CN103359808A - Porous carbonized ceramic membrane tube composite anode carrying Pt and Ir as well as preparation and application thereof - Google Patents
Porous carbonized ceramic membrane tube composite anode carrying Pt and Ir as well as preparation and application thereof Download PDFInfo
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- CN103359808A CN103359808A CN2013102556031A CN201310255603A CN103359808A CN 103359808 A CN103359808 A CN 103359808A CN 2013102556031 A CN2013102556031 A CN 2013102556031A CN 201310255603 A CN201310255603 A CN 201310255603A CN 103359808 A CN103359808 A CN 103359808A
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Abstract
The invention discloses a porous carbonized ceramic membrane tube composite anode carrying Pt and Ir as well as a preparation and an application thereof. The porous carbonized ceramic membrane tube composite anode carrying the Pt and the Ir is characterized in that an Al2O3 porous ceramic tube is prepared by utilizing a vapor deposition method, then Pt and Ir are simultaneously introduced by utilizing a dipping-drying method, and finally the porous carbonized ceramic membrane tube composite anode carrying Pt and Ir is obtained by carrying out hydrogen reduction. The membrane tube composite anode has a filtration function and an electrocatalytic oxidation function, has good stability, can be used for dynamically processing phenolic wastewater through electrocatalytic oxidation and shows an excellent degradation effect.
Description
Technical field
The present invention relates to porous carbonization ceramic-film tube composite anode of a kind of supporting Pt, Ir and preparation method thereof, and use By Electrocatalytic Oxidation dynamichandling phenolic wastewater.
Background technology
At present, the main methods of organic waste water has biological process, extraction process, active carbon adsorption, high temperature incineration method and chemical oxidization method etc. both at home and abroad, and these methods all have certain effect to the processing of organic phenol waste water, but also come with some shortcomings.By Electrocatalytic Oxidation, be not only applicable to the purifying treatment of the organic pollutant of biological process refractory reason, and can avoid producing secondary pollution, the aftertreatment ratio is easier to, have that selectivity is good, equipment is simple, be easy to the advantages such as control, so electrochemical catalytic oxidation method degradation of organic waste water has obtained extensive concern in recent years.In the process of Electro-catalytic Oxidation Technique in Organic Wastewater Treatment, anode material is particularly important, and the research that can be used for By Electrocatalytic Oxidation dynamichandling phenolic wastewater is also rare at home at present.
About the anode material of Electro-catalytic Oxidation Technique in Organic Wastewater Treatment, existing document: Treatment of Industrial Water, 2006,26(3) 4-7; Environmental science and management, 2007,32(1) 107-110 has carried out the summary of system to development in recent years.Simultaneously also there is the part Chinese patent that Electro-catalytic Oxidation Technique in Organic Wastewater Treatment is reported, such as 200610096628.1,201110453737.5,201210398371,201210429747 etc.
But with Al
2O
3Porous ceramic pipe is carrier, and through carbonizing treatment, the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir not yet has document or patent report simultaneously.In view of promoting mutually activity under Pt and the common existence condition of Ir, in this patent, we are with Al
2O
3Porous ceramic pipe is carrier, after pre-treatment and carbonization, pickling process is introduced Pt, Ir ion, through hydrogen reducing, make the porous carbonization ceramic-film tube composite anode that Pt, Ir mix, and being used for the catalytic oxidation process of dynamichandling phenolic wastewater, this film tube type composite anode has shown excellent performance.
Summary of the invention
The present invention's purpose is to provide a kind of a kind of supporting Pt of catalytic oxidation dynamichandling phenolic wastewater, porous carbonization ceramic-film tube composite anode of Ir and preparation method thereof of being applied to.
