CN100493709C - Carbon tube carried nano-tungsten carbide catalyzer and method of preparing the same - Google Patents
Carbon tube carried nano-tungsten carbide catalyzer and method of preparing the same Download PDFInfo
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- CN100493709C CN100493709C CNB2007101562222A CN200710156222A CN100493709C CN 100493709 C CN100493709 C CN 100493709C CN B2007101562222 A CNB2007101562222 A CN B2007101562222A CN 200710156222 A CN200710156222 A CN 200710156222A CN 100493709 C CN100493709 C CN 100493709C
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Abstract
The present invention discloses a carbon tube supported nano tungsten carbide catalyst, which comprises nano tungsten carbide granules and carbon nano tube. The nano tungsten carbide granules are evenly distributed on the external surface of the carbon nano tubes. The preparation method of the catalyst is as follows: the carbon tubes are dispersed in a thick nitric acid solution for purification through refluxing, and then purified carbon tubes are got after the post treatment; the purified carbon tubes are dispersed in a tungsten metal salt water solution, and are agitated for reaction; then the reaction solution is channeled into a spray drier for spray drying, and the tungsten metal salt and the carbon tube granule prosecutor are got; the tungsten metal salt and the carbon tube granule prosecutor are calcined, reduced and carbonized in the CO/CO<SUB>2</SUB> reducing and carbonization atomosphere; after the reaction is completed, the product is cooled down to the room temperature under the protection of inert gas and then the carbon tube supported nano tungsten carbide catalyst is got. The present invention is provided with the simple preparation technique, which can be easily controlled. The catalyst granules made are small and are evenly distributed. The catalyst shows the good electric catalysis performance and is provided with a wide application prospect.
Description
(1) technical field
The present invention relates to the preparation method of a kind of nanometer carbon tube tungsten carbide catalyzer and nanometer carbon tube tungsten carbide catalyzer.
(2) technical background
Tungsten carbide (WC) is a kind of good new function material of high rigidity, high stability and anti-wear performance that has, and has promptly obtained in the carbide alloy field using widely from nineteen twenty.Earlier 1960s, discovery WC such as Gaziev have good catalytic activity to cyclohexane dehydrogenation, ethyl benzene dehydrogenation preparation of styrene, thereby have caused catalytic science worker's concern, for a brand-new field has been expanded in the research and development of WC.
Studies show that up to now, WC not only has catalytic activity preferably to some organic synthesis, as showing the catalytic activity that is similar to Pt family noble metal catalyst in hydrogenation, the dehydrogenation reaction, and some reaction also had an optionally catalytic action, as WC the hydrogenation reaction of aromatic nitro compound, fragrant nitroso compound, aliphatic nitro compound, quinone, alkene is had good catalytic activity.In electrochemical field, WC not only has electrocatalysis to the hydrogen anode in the acidic fuel cell, and the direct anodic oxidation of methyl alcohol is also had certain electro catalytic activity.Discover that further WC also has the H of very strong acid resistance, good electrical conductivity, the CO that is not subjected to any concentration, hydro carbons and several PPM
2Advantages such as S poisoning.
CNT has superior Electronic Performance, and can adopt the corresponding techniques means that it is regulated and control.This special performance of CNT makes it can be applicable to composite, and improves the various performances of composite well.Aspect Composite Preparation, CNT is the excellent carriers candidate material of stability of composite materials because of its superior electronics and mechanical performance.Studies show that on CNT, the photocatalysis performance of the hybrid material of generation is than Ru with Ru, Pt and Au nanoparticle precipitate, Pt and Au nano particle good.At TiO
2In/C the catalyst, metal oxide and carbon embody good cooperative effect or cooperative effect between mutually, when metal oxide particle carbon mutually in dispersion when fine, above-mentioned effect can be strengthened.Above-mentioned result of study shows, if tungsten carbide particle is deposited on the CNT, can strengthen its catalytic performance equally.
