010155321 CN 201010155321 CN 201010155321 A CN201010155321 A CN 201010155321A CN 102234145 A CN102234145 A CN 102234145A
- Authority
- CN
- China
- Prior art keywords
- electro
- adsorption
- defluorination
- mixture
- preparation
- 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.)
- Pending
Links
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a preparation method of a fluoride removal electro adsorption electrode for drinking water and a fluoride removal electro adsorption electrode. The method comprises the following steps: (1) mixing a conductive material and an adsorbent to obtain a conductive mixture, wherein a weight ratio of the conductive material and the adsorbent is 3-55: 45-97; (2) adding hot melt adhesive into the mixture obtained in the above step to stir uniformly and obtaining an electro adsorption mixture, wherein a weight ratio of the hot melt adhesive and the conductive mixture is 5-50: 50-95; (3) adding the electro adsorption mixture into a mould, and followed by hot pressing moulding to obtain the fluoride removal electro adsorption electrode. Combined electrode prepared with the method in the invention has the advantages of strong fluoride removal and adsorption capability, high strength, no fragmentation in long-term use, small mass loss, no digestion, free of secondary pollution, safety and reliability, and is suitable for long-term usage under a condition of big change of water flow pressure.
Description
Technical field
The invention belongs to the sorbing material technical field, particularly a kind of drinking water defluorination absorbent powder forming method that is used for.
Background technology
Fluorine is that human body not only can not lack but also can not absorb too much critical element, the soundness of an amount of fluorine (0.5-1.0mg/L) energy enhances skeletal, certain carious tooth effect of preventing and treating is arranged, but the content of fluorion can cause damage to HUMAN HEALTH above finite concentration in the tap water, cause fluorosis, show as dentine crisp, damaged or come off, lumbago and skelalgia, osteoarthrosis are fixed, deformity etc., also can cause thyroid function imbalance, renal tubal dysfunction etc.
Water of high fluorine content worldwide distributes very extensive, drinks the health problem that water of high fluorine content causes and has caused the national governments and the common people's concern.The World Health Organization (WHO) is defined as 0.6-1.5mg/L with the limit value of tap water fluorine, and China is in the formal sanitary standard for drinking water of implementing (GB5479-2006) on July 1st, 2007, and the limit value of regulation Drinking Water fluorine is 1.0mg/L.The enforcement of strict standard is had higher requirement to the water of high fluorine content treatment technology.At present, drinking water defluorination method mainly contains chemical precipitation method, adsorption filtration method, also have ion exchange method, electroosmose process, reverse osmosis method, electrocoagulation, electro-adsorption method etc. in addition, wherein the electro-adsorption method is little because of its energy consumption, running cost is low, non-secondary pollution, the easy concentrated water treatment that is particularly suited for small community of regeneration.
The key of electro-adsorption is the performance of the especially electric short absorption of performance of combined electrode, and still, there are the following problems in the research and development of drinking water defluorination electro-adsorption electrode and practical application at present:
(1) electrode materials lacks novelty, and causing the short absorption of most of electricity to rest on simple is the stage of adsorption electrode with the graphite cake.
(2) lack suitable forming method and technology, cause most of R﹠D processes to rest on the laboratory, rest on the two-dimensional flat plate electrode stage.
(3) some formed absorbent intensity differences, easily broken; Generally can be seated in after the sorbing material moulding of absorption method drinking water defluorination in adsorption tower/jar/post and use.But because adsorption bed is conducted oneself with dignity, hydrostaticpressure, treating processes water flow dynamic energy, the instantaneous high velocity flow function of recoil process all might cause the absorbent particles fragmentation, can cause sorbent material to run off on the one hand, and system can not for a long time effectively move; Delivery turbidity raises in a short time on the other hand, and the chemical element stripping discharges and causes safe drinking water hidden danger.
(4) some moulding processes and formed material contain objectionable impurities, can not ensure safe drinking water.
(5) loss of combined electrode moulding process chemisorption capacity causes the short DeGrain of electricity greatly.
The ratio electric capacity of the drinking water defluorination electro-adsorption electrode that uses is little at present; Loading capacity is low; Loading capacity is lost greatly in the preparation process, and the intensity difference of finished product defluorination adsorption electrode is broken easily, easy swelling, and extract is many, and the water outlet poor stability after the processing is not suitable for long-term continuous operation use.
Carbon nanotube and activated carbon fiber are as nano material, and be not only in light weight, but also have mechanics, electricity and the chemical property of many excellences, is the bigger and high conductive electrode materials of effective surface area.The two special hollow structure, big specific surface area, low resistivity and high stability make it be widely used in fields such as battery material, electrode materials, chemical sensor.Studies show that, in Graphite Powder 99, add the resistivity decreased about 90% that certain quantity of carbon nanometer pipe can make composite powder, have good electrical conductivity.