The porous carbonization ceramic-film tube composite anode of a kind of supporting Pt provided by the invention, Ir, this composite anode is with Al
2O
3Porous ceramic pipe is carrier, introduces Pt, Ir component after pre-treatment and carbonization, obtains Pt-Ir/C/Al
2O
3Film pipe composite anode, wherein Al
2O
3Porous ceramic pipe external diameter 16mm, thickness 2mm, high 100mm, Pt content are Al
2O
31～5% of porous ceramic pipe quality, Ir content are Al
2O
30.1～1.0% of porous ceramic pipe quality.
The present invention also provides the preparation method of the porous carbonization ceramic-film tube composite anode of a kind of described supporting Pt, Ir, has the following steps:
1) with Al
2O
3Porous ceramic pipe is heated to 500 ℃ in retort furnace, the organism of its surperficial dust and absorption is removed in thermal treatment 3 hours, is dipping 4 hours in 5% the nickel nitrate solution at massfraction then, 100 ℃ of roll-dryings 6 hours are finished the pre-treatment before the porous ceramic pipe carbonization;
2) in tube furnace, carry out carbonizing treatment;
3) adopt repeatedly dipping-desiccating method supporting Pt, Ir, under hydrogen, reduce, make the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir.
Described step 2) in, the carbonizing treatment temperature is 500～900 ℃, and carbonization time is 2～6 h, and temperature rise rate is 10 ℃/min, and carbon-source gas is oil liquefied gas, and the carbon-source gas flow is 2～10 ml/min.
In the described step 3), the Pt of load source Platinic chloride H
2PtCl
66H
2O solution, the Ir source iridous chloride IrCl of load
33H
2O solution.
In the described step 3), repeatedly dipping-desiccating method supporting Pt, Ir are with Al
2O
3Porous ceramic pipe is immersed in H
2PtCl
66H
2O and IrCl
33H
2After fully absorbing in the mixing solutions of O, drying absorbs again, drying, until mixing solutions is completely absorbed, each drying conditions is 100 ℃, and the time is 2 hours.
In the described step 3), the hydrogen reducing condition is 150～300 ℃, and the recovery time is 1 ~ 3h, and temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 2～10 ml/min.
The present invention also provides a kind of described composite anode to be applied to catalytic oxidation dynamichandling phenolic wastewater.
The invention has the beneficial effects as follows:
The invention provides the porous carbonization ceramic-film tube composite anode that a kind of efficient Pt, Ir for catalytic oxidation dynamichandling phenols organic waste water mixes, collection carbon material electrode, the advantage of noble metal electrode and coated electrode, promoted the phenols degraded, simple carbon material electrode and the shortcoming of noble metal electrode have been avoided simultaneously, have better stability and electrocatalytic oxidation property, can be applicable to simultaneously the dynamichandling of multiple organic waste water.This composite anode is applied to the organic waste water dynamichandling, and technique is simple, and is easy to operate, high to organic degradation rate, can be converted into water and carbonic acid gas to organism.
Description of drawings
The Pt of Fig. 1 embodiment 4 preparations
0.02Ir
0.003/ C/Al
2O
3The XRD spectra of film pipe composite anode.
The Pt of Fig. 2 embodiment 4 preparations
0.02Ir
0.003/ C/Al
2O
3The SEM spectrogram of film pipe composite anode.
Fig. 3 film pipe of the present invention composite anode is applied to the setting drawing that catalytic oxidation is processed organic phenolic wastewater.
Among Fig. 3: 1. phenolic wastewater groove, 2. peristaltic pump, 3. hydraulic pipe, 4. stainless steel cathode, 5. composite anode, 6. wiring, 7. direct supply, 8. insulating plug.
