CN102476042B - Electricity-actuated fluorine-removing absorbing composite plate and preparation method thereof - Google Patents
Electricity-actuated fluorine-removing absorbing composite plate and preparation method thereof Download PDFInfo
- Publication number
- CN102476042B CN102476042B CN201010574158.1A CN201010574158A CN102476042B CN 102476042 B CN102476042 B CN 102476042B CN 201010574158 A CN201010574158 A CN 201010574158A CN 102476042 B CN102476042 B CN 102476042B
- Authority
- CN
- China
- Prior art keywords
- electricity
- fluorine
- short
- defluorination
- actuated
- 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.)
- Expired - Fee Related
Links
Abstract
The invention relates to the field of fluorine removing, and specifically relates to electricity-actuated fluorine-removing absorbing composite particles, an electricity-actuated fluorine-removing absorbing composite plate, and a preparation method thereof. According to the invention, the electricity-actuated fluorine-removing absorbing composite particles and the electricity-actuated fluorine-removing absorbing composite plate comprise active metal oxides, a conductive medium, and a dispersing agent, wherein the ratio of the conductive medium to the metal oxides to the dispersing agent is 5-45:55-93:2-10. The dispersing agent is a mixed liquid of absolute alcohol and montmorillonite with a ratio of 4mL:1g. The composite electricity-actuated fluorine-removing absorbing materials provided by the invention have good fluorine-removing effects. The prepared particle-shaped electricity-actuated fluorine-removing material is advantaged in appropriate particle density, stable property, loss resistance, and suitability for a fixed-bed electricity-actuated fluorine-removing process. The electricity-actuated fluorine-removing plate is used as an anode material. The electricity-actuated fluorine-removing plate can be directly used in electricity-actuated fluorine removing, and can be used in combination with other fluorine-removing materials.
Description
Technical field
The present invention relates to defluorination field, particularly, the present invention relates to the short defluorination absorption of electricity composite particles, the short defluorination absorbing composite plate of electricity and preparation method.
Background technology
Fluorine is one of trace element necessary in human body.The absorption of the appropriate fluorine of human body can make bone, tooth solid, reduces morbidity of dental caries, also neural excitability conduction, alcium and phosphor metabolization, parathyroid function, cellular enzymes system and reproductive process is had to benifit.But the strong electronegativity due to fluorine ion, fluorine has very strong affinity for positively charged calcium ion, and the fluorine of long-term excess intake, also can produce various poisoning symptoms, as fluorine dental plaque, fluorosis of bone, textured bone, the anchylosis symptom such as even paralyse, serious threat human health.In addition, the fluoride of long-term excess intake has larger damage to central nervous system, biological behavior and reproductive system, causes chromosome aberration and cell micronucleus, has carcinogenic, teratogenic effect.Therefore, in control water body, the content of fluorine has great importance to health.
Absorption method is one of main method of current Treatment of High Fluoride Drinking Water.Common de-fluoridation adsorbent mainly contains reactive metal oxides (as activated alumina, activated magnesia, active oxidation titanium etc.), hydroxyapatite, active carbon, rare earth metal oxide (Ce, La, Ti, Zr etc.) etc., and wherein activated alumina is most widely used.There are some researches show, the multivalence hydrated metal oxides such as rare earth, zirconium, titanium, aluminium, magnesium have unique close fluorine ability, can be used as defluorination material, but exist, sorbing material large usage quantity, unit mass defluorination capacity are lower, adsorption capacity loss more greatly, easily causes secondary pollution problems.Can be more for the sorbing material of defluorination, but be applied to the processing of actual fluorinated water, its application mode is limited, mainly contains granular (column, spherical etc.) and support type.Wherein, conventional is bulk material, but the preparation process of bulk material comprises and interpolation and the granulation process of binding agent can cause larger adsorption capacity loss.