Hot melt adhesive is to be main component with thermoplastic resin or thermoplastic elastomer, adds compositions such as softening agent, tackifying resin, oxidation inhibitor, fire retardant and filler, the not solvent-laden solid adhesive agent of making through melting mixing.Have that bonding speed is fast, nontoxic, adhesion process is simple, bonding strength and snappiness, anti-solvent, advantage such as wear-resisting are arranged again preferably, can be used for the bonding of various materials, be called as " green sizing agent " thus.Chinese patent CN101070455 (2007-11-14) has announced a kind of reaction type EVA hot-melt adhesive, because the molecular structure of reaction type EVA hot-melt adhesive changes the cross-linking type structure into by line style, thereby improved cohesive strength, bonding strength, thermotolerance and solvent resistance etc. significantly, can replace type hot melt adhesives such as nylon, polyester, urethane in some aspects.
Summary of the invention
The objective of the invention is provides a kind of drinking water defluorination electro-adsorption electrode and preparation method thereof at the problem that above-mentioned prior art exists.The defluorination high adsorption capacity of the combined electrode of the inventive method preparation, intensity height, life-time service are not broken, and mass loss is little, no stripping, the non-secondary pollution problem, safe and reliable, be suitable for long-term and under water flow pressure variation situation greatly, use.
For realizing purpose of the present invention, one aspect of the present invention provides a kind of preparation method who is used for the defluorination electro-adsorption electrode of tap water, comprises following step in sequence:
1) electro-conductive material and sorbent material are mixed, make conductive mixture, wherein, described electro-conductive material is 3-55: 45-97 with the ratio of the weight part of sorbent material;
2) hot melt adhesive is joined in the conductive mixture, mix, make the electro-adsorption mixture, wherein, hot melt adhesive is 5-50: 50-95 with the ratio of the weight part of conductive mixture;
3) the electro-adsorption mixture is put into mould, hot-forming forming.
Wherein, electro-conductive material described in the step 1) is that carbon nanotube or activated carbon fiber and graphite mix.
Particularly, described carbon nanotube is a multi-walled carbon nano-tubes, and specific surface area is greater than 110m
2/ g has excellent conducting performance;
Described activated carbon fiber specific surface area is 800-1600m
2/ g, particle diameter≤150 μ m.
Particularly, the weight part proportioning of described graphite and carbon nanotube is 50-90: 10-50; The weight part proportioning of described graphite and activated carbon fiber is 50-90: 10-50.
Wherein, sorbent material described in the step 1) is selected one or more in hydration hydroxyl oxidize zirconium, aluminum oxide, titanium dioxide, the magnesium oxide.
Particularly, described aluminum oxide is selected activated alumina; Described titanium dioxide is selected active titanic dioxide; Described magnesium oxide is selected activated magnesia.
Wherein, the specific surface area of described activated alumina is 280-360m
2/ g, particle diameter≤150 μ m.
Wherein, described active titanic dioxide is an anatase titanium dioxide.
Particularly, described active titanic dioxide is with anatase titanium dioxide calcination 3h under 450 ℃ high temperature, grinds to particle diameter≤150 μ m.
Wherein, the median size of described activated magnesia is less than 2000nm, and specific surface area is 5-20m
2/ g.
Wherein, the hot melt adhesive step 2) is selected ethylene-vinyl alcohol copolymer, tetrafluoroethylene, Polyurethane thermoplastic elastomer, one or more in the urethane; Hot-forming pressure is 5-30MPa described in the step 3), and temperature is 180-330 ℃, and hot pressing time is 10-60min.
Wherein, electro-conductive material described in the step 1) is preferably 5-45: 55-95 with the ratio of the weight part of de-fluoridation adsorbent; Step 2) hot melt adhesive described in is preferably 5-30: 70-95 with the ratio of the weight part of conductive mixture.
Wherein, the mould described in the step 3) is a sheet or cylindric.
Particularly, comprise that also hot-forming defluorination electro-adsorption electrode is carried out high-temperature cross-linking to be handled, wherein the temperature of high-temperature cross-linking processing is 500-900 ℃, and the treatment time is 1-10h.
Especially, it is that hot-forming defluorination electro-adsorption electrode is put into charring furnace that described high-temperature cross-linking is handled, and is heated to 500-900 ℃ under nitrogen protection, and 1-10h is handled in insulation.
Particularly, the temperature of high-temperature cross-linking processing is preferably 700-900 ℃, preferred 1-5h of treatment time.
The present invention provides a kind of drinking water defluorination electro-adsorption electrode that is prepared from according to the method described above on the other hand.
