CN101665276B - Composite activated carbon fiber polar plate - Google Patents
Composite activated carbon fiber polar plate Download PDFInfo
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- CN101665276B CN101665276B CN2009101529651A CN200910152965A CN101665276B CN 101665276 B CN101665276 B CN 101665276B CN 2009101529651 A CN2009101529651 A CN 2009101529651A CN 200910152965 A CN200910152965 A CN 200910152965A CN 101665276 B CN101665276 B CN 101665276B
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- activated carbon
- carbon fiber
- polar plate
- ruthenium
- dioxide
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- -1 aromatic organic compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a composite activated carbon fiber polar plate which takes activated carbon fiber as a carrier and is sintered with iridic oxide and ruthenium dioxide on the surface thereof, wherein iridic oxide accounts for 0.3%-0.5% of activated carbon, ruthenium dioxide accounts for 0.1%-0.3% of activated carbon. In the invention, rare metal iridium and ruthenium are added on an ACF plate, thus enabling an electrochemical reactor to have better processing effect.
Description
Technical field
The invention belongs to technical field of sewage, particularly relate to the dispose of sewage pole plate of usefulness of a kind of electrochemical process, more specifically, relate to a kind of composite activated carbon fiber polar plate.
Background technology
In recent years, utilize solvability or the organic research of suspended state bio-refractory in the electrochemical method treating water more and more.This mainly concentrates on anodic oxidation and cathodic reduction to aspects such as the principle method of removing pollutent and Technologies.Traditional plate material has iron, aluminium etc., and newer invention and research mainly are at utilizing the anodic oxidation degradation of organic substances, and chamber, the two poles of the earth electrolyzer also uses the oxygen evolution potential electrode usually, as PbO
2And SnO
2Electrode, the effect of cathodic electricity catalyzed degradation does not then cause enough attention.
Utilize electrochemical techniques degradation of organic substances between negative electrode, it mainly is the strong oxidizing property intermediate material oxidize contaminants that produces by electrochemistry.At graphite or reticulated vitreous carbon cathode surface two electronic reduction reactions generation H takes place by dissolved molecular oxygen at cathode compartment normally
2O
2, under slightly acidic (pH-3) condition and Fe
2+Generation Fenton reaction, the OH of generation strong oxidizing property, do not have selectively rapid and three kinds of forms reactions of aromatic organic compounds generation: the addition reaction and the electron-transfer reaction of dehydrogenation reaction, destruction C=C unsaturated link(age) make it that chemical degradation take place.Fe in the reaction
3+Can become Fe in cathodic reduction
2+, continue and H
2O
2The Fenton reaction takes place, so Fe
2+In reaction, play the effect of catalyzer.The Fenton reaction mechanism is as follows:
O
2(g)+2H
++2e→H
2O
2
Fe
2++H
2O
2+H
+→Fe
3++H
2O+OH
OH+RH→R+H
2O
Fe
3+The reversible Fe of+e
2+
The essence of Fenton method is the Fe that will produce in the electrochemical reaction process
2+And H
2O
2Lasting source as Fenton reagent.The Fenton method is compared with light Fenton method, has automatic generation H
2O
2More perfect, the H of mechanism
2O
2Utilization ratio height, the more advantages such as (except that the oxygenizement of OH, also having anodic oxidation, electro-adsorption) of organic matter degradation factor.Therefore, the Fenton method is one of important directions of Fenton method development.