Electricity absorption is one " new technology " in current desalination field, former water flows between anodic-cathodic, during energising water intermediate ion by respectively to the electrode migration of oppositely charged and by this electrode adsorption at electrode surface, reach enrichment concentrated, the concentration of dissolved salts, colloidal solid and other charge specieses in channel water is reduced, thus realized water desalination, go hardness and purification.At present the research of electricity absorption is focused mostly in two-dimensional electrode plate material research aspect, but cost is higher.The latter stage sixties, Bickhuxst has proposed three-diemsnional electrode/ternary electrode, between traditional two-dimentional electrolytic tank electrode, load granular or other clastic electrode material, a new utmost point (the 3rd utmost point) in energising in the situation that makes that the granule electrode material surface of filling is charged to become system, be conducive to improve the specific area of electrode, improve material mass transfer effect, improve current efficiency.Research for mosaic electrode focuses mostly in electrochemical degradation organic contamination, reclaims in water body and pollute the fields such as metal, and its adsorption effect is still limited, needs further to be improved.
Therefore, above-mentioned two kinds of defluorination methods are all there being defect aspect defluorination effect and commercial Application, to be improved at present.
Summary of the invention
Therefore, an object of the present invention is to provide the short defluorination absorption of electricity composite particles.
A further object of the present invention is to provide the short defluorination absorbing composite plate of electricity.
According to the short defluorination absorption of electricity of the present invention composite particles, comprise: reactive metal oxides, conducting medium, dispersant, wherein, conducting medium: metal oxide: the ratio of dispersant is 5～45: 55～93: 2～10, dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g.
Preferably, according to the short defluorination absorption of electricity of the present invention composite particles, comprise adhesive, the addition ratio of binding agent and prefabricated mixed-powder is 90mL-150mL: 100g.
According to the short defluorination absorption of electricity of the present invention composite particles, wherein, described binding agent is polyvinyl alcohol, with one or more in maleic acid, ethanedioic acid, malonic acid, succinic acid, citric acid or malic acid, concentration is 5%～30%, mass volume ratio, m/v, be in 100mL water, to add polyvinyl alcohol 5～30g polyvinyl alcohol, esterification and crosslinking reaction makes.Wherein, the described polyvinyl alcohol degree of polymerization is 500～2500, and the concentration of polyvinyl alcohol is 5%～30%, in 100mL water, adds polyvinyl alcohol 5～30g polyvinyl alcohol; In polyvinyl alcohol, add carboxylic acid solution to carry out esterification and crosslinking, the degree of cross linking is 5～20%, and the esterification and crosslinking time is 0.5～4 hour; Wherein said carboxylic acid can be one or more in maleic acid, ethanedioic acid, malonic acid, succinic acid, citric acid or malic acid, and concentration is 5%～30%, mass volume ratio, and m/v, adds polyvinyl alcohol 5～30g polyvinyl alcohol in 100mL water.
Pulverous conducting medium is mixed according to certain ratio with pulverous defluorination absorbing material, add binding agent to mix, the short defluorination absorbing material of granular compound electricity with electric conductivity is made in granulation.The short defluorination material grain density of graininess electricity prepared by the method is moderate, and stable in properties, is difficult for running off, and is applicable to the short defluorination process of fixed bed electricity.
Or the method for preparing the short defluorination absorption of electricity composite particles comprises the following steps:
1) metal oxide is made granular;
2) at the surface spraying conducting medium material of granular metal oxide,
Wherein, conducting medium: the mass ratio of metal oxide is 5-45: 55-95.
The short defluorination material particle conducting medium of graininess electricity prepared by the method is attached to metal oxide particle surface, less on the impact of defluorination material self adsorption capacity, and after materials'use, it is separated that particle and conducting medium are easy to, and is conducive to the recycling of metal oxide and conducting medium material.
According to the short defluorination absorbing composite plate of electricity of the present invention, wherein, the short defluorination absorbing composite plate of described electricity comprises conducting medium, reactive metal oxides, dispersant and binding agent, wherein, conducting medium: reactive metal oxides: the ratio 10～45: 55～90: 2～10 of dispersant, the addition ratio of binding agent and prefabricated mixed-powder is 90mL-150mL: 100g.