The defluorination electro-adsorption electrode of the present invention's preparation has following advantage:
1, the ion selectivity of defluorination combined electrode of the present invention is good, at its object removal ion (fluorion) higher selectivity is arranged, and other common negatively charged ion all do not have obviously influence in the water in the tap water scope;
2, defluorination combined electrode of the present invention is by effects such as covalent linkage chemisorption, electrostatic adsorption, ion-exchange absorption, absorption and fixing fluorine cpd in the tap water, loading capacity height to fluorine, at pH is under the neutrallty condition, when voltage was 5V, the saturated adsorption capacity of defluorination combined electrode was 18.6-92.8mg/g; When voltage was 0V, the saturated adsorption capacity of defluorination combined electrode was 12.2-63.1mg/g, and electricity promotes treatment effect to improve 40-60%;
3, defluorination combined electrode of the present invention than electric capacity height, reach 100-130F/g, volume resistivity is low, reaches 6.0 * 10
7-8.6 * 10
7Ω cm;
4, the cohesive strength of defluorination combined electrode of the present invention, bonding strength height, the crushing strength height, the dry state compressive strength reaches more than the 35N, and the sorbent material rate of loss is less than 1%, and life-time service is not broken, is suitable for long-term and uses under water flow pressure changes big situation;
5, mass loss is little in the defluorination combined electrode of the present invention use, no stripping, and swelling not, toxicological harmless, the non-secondary pollution problem, it is reliable to handle the back water quality safety.
Embodiment
Embodiment 1
1, preparation conductive mixture
At first, multi-walled carbon nano-tubes joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and carbon nanotube is 9: 1, and the specific surface area of multi-walled carbon nano-tubes is greater than 110m
2/ g;
Then, sorbent material hydration hydroxyl oxidize zirconium and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and hydration hydroxyl oxidize zirconium is 1: 19;
Wherein, the hydration hydroxyl oxidize zirconium step of carrying out in the following order is prepared from:
1) be that to be added dropwise to volume with the speed of 20ml/min be that 30L, concentration are the Zr (SO of 0.35mol/l for the NaOH solution of 6mol/l with concentration
4)
2In the solution, be 7.0 until the pH of solution value;
2) remove supernatant liquor after staticly settling 12h, be precipitated to the specific conductivity of washings less than 1ms/cm with the clear water repetitive scrubbing;
3) be deposited in the stoving oven after drying to constant weight under 90 ℃ the temperature, ground 100 mesh sieves, promptly;
Hydration hydroxyl oxidize zirconium adopts ASAP Micromeritics, and (Macross, USA) to record the specific surface area of zirconium powder be 120-134m to the specific surface determinator
2/ g, pore texture are based on mesopore, and mean pore size is
Hydration hydroxyl oxidize zirconium fluorine adsorptive capacity when pH=4 can reach 124mg/g, and the fluorine adsorptive capacity reaches 68mg/g when pH=7.
Wherein, the step of carrying out in the following order is prepared from hydration hydroxyl oxidize zirconium and all is applicable to the present invention:
At first: the NaOH solution that with concentration is 3-10mol/L is added drop-wise to the Zr (SO that concentration is 0.1-0.6mol/L with the speed of 10-50ml/min
4)
2In the solution, be 7.0 until the pH of solution value;
Then: staticly settle and remove supernatant liquor, repetitive scrubbing is precipitated to the specific conductivity of washings less than 1ms/cm;
Then: be deposited in dry to constant weight under the 40-100 ℃ of condition after, ground 100 mesh sieves, promptly.
Particularly, the specific surface area of described hydration hydroxyl oxidize zirconium is 120-134m
2/ g, mean pore size is
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder ethylene-vinyl alcohol copolymer (EVOH) joined carry out ball milling in the ball mill and mix, cross 100 mesh sieves then, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and hot melt adhesive powder EVOH is 19: 1, the EVOH molecular weight is 200-300 ten thousand, and melt temperature is 183 ℃;
3, hot-forming
Powdered electro-adsorption mixture is placed the sheet mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 200 ℃, and hot pressing pressure is 5MPa;
After insulation is 15min in the hot pressing treatment time; the combined electrode of moulding is put into charring furnace; under nitrogen protection, be heated to 850 ℃; after 2h is handled in insulation; being cooled to room temperature (25 ℃) back takes out; promptly make defluorination electro-adsorption battery lead plate finished product, the capability and performance index detected result of finished product combination electrode plate is as shown in table 1.
Do anode with the defluorination electro-adsorption battery lead plate that makes, graphite cake is a negative electrode, connect power supply and handle fluorine-containing water, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 88.2mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 88.2mg) to the adsorptive capacity of fluorine; When voltage is 0V, adsorptive capacity to fluorine is 63.1mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 63.1mg), the short defluorination treatment effect of handling of electricity has improved 40%, and wherein the fluorine absorption of the electrode of short treatment effect=(the fluorine loading capacity of the electrode when the fluorine loading capacity-voltage of the electrode when voltage is 5V is 0V) of electricity/when voltage is 0V holds * 100%.