Embodiment
Embodiment 1:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 6 hours under 500 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 2 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O is (with Al
2O
3After porous ceramic pipe is immersed in and fully absorbs in the mixing solutions, drying absorbs drying again, until mixing solutions is completely absorbed, usually absorption dehydration 7 or just mixing solutions can have been absorbed for 8 times) this mixing solutions is to account for respectively 1% and 0.1% of porous ceramic pipe quality according to Pt and Ir content to prepare; Pass through hydrogen reducing 2h at 150 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 2ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.01Ir
0.001/ C/Al
2O
3
Embodiment 2:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 4 hours under 700 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 5 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O, this mixing solutions are 3% and 1% preparations that accounts for respectively the porous ceramic pipe quality according to Pt and Ir content; Pass through hydrogen reducing 1h at 250 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 5ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.03Ir
0.01/ C/Al
2O
3
Embodiment 3:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 2 hours under 900 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 10 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O, this mixing solutions are 5% and 0.2% preparations that accounts for respectively the porous ceramic pipe quality according to Pt and Ir content; Pass through hydrogen reducing 1h at 300 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 10ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.05Ir
0.002/ C/Al
2O
3
Embodiment 4:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 3 hours under 700 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 5 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O, this mixing solutions are 2% and 0.3% preparations that accounts for respectively the porous ceramic pipe quality according to Pt and Ir content; Pass through hydrogen reducing 3h at 200 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 5ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.02Ir
0.003/ C/Al
2O
3
Embodiment 5:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 3 hours under 800 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 5 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O, this mixing solutions are 2% and 0.4% preparations that accounts for respectively the porous ceramic pipe quality according to Pt and Ir content; Pass through hydrogen reducing 3h at 200 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 5ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.02Ir
0.004/ C/Al
2O
3
Embodiment 6:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 2 hours under 800 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 8 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O, this mixing solutions are 4% and 0.6% preparations that accounts for respectively the porous ceramic pipe quality according to Pt and Ir content; Pass through hydrogen reducing 3h at 250 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 2ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.04Ir
0.006/ C/Al
2O
3
Embodiment 7:
With pretreated Al
2O
3Porous ceramic pipe carries out carbonization 2 hours under 600 ℃, temperature rise rate is 10 ℃/min, carbon-source gas flow 5 ml/min; Then absorb H through repeatedly dipping-drying
2PtCl
66H
2O and IrCl
33H
2The mixing solutions of O, this mixing solutions are 5% and 0.2% preparations that accounts for respectively the porous ceramic pipe quality according to Pt and Ir content; Pass through hydrogen reducing 1h at 300 ℃ at last, temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 10ml/min, makes the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir, is designated as: Pt
0.05Ir
0.002/ C/Al
2O
3
Embodiment 8:
The above-mentioned film pipe composite anode that the present invention makes is applied to water treatment technological process device shown in Figure 3, and wherein the condition of water treatment is: voltage 2V, ionogen are 0.1mol/L Na
2SO
4, the organic waste water flow is 150mg/L, and wastewater temperature is 25 ℃, and phenolic waste water and 4-chlorophenol waste strength are 200mg/L, and organic content detects by the COD tester before and after the catalytic oxidation Phenol-Containing Wastewater Treatment.Clearance with COD (is designated as: R
COD) expression composite anode activity.The part composite anode is shown in Table 1 at the activity data that is used for catalytic oxidation processing phenols wastewater.
The R of table 1 phenolic wastewater
COD
| Sample | The R of phenol COD | 4-chlorophenol R COD |
| Embodiment 1 | 50.3 | 57.7 |
| Embodiment 2 | 70.1 | 75.4 |
| Embodiment 3 | 98.9 | 99.5 |
| Embodiment 4 | 98.5 | 99.3 |
| |
98.6 | 99.4 |
| Embodiment 6 | 99.0 | 99.6 |
| Embodiment 7 | 62.7 | 68.6 |
Claims (7)
1. the porous carbonization ceramic-film tube composite anode of a supporting Pt, Ir, it is characterized in that: this composite anode is with Al
2O
3Porous ceramic pipe is carrier, introduces Pt, Ir component after pre-treatment and carbonization, obtains Pt-Ir/C/Al
2O
3Film pipe composite anode, wherein Al
2O
3Porous ceramic pipe external diameter 16mm, thickness 2mm, high 100mm, Pt content are Al
2O
31～5% of porous ceramic pipe quality, Ir content are Al
2O
30.1～1.0% of porous ceramic pipe quality.