According to the method for the short defluorination absorbing composite plate of electricity of the present invention, comprise the following steps:
1) by pulverous conducting medium, pulverous reactive metal oxides and dispersant, wherein, conducting medium: reactive metal oxides: the ratio of dispersant is 10～45: 55～90: 2～10, dispersant is absolute ethyl alcohol and imvite mixed liquor, its ratio is 4mL: 1g;
2) add binding agent, the addition ratio of binding agent and prefabricated mixed-powder is 90mL-150mL: 100g;
3) suppress and be dried into tabular, wherein, pressing pressure is 2-10MPa, and press temperature is 40-100 ℃.
The present invention proposes the short defluorination new ideas of electricity, the principle of the short de-fluoridation adsorbent defluorination of compound electricity based on: at reaction system negative and positive the two poles of the earth, pass in galvanic situation, each conducting particles contacting with anode is a micro anode, in fluorine-containing solution, fluorine ion is under the suction-operated of electric field and particle interface electric double layer, Migration And Concentration is around compound adsorbent, local fluorine ion concentration increases, and completes the removal to fluorine ion in this process.It acts on and feature is, on the one hand, from traditional electric adsorption technology angle, granule electrode has increased the contact area of fluorine ion in anode and solution, strengthens the adsorption capacity of granule electrode electric double layer to fluorine; On the other hand, the enrichment of fluorine ion promotes the absorption of metal oxide to fluorine in composite, under the effect of electric field, use the effect of electric field and ionic double layer enrichment fluorine ion, improve the concentration of fluorine ion in metal oxide surrounding environment, promote the absorption of metal oxide to fluorine ion, thereby produced " electricity is short " effect, the adsorbance of the short de-fluoridation adsorbent of the compound electricity of unit mass to fluorine ion in raising system.
The short adsorption process of electricity is in conjunction with electricity absorption and traditional adsorption theory, and the application of sorbing material can adopt traditional adsorbent application process, also has other to be applicable to method and the technology of the short absorption of electricity simultaneously.The present invention, mainly according to the principle of the short defluorination material of electricity, provides the short defluorination material application process of multiple compound electricity and technology.
According to technical scheme of the present invention, described carbonaceous conductive material be this area existing there is electric conductivity can be as the material of electrode, as carbon black, electrically conductive graphite, conductive carbon fibre and/or conduction expanded graphite.Wherein conductive carbon black specific area is 60-150m
2/ g, particle diameter≤100nm, resistivity≤2.5 Ω m; Conductive carbon fibre resistivity≤2.5 μ Ω m, fibre diameter≤10 μ m; Electrically conductive graphite ultrafine electricity conductive graphite, resistivity≤50 μ Ω m; Resistivity≤20 μ Ω m under conduction expanded graphite normal temperature;
According to technical scheme of the present invention, described reactive metal oxides is to have unique close fluorine ability, can be used as the metal oxide of defluorination material, the metal oxide with Adsorption of fluoride ionic nature well known in the prior art is all suitable for the present invention, as, rare-earth oxide, hydration hydroxyl oxidize zirconium, activated alumina, activated magnesia and/or active oxidation titanium etc.
The standby mixed type electricity of this legal system is urged defluorination plate as anode material, is directly used in the short defluorination of electricity, and use also can combine with other defluorination materials.
The invention has the advantages that:
1) de-fluoridation adsorbent of the present invention is the compound absorption system that contains reactive metal oxides and material with carbon element, utilize the non-Characteristic Adsorption of the electric double layer in course of reaction and the exchange reaction of Characteristic Adsorption and defluorination material and fluorine ion to promote the absorption to fluorine, adsorption capacity is large, applied range;
2) preferred carbon series conductive material in the present invention, has very strong electric conductivity, and the de-fluoridation adsorbent of preparing is higher than electric capacity, and, and price is lower for resistivity;
3) in the present invention, preferably imvite, as the dispersant of recombination process, can improve the uniformity that material mixes on the one hand, reduces the segregation phenomena of composite; Reduce on the other hand the impact of carbon black on defluorination material adsorption capacity, reduce percolation threshold, reduce conducting medium consumption, reduce costs; In addition, the interpolation of imvite can also improve material shock resistance, dimensional stability etc., and improves processing characteristics;
4) in the present invention, absorbent preparation method is simple, and preparation process condition is gentle;
5) in the present invention, adsorbent, in defluorination, also has larger adsorption capacity to the P of water body intermediate ion form, As;
6) in the present invention, the spendable metal oxide materials of adsorbent is more, and preparation method is simple, and preparation method is various;
7) the short de-fluoridation adsorbent of electricity of the present invention in use, without stripping, nonhazardous, permeate safety is reliable and non-secondary pollution, is easy to regeneration, applied widely.