In the Fenton method, the selection of cathode plate material is also few at present, and wherein a kind of is activated carbon fiber (ACF) pole plate.Activated carbon fiber (ACF) also claims fibrous activated carbon, is high-efficiency activated sorbing material and environment-friendly engineering material that performance is better than gac.Its carbon atom above 50% is positioned at surfaces externally and internally, is built into unique adsorption structure, is called as the superficiality solid.It is by fibrous presoma, forms through the certain procedure carbonization-activation.The difference of precursor material, the production technique of ACF is also obviously different with the structure of product.The production of ACF generally is that the organic precursor fiber is carried out stabilization treatment under 200 ℃～400 ℃ of low temperature, carries out (charing) activation subsequently.Activation method commonly used mainly contains: with the physical activation method of CO2 or water vapor and use ZnCI2, H3PO, H2PO4, the chemical activation method of KOH, treatment temp is between 700 ℃～1000 ℃, different treatment process (time, temperature, activation dosage etc.) corresponding product has different pore textures and performance.Organic fibre as the ACF presoma mainly contains cellulose base, the PAN base, and the phenolic aldehyde base, asphaltic base, PVA-based, vinylbenzene/olefin copolymer and lignin fibre etc.Flourishing specific surface area and narrower pore size distribution make it have adsorption/desorption speed and bigger loading capacity faster, and because it can be processed as different shapes such as felt, cloth, paper easily, and have the acid and alkali-resistance corrosion resistance characteristic, can be widely used in industrial aspect such as daily lifes such as water treatment, deodorizing and liquid phase decolouring, catalyst, gas delivery.ACF has following characteristics:
(1) there is the adsorption and diffusion effect in interfibrous space in the pore structure, and its micropore is positioned at the surface, and the aperture is little, can produce the capillary condensation effect, has strengthened adsorption effect.
(2) loading capacity is big, and adsorption process is mainly the fiber surface micro-porous adsorption, and adsorption layer is very thin, thereby rate of adsorption is very fast.
(3) a large amount of oxygen-containing functional groups is contained on the surface, as-OH, C=O ,-COOH ,-OC
nH
2n+1, also have the C-N key, N-N key etc., easy and polar adsorption matter molecule forms hydrogen bond; It can also be to the II electron production inductive capacity in the phenyl ring, so have good adsorptive power to containing water soluble organic substances such as oxygen, chlorine, aromatic ring simultaneously.
Aspect electrochemical applications, ACF has absorption, conduction and catalytic performance, be a kind of carbon electrode material, also be used as a kind of accurate three-dimensional structure electrode and be used for the organism that electro-adsorption is removed water, and the charcoal fibre felt electrode also be used as cathodic reduction generation H with applications well prospect
2O
2
Summary of the invention
The purpose of this invention is to provide a kind of electrochemical treatment that is suitable for, the composite activated carbon fiber polar plate of better effects if.
For this reason, the technical solution used in the present invention is as follows: composite activated carbon fiber polar plate is a carrier with the activated carbon fiber, and it is characterized in that: surperficial sintering has iridium dioxide and ruthenium dioxide.
Further, described iridium dioxide is the 0.3%-0.5% of activated carbon fiber, and ruthenium dioxide is the 0.1%-0.3% (being weight ratio) of activated carbon fiber.
Described activated carbon fiber is a graphite felt.
Preparation method of the present invention is such: at first prepare activated carbon fiber polar plate, at quantitative iridium dioxide of surface coated and ruthenium dioxide, then at 1600-1800 ℃ of sintering, ruthenium, iridium are got attached to polar board surface.
The present invention follows catalyzed reaction owing to added rare metal iridium, ruthenium on the ACF plate in reaction process, produce the higher H of concentration
2O
2, and produce the stronger hydroxyl of oxidisability, thus make electrochemical reactor that better treatment effect is arranged.
Embodiment
One, the preparation of compound polar plate
At first prepare the graphite felt pole plate, control thickness is 5mm, and heatproof is 2000 ℃; At the iridium dioxide of surface coated 0.4% and 0.2% ruthenium dioxide; 1700 ℃ of high temperature sinterings 40 minutes.
The comparison of two, invention effect
Respectively with equal area pole plate of the present invention, ACF plate and graphite cake as negative electrode, anode adopts the iron pole plate.By colourity in the electrochemical treatment dyeing and printing sewage and COD.Reaction times is 3 minutes, 5 minutes, 7 minutes, voltage 110V, electric current 3A.Former water COD is 850mg/l.Result is as shown in the table.
H when pole plate of the present invention, ACF and graphite cake are negative electrode
2O
2The contrast of electrochemistry growing amount, as shown in the table.Unit: umolL
-1
| 3min | 5min | 7min | |
| The present invention | 300 | 570 | 670 |
| ACF | 270 | 450 | 480 |
| Graphite cake | 50 | 70 | 90 |
The H that electrochemical reaction produced
2O
2Effective degradable organic pollutant.In solution, there is Fe
2+In the time of (1.0mmolL-1), Fe
2+The H that can produce with electrochemistry
2O
2The homogeneous catalytic reaction generation takes place have the cause of highly active OH, H
2O
2When concentration was high, COD and chroma removal rate relatively also improved.