Measure the mass loss rate of defluorination combined electrode as follows:
An amount of defluorination electro-adsorption battery lead plate is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%;
Adopt the ratio electric capacity of cyclic voltammetry electrode; Adopt volometer to measure the volume resistivity of electrode; Adopt YHKC-2A type digital display granule strength determinator to measure the crushing strength of electrode, measurement result is as shown in table 1.
Embodiment 2
1, preparation conductive mixture
At first, activated carbon fiber joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and activated carbon fiber is 9: 1, and the specific surface area of activated carbon fiber is 800-1600m
2/ g, particle diameter≤150 μ m;
Then, sorbent material hydration hydroxyl oxidize zirconium and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and hydration hydroxyl oxidize zirconium is 3: 7;
Wherein, the hydration hydroxyl oxidize zirconium step of carrying out in the following order is prepared from:
1) be that to be added dropwise to volume with the speed of 50ml/min be that 30L, concentration are the Zr (SO of 0.6mol/l for the NaOH solution of 3mol/l with concentration
4)
2In the solution, be 7.0 until the pH of solution value;
2) remove supernatant liquor after staticly settling 12h, be precipitated to the specific conductivity of washings less than 1ms/cm with the clear water repetitive scrubbing;
3) be deposited in and under 50 ℃ temperature, dry to constant weight in the stoving oven, ground 100 mesh sieves, promptly;
Hydration hydroxyl oxidize zirconium adopts ASAP Micromeritics, and (Macross, USA) to record the specific surface area of zirconium powder be 120-134m to the specific surface determinator
2/ g, pore texture are based on mesopore, and mean pore size is
, hydration hydroxyl oxidize zirconium fluorine adsorptive capacity when pH=4 can reach 124mg/g, and the fluorine adsorptive capacity reaches 68mg/g when pH=7.
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder ethylene-vinyl alcohol copolymer (EVOH) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and ethylene-vinyl alcohol copolymer is 8: 2, the EVOH molecular weight is 200-300 ten thousand, and melt temperature is 183 ℃;
3, hot-forming
Powdered electro-adsorption mixture is placed columnar mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 200 ℃, and hot pressing pressure is 5MPa;
After insulation is 20min in the hot pressing treatment time; be cooled to room temperature (20 ℃); adopting cutting machine to cut into length the combined electrode of moulding is 10-20 purpose particle; put into charring furnace then; under nitrogen protection, be heated to 700 ℃, after 1h is handled in insulation, be cooled to room temperature (20 ℃) back and take out; promptly make particulate state defluorination electro-adsorption electrode finished product, finished product combined electrode particulate capability and performance index detected result is as shown in table 1.
With graphite cake as anode and negative plate, it is particles filled in cathode compartment, anolyte compartment to make combined electrode, adopt the fluorine-containing water of open processing, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, connects power supply, energising, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 92.8mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 92.8mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 58.3mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 58.3mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 60%.
An amount of defluorination electro-adsorption electrode particle is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%;
Embodiment 3
1, preparation conductive mixture
At first, multi-walled carbon nano-tubes joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and carbon nanotube is 1: 1, and the specific surface area of multi-walled carbon nano-tubes is greater than 110m
2/ g;
Then, adsorbent activity aluminum oxide and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and activated alumina is 3: 7, and the specific surface area of activated alumina is 280-360m
2/ g, particle diameter≤150 μ m;
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder polytetrafluoroethylene (PTFE) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and tetrafluoroethylene is 8: 2, the PTFE molecular weight is 600-1000 ten thousand, and melt temperature is 327～342 ℃;
3, hot-forming
Powdered electro-adsorption mixture is placed columnar mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 330 ℃, and hot pressing pressure is 15MPa;
After insulation is 15min in the hot pressing treatment time; be cooled to room temperature (20 ℃); adopt cutting machine to cut into length 10-20 purpose particle the combined electrode of moulding; put into charring furnace then; under nitrogen protection, be heated to 700 ℃, after 3h is handled in insulation, be cooled to room temperature (20 ℃) back and take out; promptly make particulate state defluorination electro-adsorption electrode finished product, finished product combined electrode particulate capability and performance index detected result is as shown in table 1.
With graphite cake as anode and negative plate, it is particles filled in cathode compartment, anolyte compartment to make combined electrode, adopt the fluorine-containing water of open processing, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, connects power supply, energising, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 21.0mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 21.0mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 15.1mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 15.1mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 40%.
An amount of defluorination electro-adsorption electrode particle is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%.