8) provided by the inventionly provide compound electricity to urge defluorination absorbing material, defluorination effect is good, and the short defluorination material grain density of graininess electricity of preparation is moderate, and stable in properties, is difficult for running off, and is applicable to the short defluorination process of fixed bed electricity; The short defluorination plate of electricity, as anode material, is directly used in the short defluorination of electricity, and use also can combine with other defluorination materials.
The specific embodiment
The short defluorination material of embodiment 1 mixed type granulated active alumina/conduction expansion graphite composite electricity
1, material preparation
(1) Powdered activated alumina, conduction expanded graphite and dispersant is even.Wherein, in absorbent powder, the mass ratio of activated alumina, conduction expanded graphite powder and dispersant is 55: 40: 5, and dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g.
(2) in above-mentioned 100g mixed-powder, add 120mL binding agent, binding agent is that 5% poly-vinyl alcohol solution mixes esterification and crosslinking with 5% maleic acid solution by the degree of cross linking 5% and makes; And be squeezed into bar shaped under the pressure of 2MPa, and segment obtains hygrometric state particle, and diameter is 2mm, is then placed in baking oven and carries out rear Cross-linked processing and dry, and rear Cross-linked and baking temperature are 40 ℃, and drying time 24h obtains electric adsorption-defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h
-1, in the situation that particle defluorination material filling quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 72 that the fluorinated water of the short de-fluoridation adsorbent of particle defluorination material electricity is processed times column volume, particle adsorbance reaches 0.85mg/g, and the in the situation that of additional 5V DC voltage, the fluorinated water of the short de-fluoridation adsorbent of particle defluorination material electricity is processed a times column volume and is reached 128, particle adsorbance reaches 1.52mg/g, and electricity is short has improved 0.76 times by material adsorption effect.
The compound electricity of embodiment 2 mixed type granular activated magnesia/conductive acetylene carbon black is urged defluorination material
1, material preparation
(1) Powdered activated magnesia, conductive acetylene carbon black and dispersant is even.Wherein, in absorbent powder, the mass ratio of activated magnesia, conductive acetylene carbon black, dispersant is 80: 15: 5, and dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g;
(2) in above-mentioned 100g mixed-powder, add 150mL binding agent, binding agent is that 15% poly-vinyl alcohol solution mixes esterification and crosslinking with 10% ethanedioic acid solution by the degree of cross linking 10% and makes; And be squeezed into bar shaped under the pressure of 5MPa, and segment obtains hygrometric state particle, and diameter is 2mm, is then placed in baking oven and carries out rear Cross-linked processing and dry, and rear Cross-linked and baking temperature are 60 ℃, drying time 24h.Obtain electric adsorption-defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1, and in the situation that particle defluorination material filling quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 118 that the fluorinated water of the short de-fluoridation adsorbent of particle defluorination material electricity is processed times column volume, particle adsorbance reaches 1.52mg/g, and the in the situation that of additional 5V DC voltage, the fluorinated water of the short de-fluoridation adsorbent of mixed type bulk material electricity is processed a times column volume and is reached 193, mixed type bulk material adsorbance reaches 2.49mg/g, and electricity is short has improved 0.62 times by material adsorption effect.
The compound electricity of the embodiment granular active oxidation titanium/conductive carbon fibre of 3 mixed type is urged defluorination material
1, material preparation
(1) Powdered active oxidation titanium, conductive carbon fibres peacekeeping dispersant is even.Wherein, in absorbent powder, the mass ratio of active oxidation titanium, conductive carbon fibre, dispersant is 65: 25: 10, and dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g;
(2) in above-mentioned 100g mixed-powder, add 100mL binding agent, binding agent is that 25% poly-vinyl alcohol solution mixes esterification and crosslinking with 20% malonic acid solution by the degree of cross linking 10% and makes; And be squeezed into bar shaped under the pressure of 7MPa, and segment obtains hygrometric state particle, and diameter is 2mm, is then placed in baking oven and carries out rear Cross-linked processing and dry, and rear Cross-linked and baking temperature are 90 ℃, drying time 24h.Obtain electric short defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1, and in the situation that particles filled quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 116 that the fluorinated water of particle defluorination material is processed times column volume, particle adsorbance reaches 1.20mg/g, and the in the situation that of additional 5V DC voltage, the fluorinated water of particle defluorination material is processed a times column volume and is reached 208, particle adsorbance reaches 2.14mg/g, and electricity is short has improved 0.78 times by material adsorption effect.