As seen, the present invention can obviously improve the performance of ACF pole plate, finishes goal of the invention.
Claims (3)
1. composite activated carbon fiber polar plate, with the activated carbon fiber is carrier, it is characterized in that: surperficial sintering has iridium dioxide and ruthenium dioxide, and described iridium dioxide is the 0.3%-0.5% of activated carbon fiber, and ruthenium dioxide is the 0.1%-0.3% (being weight ratio) of activated carbon fiber.
2. composite activated carbon fiber polar plate as claimed in claim 1 is characterized in that: described activated carbon fiber is a graphite felt.
3. composite activated carbon fiber polar plate as claimed in claim 1 or 2, it is characterized in that: it is at first to prepare activated carbon fiber polar plate, at quantitative iridium dioxide of surface coated and ruthenium dioxide,, ruthenium, iridium are got attached to polar board surface then at 1600-1800 ℃ of sintering.
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|---|---|---|---|
| CN2009101529651A CN101665276B (en) | 2009-09-23 | 2009-09-23 | Composite activated carbon fiber polar plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101529651A CN101665276B (en) | 2009-09-23 | 2009-09-23 | Composite activated carbon fiber polar plate |
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| Publication Number | Publication Date |
|---|---|
| CN101665276A CN101665276A (en) | 2010-03-10 |
| CN101665276B true CN101665276B (en) | 2011-04-20 |
Family
ID=41802089
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|---|---|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106400048B (en) * | 2016-09-10 | 2018-07-20 | 华南理工大学 | A kind of electric Fenton cathode material and preparation method thereof based on lignin |
| CN107188273A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | A kind of preparation method of three-dimensional carbon metal oxides electro catalytic electrode |
| CN109576733B (en) * | 2018-11-22 | 2020-10-27 | 太原理工大学 | Preparation method of carbon fiber loaded chlorine evolution catalytic electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189395A (en) * | 1998-01-12 | 1998-08-05 | 南开大学 | Compounded active carbon fibre solid catalyst |
| CN1293263A (en) * | 2000-09-30 | 2001-05-02 | 华东师范大学 | Non-crack nm-class Ti-based anode and its preparing process |
| US6517906B1 (en) * | 2000-06-21 | 2003-02-11 | Board Of Trustees Of University Of Illinois | Activated organic coatings on a fiber substrate |
| CN1792936A (en) * | 2005-12-09 | 2006-06-28 | 中山大学 | Composite active carbon fibre and preparation process thereof |
| CN1943851A (en) * | 2006-10-13 | 2007-04-11 | 中国石油大学(华东) | Carbon base optic catalytic composite material and its preparing method and using method |
-
2009
- 2009-09-23 CN CN2009101529651A patent/CN101665276B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189395A (en) * | 1998-01-12 | 1998-08-05 | 南开大学 | Compounded active carbon fibre solid catalyst |
| US6517906B1 (en) * | 2000-06-21 | 2003-02-11 | Board Of Trustees Of University Of Illinois | Activated organic coatings on a fiber substrate |
| CN1293263A (en) * | 2000-09-30 | 2001-05-02 | 华东师范大学 | Non-crack nm-class Ti-based anode and its preparing process |
| CN1792936A (en) * | 2005-12-09 | 2006-06-28 | 中山大学 | Composite active carbon fibre and preparation process thereof |
| CN1943851A (en) * | 2006-10-13 | 2007-04-11 | 中国石油大学(华东) | Carbon base optic catalytic composite material and its preparing method and using method |
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| Publication number | Publication date |
|---|---|
| CN101665276A (en) | 2010-03-10 |
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Assignee: Hangzhou Huishui Technology Co., Ltd. Assignor: Wang Wanshou Contract record no.: 2011330001086 Denomination of invention: Composite activated carbon fiber polar plate Granted publication date: 20110420 License type: Exclusive License Open date: 20100310 Record date: 20110819 |
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