Embodiment 4
1, preparation conductive mixture
At first, activated carbon fiber joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and activated carbon fiber is 9: 1, and the activated carbon fiber specific surface area is 800-1600m
2/ g, particle diameter≤150 μ m;
Then, adsorbent activity aluminum oxide and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and activated alumina is 9: 11, and activated alumina is that specific surface area is 280-360m
2The white spherical particle of/g, particle diameter≤150 μ m;
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder Polyurethane thermoplastic elastomer (TPU) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and Polyurethane thermoplastic elastomer TPU is 7: 3, the TPU molecular weight is 170-200 ten thousand, and density is 1.14-1.22g/cm
3, melt temperature is at 170-205 ℃;
3, hot-forming
Powdered electro-adsorption mixture is placed the sheet mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 220 ℃, and hot pressing pressure is 30MPa;
After insulation is 60min in the hot pressing treatment time; the combined electrode of moulding is put into charring furnace; under nitrogen protection, be heated to 900 ℃; after 5h is handled in insulation; being cooled to room temperature (25 ℃) back takes out; promptly make defluorination electro-adsorption battery lead plate finished product, the capability and performance index detected result of finished product combined electrode sheet is as shown in table 1.
Do anode with the defluorination electro-adsorption battery lead plate that makes, graphite cake is a negative electrode, connect power supply and handle fluorine-containing water, adopt the fluorine-containing water of open processing, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, carries out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 18.6mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 18.6mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 12.2mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 12.2mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 45%.
An amount of defluorination electro-adsorption battery lead plate is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%.
Embodiment 5
1, preparation conductive mixture
At first, multi-walled carbon nano-tubes joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and carbon nanotube is 9: 1, and the specific surface area of multi-walled carbon nano-tubes is greater than 110m
2/ g;
Then, adsorbent activity titanium dioxide and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and active titanic dioxide is 1: 4, active titanic dioxide is with anatase titanium dioxide calcination 3h under 450 ℃ high temperature, grinds to particle diameter≤150 μ m;
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder urethane (PU) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and Polyurethane is 9: 1, PU is a no-solvent type PU glue, molecular weight is 90-130 ten thousand, and melt temperature is the 120-180 degree;
3, hot-forming
Powdered electro-adsorption mixture is placed the sheet mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 180 ℃, and hot pressing pressure is 10MPa;
After insulation is 20min in the hot pressing treatment time; the combined electrode of moulding is put into charring furnace; under nitrogen protection, be heated to 800 ℃; after 1h is handled in insulation; being cooled to room temperature (25 ℃) back takes out; promptly make defluorination electro-adsorption battery lead plate finished product, the capability and performance index detected result of finished product combined electrode sheet is as shown in table 1.
Do anode with the defluorination electro-adsorption battery lead plate that makes, graphite cake is a negative electrode, connect power supply, the fluorine-containing water of open processing is adopted in energising, and the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 47.4mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 47.4mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 30.3mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 30.3mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 58%.
An amount of defluorination electro-adsorption battery lead plate is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%.
Embodiment 6
1, preparation conductive mixture
At first, activated carbon fiber joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and activated carbon fiber is 9: 1, and the activated carbon fiber specific surface area is 800-1600m
2/ g pulverizes the back by ball mill and crosses the use of 100 mesh sieves;
Then, adsorbent activity titanium dioxide and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and active titanic dioxide is 3: 7, active titanic dioxide is with anatase titanium dioxide calcination 3h under 450 ℃ high temperature, grinds to particle diameter≤150 μ m;
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder Polyurethane thermoplastic elastomer (TPU) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and Polyurethane thermoplastic elastomer (TPU) is 8: 2, the TPU molecular weight is 170-200 ten thousand, and density is 1.14-1.22g/cm
3, melt temperature is at 170-205 ℃;
3, hot-forming
Powdered electro-adsorption mixture is placed columnar mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 220 ℃, and hot pressing pressure is 20MPa;
After insulation is 15min in the hot pressing treatment time; be cooled to room temperature (25 ℃); adopt cutting machine to cut into length 10-20 purpose particle the combined electrode of moulding; put into charring furnace then; under nitrogen protection, be heated to 850 ℃, after 2h is handled in insulation, be cooled to room temperature (25 ℃) back and take out; promptly make particulate state defluorination electro-adsorption electrode finished product, finished product combined electrode particulate capability and performance index detected result is as shown in table 1.
With graphite cake as anode and negative plate, to make the combined electrode particle is filled in respectively in cathode compartment, the anolyte compartment, adopt the fluorine-containing water of open processing, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, connects power supply, energising, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 37.5mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 37.5mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 25.7mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 25.7mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 50%.
An amount of defluorination electro-adsorption electrode particle is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%.