The compound electricity of the embodiment granular hydroxyl oxidize zirconium/conductive carbon fibre of 4 mixed type is urged defluorination material
1, material preparation
(1) Powdered hydroxyl oxidize zirconium, conductive carbon fibres peacekeeping dispersant is even.Wherein, in absorbent powder, the ratio of hydroxyl oxidize zirconium, conductive carbon fibre, dispersant is 90: 5: 5, and dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g;
(2) in above-mentioned 100g mixed-powder, add 90mL binding agent, binding agent is that 30% poly-vinyl alcohol solution mixes esterification and crosslinking with 12% citric acid solution by the degree of cross linking 5% and makes; And be squeezed into bar shaped under the pressure of 9MPa, and segment obtains hygrometric state particle, and diameter is 2mm, is then placed in baking oven and carries out rear Cross-linked processing and dry, and rear Cross-linked and baking temperature are 100 ℃, drying time 24h.Obtain electric short defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1, and in the situation that particles filled quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 162 that the fluorinated water of particle defluorination material is processed times column volume, particle adsorbance reaches 5.01mg/g, and the in the situation that of additional 5V DC voltage, the fluorinated water of particle defluorination material is processed a times column volume and is reached 272, particle adsorbance reaches 7.83mg/g, and electricity is short has improved 0.56 times by material adsorption effect.
The compound electricity of embodiment 5 conducting medium attached type granulated active alumina/conductive acetylene carbon black is urged defluorination material
1, material preparation
(1) in the conductive acetylene carbon black of 15 parts of quality, add binding agent to mix, the ratio of carbon and binding agent is 20g: 100mL; Wherein, binding agent is that 25% poly-vinyl alcohol solution mixes esterification and crosslinking with 15% malic acid solution by the degree of cross linking 15% and makes;
(2) granulated active alumina of 85 parts of quality is immersed in conductive acetylene carbon black/binding agent, gently stir standing 20min, then leach shot-like particle, be placed in baking oven and carry out rear Cross-linked processing and dry, rear Cross-linked and baking temperature are 40 ℃, drying time 24h.Obtain electric short defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1, and in the situation that particles filled quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 92 that the fluorinated water of the short de-fluoridation adsorbent of the compound activated alumina electricity of attached type is processed times column volume, attached type bulk material adsorbance reaches 1.55mg/g, and the in the situation that of additional 5V DC voltage, attached type bulk material fluorinated water is processed a times column volume and is reached 147, attached type bulk material adsorbance reaches 2.46mg/g, and electricity is short has improved 0.58 times by material adsorption effect.
The compound electricity of embodiment 6 conducting medium attached type granular hydroxyl oxidize zirconium/electrically conductive graphite powder is urged defluorination material
1, material preparation
(1) in the electrically conductive graphite powder of 30 parts of quality, add binding agent to mix, the ratio of carbon and binding agent is 20g: 100mL; Wherein, binding agent is that 30% poly-vinyl alcohol solution mixes esterification and crosslinking with 10% succinic acid solution by the degree of cross linking 10% and makes;
(2) the granular hydroxyl oxidize zirconium of 70 parts of quality is immersed in electrically conductive graphite/binding agent, gently stir standing 20min, then leach shot-like particle, be placed in baking oven and carry out rear Cross-linked processing and dry, rear Cross-linked and baking temperature are 80 ℃, drying time 24h.Obtain electric short defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1, and in the situation that particles filled quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 130 that the fluorinated water of attached type bulk material is processed times column volume, attached type bulk material adsorbance reaches 3.76mg/g, and the in the situation that of additional 5V DC voltage, the fluorinated water of attached type bulk material is processed a times column volume and is reached 205, attached type bulk material adsorbance reaches 5.76mg/g, and electricity is short has improved 0.53 times by material adsorption effect.