2. the preparation method of the porous carbonization ceramic-film tube composite anode of the described supporting Pt of claim 1, Ir is characterized in that following steps:
1) with Al
2O
3Porous ceramic pipe is heated to 500 ℃ in retort furnace, the organism of its surperficial dust and absorption is removed in thermal treatment 3 hours, is dipping 4 hours in 5% the nickel nitrate solution at massfraction then, 100 ℃ of roll-dryings 6 hours are finished the pre-treatment before the porous ceramic pipe carbonization;
2) in tube furnace, carry out carbonizing treatment;
3) adopt repeatedly dipping-desiccating method supporting Pt, Ir, under hydrogen, reduce, make the porous carbonization ceramic-film tube composite anode of supporting Pt, Ir.
3. preparation method according to claim 2, it is characterized in that: described step 2), the carbonizing treatment temperature is 500～900 ℃, carbonization time is 2～6 h, temperature rise rate is 10 ℃/min, and carbon-source gas is oil liquefied gas, and the carbon-source gas flow is 2～10 ml/min.
4. preparation method according to claim 2 is characterized in that: in the described step 3), and the Pt of load source Platinic chloride H
2PtCl
66H
2O solution, the Ir source iridous chloride IrCl of load
33H
2O solution.
5. preparation method according to claim 2, it is characterized in that: in the described step 3), repeatedly dipping-desiccating method supporting Pt, Ir are with Al
2O
3Porous ceramic pipe is immersed in H
2PtCl
66H
2O and IrCl
33H
2After fully absorbing in the mixing solutions of O, drying absorbs again, drying, until mixing solutions is completely absorbed, each drying conditions is 100 ℃, and the time is 2 hours.
6. preparation method according to claim 2, it is characterized in that: in the described step 3), the hydrogen reducing condition is 150～300 ℃, and the recovery time is 1 ~ 3h, and temperature rise rate is 10 ℃/min, and hydrogen flowing quantity is 2～10 ml/min.
7. a composite anode claimed in claim 1 is applied to catalytic oxidation dynamichandling phenolic wastewater.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255603.1A CN103359808B (en) | 2013-06-25 | 2013-06-25 | Porous carbonized ceramic membrane tube composite anode carrying Pt and Ir as well as preparation and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255603.1A CN103359808B (en) | 2013-06-25 | 2013-06-25 | Porous carbonized ceramic membrane tube composite anode carrying Pt and Ir as well as preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103359808A true CN103359808A (en) | 2013-10-23 |
| CN103359808B CN103359808B (en) | 2015-03-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341658A (en) * | 2018-05-03 | 2018-07-31 | 东莞市石鼓污水处理有限公司 | A kind of ceramic filter membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324321A (en) * | 2011-08-26 | 2012-01-18 | 吉林大学 | Metallic nickel oxide/carbon composite electrode material carried by nickel foam substrate |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
-
2013
- 2013-06-25 CN CN201310255603.1A patent/CN103359808B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| CN102324321A (en) * | 2011-08-26 | 2012-01-18 | 吉林大学 | Metallic nickel oxide/carbon composite electrode material carried by nickel foam substrate |
Non-Patent Citations (2)
| Title |
|---|
| BRYAN K. BOGGS等: "Optimization of Pt–Ir on carbon fiber paper for the electro-oxidation of ammonia in alkaline media", 《ELECTROCHIMICA ACTA》 * |
| ZHENYOU WANG等: "Carbonized porous anodic alumina as electrocatalyst support for alcohol oxidation", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341658A (en) * | 2018-05-03 | 2018-07-31 | 东莞市石鼓污水处理有限公司 | A kind of ceramic filter membrane |
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