Embodiment 7
1, preparation conductive mixture
At first, multi-walled carbon nano-tubes joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and carbon nanotube is 1: 1, and the specific surface area of multi-walled carbon nano-tubes is greater than 110m
2/ g;
Then, adsorbent activity magnesium oxide and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and activated magnesia is 1: 9, the median size of activated magnesia is less than 2000nm, and specific surface area is 5-20m
2/ g;
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder ethylene-vinyl alcohol copolymer (EVOH) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and ethylene-vinyl alcohol copolymer is 8: 2, the EVOH molecular weight is 200-300 ten thousand, 183 ℃ of melt temperatures;
3, hot-forming
Powdered electro-adsorption mixture is placed columnar mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 200 ℃, and hot pressing pressure is 5MPa;
After insulation is 20min in the hot pressing treatment time; be cooled to room temperature (15 ℃); adopt cutting machine to cut into length 10-20 purpose particle the combined electrode of moulding; put into charring furnace then; under nitrogen protection, be heated to 700 ℃, after 1h is handled in insulation, be cooled to room temperature (15 ℃) back and take out; promptly make particulate state defluorination electro-adsorption electrode finished product, finished product combined electrode particulate capability and performance index detected result is as shown in table 1.
With graphite cake as anode and negative plate, to make the combined electrode particle is filled in respectively in cathode compartment, the anolyte compartment, adopt the fluorine-containing water of open processing, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, connects power supply, energising, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 26.5mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 26.5mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 18.9mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 18.9mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 40%.
An amount of defluorination electro-adsorption electrode particle is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%.
Embodiment 8
1, preparation conductive mixture
At first, activated carbon fiber joined in the graphite stir, mixing makes electro-conductive material, and wherein, the weight part proportioning of graphite and activated carbon fiber is 9: 1, and the activated carbon fiber specific surface area is 800-1600m
2/ g, particle diameter≤150 μ m;
Then, adsorbent activity magnesium oxide and electro-conductive material joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered conductive mixture, wherein, the weight part proportioning of electro-conductive material and activated magnesia is 1: 4, the median size of activated magnesia is less than 2000nm, and specific surface area is 5-20m
2/ g;
2, preparation electro-adsorption mixture
Powdered conductive mixture and hot melt adhesive powder urethane (PU) joined carry out ball milling in the ball mill and mixed 100 mesh sieves, make Powdered electro-adsorption mixture, wherein, the weight part proportioning of conductive mixture powder and urethane (PU) is 4: 1, PU is a no-solvent type PU glue, molecular weight is 90-130 ten thousand, and melt temperature is 120-180 ℃;
3, hot-forming
Powdered electro-adsorption mixture is placed the sheet mould, and heating is carried out hot-formingly, and wherein, hot pressed temperature is 180 ℃, and hot pressing pressure is 20MPa;
After insulation is 15min in the hot pressing treatment time; the combined electrode of moulding is put into charring furnace; under nitrogen protection, be heated to 850 ℃; after 2h is handled in insulation; being cooled to room temperature (20 ℃) back takes out; promptly make defluorination electro-adsorption battery lead plate finished product, the capability and performance index detected result of finished product combined electrode sheet is as shown in table 1.
Do anode with the defluorination electro-adsorption battery lead plate that makes, graphite cake is a negative electrode, adopt the fluorine-containing water of open processing, the fluorion equilibrium concentration is 30mg/L in the water, under pH=7.0 ± 0.1 condition, connects power supply, energising, carry out the defluorination experiment respectively when voltage is 5V, 0V, the result shows when voltage is 5V that defluorination electro-adsorption battery lead plate is 27.8mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 27.8mg) to the adsorptive capacity of fluorine; When voltage is 0V, be 17.4mg/g (being the fluorine of every gram defluorination electro-adsorption battery lead plate absorption 17.4mg) to the adsorptive capacity of fluorine, electric promoted defluorination treatment effect has improved 40%.
An amount of defluorination electro-adsorption battery lead plate is placed the Erlenmeyer flask that the 100mL deionized water is housed, behind 150rpm vibration 24h on the shaking table, combination electrode plate is taken out, water flushing combination electrode plate, then in baking oven, dry 12h down in 65 ℃, the quality of the combined electrode after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding combined electrode of test, 24h shakes bottle mass loss of test compound electrode less than 1%.
Table 1 defluorination electro-adsorption electrode performance detected result
| Than electric capacity (F/g) | Volume resistivity (Ω cm) | Crushing strength (N) | Rate of loss (%) | |
| Embodiment 1 | 100 | 8.0×10 7 | ?＞35 | ＜1 |
| Embodiment 2 | 120 | 6.8×10 7 | ?＞38 | ＜1 |
| Embodiment 3 | 110 | 7.5×10 7 | ?＞38 | ＜1 |
| Embodiment 4 | 121 | 6.9×10 7 | ?＞40 | ＜1 |
| Embodiment 5 | 130 | 6.2×10 7 | ?＞35 | ＜1 |
| Embodiment 6 | 114 | 7.1×10 7 | ?＞38 | ＜1 |
| Embodiment 7 | 108 | 8.6×10 7 | ?＞38 | ＜1 |
| Embodiment 8 | 130 | 6.0×10 7 | ?＞40 | ＜1 |
Detected result shows:
1, the loading capacity height of defluorination combined electrode of the present invention is under the neutrallty condition at pH, and when voltage was 5V, the saturated adsorption capacity of defluorination combined electrode was 18.6-92.8mg/g, and the short treatment effect of electricity improves 40-60%;
2, defluorination combined electrode of the present invention than electric capacity height, reach 100-130F/g, volume resistivity is low, is 6.0 * 10
7-8.6 * 10
7Ω cm, high ratio electric capacity and lower volume resistivity make the conductivity of combined electrode of the present invention improve, thereby the short defluorination effect of electricity is remarkable.