The compound electricity of embodiment 7 conducting medium attached type granular activated magnesia/conductive acetylene carbon black is urged defluorination material
1, material preparation
(1) in the conductive acetylene carbon black of 5 parts of quality, add binding agent to mix, the ratio of carbon and binding agent is 20g: 100mL; Wherein, binding agent is that 30% poly-vinyl alcohol solution mixes esterification and crosslinking with 5% malic acid solution by the degree of cross linking 10% and makes;
(2) the granular activated magnesia of 95 parts of quality is immersed in conductive acetylene carbon black/binding agent, gently stir standing 20min, then leach shot-like particle, be placed in baking oven and carry out rear Cross-linked processing and dry, rear Cross-linked and baking temperature are 100 ℃, drying time 24h.Obtain electric short defluorination granule adsorbent.
2, effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1, and in the situation that particles filled quality is 20g, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, it is 132 that the fluorinated water of attached type bulk material is processed times column volume, attached type bulk material adsorbance reaches 1.85mg/g, and the in the situation that of additional 5V DC voltage, the fluorinated water of attached type bulk material is processed a times column volume and is reached 208, attached type bulk material adsorbance reaches 2.86mg/g, and electricity is short has improved 0.58 times by material adsorption effect.
The compound electricity of embodiment 8 mixed type tabular activated alumina/electrically conductive graphite powder is urged defluorination material
1, material preparation
(1) pulverous activated alumina, electrically conductive graphite powder, dispersant are mixed with mass ratio.Wherein, the mass ratio of activated alumina, electrically conductive graphite powder, dispersant is 70: 20: 10, and dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g;
(2) in above-mentioned 100g mixed-powder, add 90mL binding agent to mix, binding agent be 30% poly-vinyl alcohol solution and 5% maleic acid acid solution by the degree of cross linking 10%, mix esterification and crosslinking and make; And under the pressure and 70 ℃ of conditions of 2MPa, be pressed into the board-like material of thick 4mm, under this condition, keep 24h.Obtain the short defluorination material of the tabular electricity of mixed type.
2. effect
At former water fluorinion concentration, be 10mg/L, SV is 5h
-1(take plate bulk as reference), in the situation of monolithic compoboard, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, the short defluorination material adsorbance of the tabular electricity of mixed type reaches 1.35mg/g, and the in the situation that of additional 5V DC voltage, the short defluorination material adsorbance of the tabular electricity of mixed type reaches 2.32mg/g, and electricity is short has improved 0.70 times by material adsorption effect.
The compound electricity of embodiment 9 mixed type tabular hydroxyl oxidize zirconium/conductive acetylene carbon black is urged defluorination material
1, material preparation
(1) pulverous hydroxyl oxidize zirconium, conductive acetylene carbon black, dispersant are mixed in certain mass ratio.Wherein, the mass ratio of hydroxyl oxidize zirconium, conductive acetylene carbon black, dispersant is 90: 7: 3, and dispersant is absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g;
(2) in above-mentioned 100g mixed-powder, add 150mL binding agent, mix and under the pressure and 40 ℃ of conditions of 5MPa, be pressed into the board-like material of thick 4mm, under this condition, keep 24h.Obtain the short defluorination material of the tabular electricity of mixed type.
2. effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1 (take plate bulk as reference), and in the situation of monolithic compoboard, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, the short defluorination material adsorbance of the tabular electricity of mixed type reaches 3.48mg/g, and the in the situation that of additional 5V DC voltage, the short defluorination material adsorbance of the tabular electricity of mixed type reaches 6.26mg/g, and electricity is short has improved 0.79 times by material adsorption effect.
The short defluorination material of the tabular active oxidation titanium/conduction of embodiment 10 mixed type expansion graphite composite electricity
1, material preparation
(1) pulverous active oxidation titanium, conduction expanded graphite, dispersant are mixed in certain mass ratio.Wherein, the mass ratio of active oxidation titanium, conduction expanded graphite, dispersant is that 50: 45: 5 dispersants are absolute ethyl alcohol and imvite mixed liquor, and its ratio is 4mL: 1g;
(2) in above-mentioned 100g mixed-powder, add 120mL binding agent, mix and under the pressure and 100 ℃ of conditions of 10MPa, be pressed into the board-like material of thick 4mm, under this condition, keep 24h.Obtain the short defluorination material of the tabular electricity of mixed type.
2. effect
At former water fluorinion concentration, be 10mg/L, SV is 5h-1 (take plate bulk as reference), and in the situation of monolithic compoboard, the water outlet fluorinion concentration of take reaches 1mg/L as experiment terminating point.In the situation that not powering up, the short defluorination material adsorbance of the tabular electricity of mixed type reaches 1.12mg/g, and the in the situation that of additional 5V DC voltage, the short defluorination material adsorbance of the tabular electricity of mixed type reaches 1.75mg/g, and electricity is short has improved 0.56 times by material adsorption effect.
Claims (3)
1. the short defluorination absorbing composite plate of electricity, is characterized in that, the short defluorination absorbing composite plate of described electricity comprises conducting medium, reactive metal oxides, and dispersant and binding agent,
Wherein,
Described conducting medium is conductive carbon black, electrically conductive graphite, conductive carbon fibre and/or conduction expanded graphite, and conductive carbon black specific area is 60-150m
2/ g, particle diameter≤100nm, resistivity≤2.5 Ω m; Conductive carbon fibre resistivity≤2.5 μ Ω m, fibre diameter≤10 μ m; Ultrafine electricity conductive graphite, resistivity≤50 μ Ω m; Resistivity≤20 μ Ω m under conduction expanded graphite normal temperature;
Described reactive metal oxides is rare-earth oxide, hydration hydroxyl oxidize zirconium, activated alumina, activated magnesia and/or active oxidation titanium;
Described dispersant is absolute ethyl alcohol and imvite, and its ratio is 4mL:1g;
Conducting medium: reactive metal oxides: ratio 10～45:55～90:2～10 of dispersant.
2. the short defluorination absorbing composite plate of electricity according to claim 1, is characterized in that, the mixture based on reactive metal oxides, conducting medium and dispersant described in 100g, and the short defluorination absorbing composite plate of described electricity comprises the binding agent of 90-150mL.
3. a method of preparing the short defluorination absorbing composite plate of electricity claimed in claim 1, is characterized in that, said method comprising the steps of:
1) by pulverous conducting medium, pulverous reactive metal oxides and dispersant, wherein, conducting medium: reactive metal oxides: mass ratio 10～45:55～90:2～10 of dispersant,
Described conducting medium is conductive carbon black, electrically conductive graphite, conductive carbon fibre and/or conduction expanded graphite, and conductive carbon black specific area is 60-150m
2/ g, particle diameter≤100nm, resistivity≤2.5 Ω m; Conductive carbon fibre resistivity≤2.5 μ Ω m, fibre diameter≤10 μ m; Ultrafine electricity conductive graphite, resistivity≤50 μ Ω m; Resistivity≤20 μ Ω m under conduction expanded graphite normal temperature,
Described reactive metal oxides is rare-earth oxide, hydration hydroxyl oxidize zirconium, activated alumina, activated magnesia and/or active oxidation titanium,
Described dispersant is absolute ethyl alcohol and imvite, and its ratio is 4mL:1g;
2) add binding agent, the addition ratio of binding agent and prefabricated mixed-powder is 90mL-150mL:100g;
3) suppress and be dried into tabular, wherein, pressing pressure is 2-10MPa, and press temperature is 40-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010574158.1A CN102476042B (en) | 2010-11-30 | 2010-11-30 | Electricity-actuated fluorine-removing absorbing composite plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010574158.1A CN102476042B (en) | 2010-11-30 | 2010-11-30 | Electricity-actuated fluorine-removing absorbing composite plate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102476042A CN102476042A (en) | 2012-05-30 |
| CN102476042B true CN102476042B (en) | 2014-11-26 |
Family