3, the cohesive strength of defluorination combined electrode of the present invention, bonding strength height, the crushing strength height, the dry state compressive strength reaches more than the 35N, and the sorbent material rate of loss is less than 1%, and life-time service is not broken, is suitable for long-term and uses under water flow pressure changes big situation.
Claims (10)
1. the preparation method of a drinking water defluorination electro-adsorption electrode comprises following step in sequence:
1) electro-conductive material and sorbent material are mixed, make conductive mixture, wherein, described electro-conductive material is 3-55: 45-97 with the ratio of the weight part of sorbent material;
2) hot melt adhesive is joined in the conductive mixture, mix, make the electro-adsorption mixture, wherein, hot melt adhesive is 5-50: 50-95 with the ratio of the weight part of conductive mixture;
3) the electro-adsorption mixture is put into mould, hot-forming, make defluorination electro-adsorption electrode.
2. preparation method as claimed in claim 1 is characterized in that electro-conductive material described in the step 1) is that carbon nanotube or activated carbon fiber and graphite mix.
3. preparation method as claimed in claim 2, the weight part proportioning that it is characterized in that described graphite and carbon nanotube is 50-90: 10-50; The weight part proportioning of described graphite and activated carbon fiber is 50-90: 10-50.
4. preparation method as claimed in claim 1 or 2 is characterized in that sorbent material described in the step 1) selects one or more in hydration hydroxyl oxidize zirconium, aluminum oxide, titanium dioxide, the magnesium oxide.
5. preparation method as claimed in claim 1 or 2 is characterized in that step 2) described in hot melt adhesive select in ethylene-vinyl alcohol copolymer, tetrafluoroethylene, Polyurethane thermoplastic elastomer, the urethane one or more.
6. preparation method as claimed in claim 1 or 2 is characterized in that pressure hot-forming described in the step 3) is 5-30MPa, and temperature is 180-330 ℃, and hot pressing time is 10-60min.
7. preparation method as claimed in claim 1 or 2 is characterized in that also comprising that hot-forming defluorination electro-adsorption electrode is carried out high-temperature cross-linking to be handled, and wherein the temperature of high-temperature cross-linking processing is 500-900 ℃, and the treatment time is 1-10h.
8. preparation method as claimed in claim 1 or 2 is characterized in that the electro-conductive material described in the step 1) and the ratio of the weight part of de-fluoridation adsorbent are preferably 5-45: 55-95.
9. preparation method as claimed in claim 1 or 2 is characterized in that step 2) described in the ratio of hot melt adhesive and the weight part of conductive mixture be preferably 5-30: 70-95.
10. a drinking water defluorination electro-adsorption electrode is characterized in that being prepared from according to the arbitrary described method of claim 1～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010155321 CN102234145A (en) | 2010-04-26 | 2010-04-26 | Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010155321 CN102234145A (en) | 2010-04-26 | 2010-04-26 | Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102234145A true CN102234145A (en) | 2011-11-09 |
Family
ID=44885329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010155321 Pending CN102234145A (en) | 2010-04-26 | 2010-04-26 | Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102234145A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641201A (en) * | 2013-12-03 | 2014-03-19 | 北京林业大学 | Preparation method of fluoride removal electric adsorption lanthanum-loaded electrode for drinking water and fluoride removal electrode |
| CN105819553A (en) * | 2015-03-31 | 2016-08-03 | 南京大学 | Carbon nanocage-doped binary carbon material composite electrode, preparation method thereof and application of composite electrode in electro-adsorption desalting |
| CN109096975A (en) * | 2018-07-12 | 2018-12-28 | 常州聚和新材料股份有限公司 | A kind of conductive hot melt viscose binder |
| CN111875009A (en) * | 2020-07-20 | 2020-11-03 | 中化环境科技工程有限公司 | Method for treating nitrate radical in industrial wastewater |
| CN114053992A (en) * | 2020-07-29 | 2022-02-18 | 南京大学 | Composite material for deeply removing fluorine ions in wastewater, preparation method and application |
| CN114956277A (en) * | 2022-04-27 | 2022-08-30 | 常州大学 | Electrochemical defluorination method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463927A (en) * | 2002-06-19 | 2003-12-31 | 上海维安新材料研究中心有限公司 | Condenser type sea water desalination process using nana carbon tube made electrodes |