ID=46088897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010574158.1A Expired - Fee Related CN102476042B (en) | 2010-11-30 | 2010-11-30 | Electricity-actuated fluorine-removing absorbing composite plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102476042B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324459B (en) * | 2017-07-31 | 2019-10-01 | 武汉理工大学 | A kind of production method that fish-bone charcoal removes fluoride electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778464A (en) * | 2004-11-18 | 2006-05-31 | 上海维安新材料研究中心有限公司 | Production of carbon electrode of liquid-flow electric adsorption desalting device |
| CN102371146A (en) * | 2010-08-12 | 2012-03-14 | 北京林业大学 | Forming method of efficient composite type electrical fluoride removing adsorbent |
-
2010
- 2010-11-30 CN CN201010574158.1A patent/CN102476042B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778464A (en) * | 2004-11-18 | 2006-05-31 | 上海维安新材料研究中心有限公司 | Production of carbon electrode of liquid-flow electric adsorption desalting device |
| CN102371146A (en) * | 2010-08-12 | 2012-03-14 | 北京林业大学 | Forming method of efficient composite type electrical fluoride removing adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| 吸附法除氟技术的原理与方法;王国建 等;《环境科学与管理》;20080831;第33卷(第8期);第121-124、165页 * |
| 王国建 等.吸附法除氟技术的原理与方法.《环境科学与管理》.2008,第33卷(第8期),第121-124、165页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102476042A (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lee et al. | Preparation and characterization of metal-doped carbon aerogel for supercapacitor | |
| CN103936116B (en) | A kind of manganese dioxide/carbon combined electrode for heavy metal ion in electro-adsorption water and electro-adsorption method | |
| TW526171B (en) | Method for preparing porous carbon material, porous carbon material and electrical double layer capacitor using the same | |
| CN100429155C (en) | Granular electrode catalyst stuffing for 3D electrode reactor and its preparing method | |
| CN103241807A (en) | Composite particle electrode for bipolar three-dimensional electrode reactor and preparation method of electrode | |
| CN110048126A (en) | A kind of manufacture craft and plus plate current-collecting body of aluminium foil | |
| CN106745541B (en) | Composite electrode for removing ammonia nitrogen and organic matters in water and preparation method thereof | |
| JP4609829B2 (en) | Electrode material and capacitor | |
| CN102476042B (en) | Electricity-actuated fluorine-removing absorbing composite plate and preparation method thereof | |
| KR20090085756A (en) | Activated carbon for electrode, preparation method thereof and water softener system for comprising the same | |
| CN108011087A (en) | A kind of manganese dioxide negative material of titanium dioxide modification and preparation method thereof | |
| CN101559995B (en) | Method for preparing particle-catalytic electrode material | |
| CN102173480B (en) | Method for preparing two-phase porous lead dioxide composite electrode | |
| CN102335590B (en) | Efficient electric promoting absorptive fluorine removal adsorbent and preparation method thereof | |
| CN101533715B (en) | Cathode material used for high-energy tantalum mixed capacitor and preparation method thereof | |
| CN113213598A (en) | Ti-MXene derived sodium titanium phosphate/graphene composite material and preparation method and application thereof | |
| JP4822554B2 (en) | Foamed nickel chromium current collector for capacitor, electrode using the same, capacitor | |
| CN106830223B (en) | Activated carbon electrode and preparation method and application thereof | |
| Yamazaki et al. | Application of activated carbon/DNA composite electrodes to aqueous electric double layer capacitors | |
| CN108598367B (en) | High-voltage negative plate, preparation method thereof and high-voltage lithium battery | |
| CN102358637A (en) | Electrochemically enhancing multifunctional material adsorbing and fluorine removing system, and method thereof | |
| CN102371146B (en) | Forming method of efficient composite type electrical fluoride removing adsorbent | |
| KR101094240B1 (en) | Manufacturing method of porous activated carbon and non-porous carbon material composite electrode for capacitive deionization | |
| CN112978868A (en) | Cobalt-iron layered double hydroxide @ titanium carbide electrode material and preparation method and application thereof | |
| CN1208864C (en) | Preparation method of zinc-nickel primary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141126 Termination date: 20151130 |
|
| EXPY | Termination of patent right or utility model |