| CN1544116A (en) * | 2003-11-13 | 2004-11-10 | 上海大学 | Making method for charcoal electrode of liquid flow type electroadsorption desalinization device |
| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
-
2010
- 2010-04-26 CN CN 201010155321 patent/CN102234145A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463927A (en) * | 2002-06-19 | 2003-12-31 | 上海维安新材料研究中心有限公司 | Condenser type sea water desalination process using nana carbon tube made electrodes |
| CN1544116A (en) * | 2003-11-13 | 2004-11-10 | 上海大学 | Making method for charcoal electrode of liquid flow type electroadsorption desalinization device |
| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 《环境科学与管理》 20080831 王国建等 吸附法除氟技术的原理与方法 121-124,165 4和10 第33卷, 第8期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641201A (en) * | 2013-12-03 | 2014-03-19 | 北京林业大学 | Preparation method of fluoride removal electric adsorption lanthanum-loaded electrode for drinking water and fluoride removal electrode |
| CN105819553A (en) * | 2015-03-31 | 2016-08-03 | 南京大学 | Carbon nanocage-doped binary carbon material composite electrode, preparation method thereof and application of composite electrode in electro-adsorption desalting |
| CN109096975A (en) * | 2018-07-12 | 2018-12-28 | 常州聚和新材料股份有限公司 | A kind of conductive hot melt viscose binder |
| CN111875009A (en) * | 2020-07-20 | 2020-11-03 | 中化环境科技工程有限公司 | Method for treating nitrate radical in industrial wastewater |
| CN111875009B (en) * | 2020-07-20 | 2022-11-08 | 中化环境科技工程有限公司 | Method for treating nitrate radical in industrial wastewater |
| CN114053992A (en) * | 2020-07-29 | 2022-02-18 | 南京大学 | Composite material for deeply removing fluorine ions in wastewater, preparation method and application |
| CN114053992B (en) * | 2020-07-29 | 2023-07-18 | 南京大学 | Composite material for deeply removing fluoride ions in wastewater, preparation method and application |
| CN114956277A (en) * | 2022-04-27 | 2022-08-30 | 常州大学 | Electrochemical defluorination method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102234145A (en) | Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode | |
| CN101870466B (en) | Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom | |
| Wang et al. | Hierarchical porous carbon from the synergistic “pore-on-pore” strategy for efficient capacitive deionization | |
| CN102059093B (en) | Arsenic and fluorine removing nano-composite adsorbent | |
| US20120083403A1 (en) | Method for manufacturing photocatalyst multifunctional dust-free active carbon color ball | |
| Villar et al. | Carbon materials as electrodes for electrosorption of NaCl in aqueous solutions | |
| CN108996501A (en) | Modified absorbent charcoal material, preparation method and purposes | |
| CN101973542A (en) | Preparation method of porous carbon material for supercapacitor | |
| JP5798201B2 (en) | Liquid-permeable capacitor, deionized liquid production apparatus, and deionized liquid production method | |
| JP5770550B2 (en) | Activated carbon and manufacturing method thereof | |
| CN103118783A (en) | Porous ion exchanger, water treatment device, hot-water supply device, and process for producing porous ion exchanger | |
| CN107481865A (en) | A kind of all-solid-state flexible micro super capacitor based on GQD/ cobalt hydroxide composites | |
| CN104916457B (en) | A kind of electrochemical capacitor and Electro Sorb desalination electrode material | |
| CN106206051A (en) | A kind of Graphene modified activated carbon and application thereof | |
| KR20090085756A (en) | Activated carbon for electrode, preparation method thereof and water softener system for comprising the same | |
| KR20190124709A (en) | Carbonaceous materials and electrode materials for electric double layer capacitors containing the carbonaceous materials, electrodes for electric double layer capacitors and electric double layer capacitors | |
| CN102114401B (en) | Arsenic removal adsorbent and preparation method thereof | |
| CN107892298A (en) | A kind of ultracapacitor activated carbon and preparation method thereof | |
| WO2017038220A1 (en) | Desalination treatment method using flow-through capacitor | |
| Inagaki et al. | Carbon materials for water desalination by capacitive deionization | |
| JP2017171538A (en) | Active carbon and method for producing the same, and electric double layer capacitor comprising the active carbon | |
| WO2009067312A3 (en) | Preparation of hydrogen storage materials | |
| CN102891298A (en) | Surface modification method for Mg-Ni-Nd system hydrogen storage electrode alloy | |
| CN103641201A (en) | Preparation method of fluoride removal electric adsorption lanthanum-loaded electrode for drinking water and fluoride removal electrode | |
| CN104743644A (en) | Electrode film for water treatment and its preparation method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111109 |