People's (chemical journals such as horse Chunan, 2006 the 64th volumes, the 20th phase, 2123-2126) studied WC/ CNT Composite Preparation and chemical property thereof, the WC/ CNT composite for preparing will be apparently higher than the spherical WC of meso-hole structure to the electrocatalysis characteristic of p-nitrophenol.But in preparation technology, the efficient of carbon pipe load tungsten ion group is not high, and WC particle is at carbon tube-surface skewness, and agglomeration is arranged, and still there is a big difference for the catalytic performance of this material and precious metals pt.How to optimize reaction condition is still a needs continuation research with the catalytic performance of further raising WC/ CNT composite problem.
(3) summary of the invention
The problem to be solved in the present invention provides a kind of reaction condition optimization, nanometer carbon tube tungsten carbide catalyzer that catalytic performance is higher, and the preparation method of this nanometer carbon tube tungsten carbide catalyzer.
Nanometer carbon tube tungsten carbide catalyzer of the present invention comprises nano silicon carbide tungsten particle and CNT, and the nanometer tungsten carbide uniform particles is distributed in the outer surface of CNT.The preparation method of described nanometer carbon tube tungsten carbide catalyzer is: the carbon pipe is scattered in the purifying that refluxes in the concentrated nitric acid solution, and the process post processing obtains the carbon pipe behind the purifying; Carbon pipe behind the purifying is distributed to stirring reaction in the tungsten aqueous metal salt, reactant liquor is imported carry out spray-drying in the spray dryer again, obtain tungsten slaine/carbon tube particle presoma; Then with the tungsten slaine/carbon tube particle presoma of gained at CO/CO
2Carry out calcination, reduction and carbonization reaction in the reduction and carbonization atmosphere, question response finishes, and under the protection of inert gas product is cooled to room temperature, obtains described nanometer carbon tube tungsten carbide catalyzer; Described tungsten slaine is sulfo-ammonium tungstate or six carboxyl tungsten.
The mass ratio of carrier carbon pipe and tungsten carbide is 1:1～15 in the described nanometer carbon tube tungsten carbide catalyzer, and the caliber of described carbon pipe is 10～100nm, and the particle diameter of described tungsten carbide particle is 3～30nm.
For realizing goal of the invention, the preparation method of described nanometer carbon tube tungsten carbide catalyzer adopts following scheme:
(1) the carbon pipe is scattered in the concentrated nitric acid solution,, obtains carbon pipe behind the purifying through post processing 95～150 ℃ of following backflow purifying 2～10 hours;
(2) the carbon pipe behind the purifying is distributed in the tungsten aqueous metal salt,, reactant liquor is imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma 80～120 ℃ of stirring reactions 4～10 hours; Described tungsten slaine is sulfo-ammonium tungstate or six carboxyl tungsten, and the mass ratio of described carbon pipe and tungsten slaine is 1:1～20;
(3) be reduction and carbonization atmosphere with carbon monoxide and carbon dioxide mix gas; the resulting tungsten slaine of step (2)/carbon tube particle presoma is carried out calcination, reduction and carbonization reaction; question response finishes; under the protection of inert gas, product is cooled to room temperature, obtains described nanometer carbon tube tungsten carbide catalyzer.
Further, the described spray-dired condition of step (2) is: the inlet flow velocity is 5～40mL/min, and the air intake flow velocity is 400～800L/h, and the inlet nozzle temperature of hot air nozzle is 160～250 ℃, and tail gas exit temperature is 80～120 ℃.Preferably: the inlet flow velocity is 20mL/min, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃.
The volume ratio of described carbon monoxide of step (3) and carbon dioxide is 7～15:1, and the gaseous mixture flow velocity is 0.25～0.55m/S.
The described calcination temperature of step (3) is 400～500 ℃, is preferably 450 ℃; The calcination time is 0.5～4 hour, is preferably 1～3 hour.
Described reduction and carbonization reaction temperature is 700～1000 ℃, is preferably 700～800 ℃, most preferably is 750 ℃; The reduction and carbonization reaction time is 5～15 hours, preferred 9～10 hours.
Post processing described in the step (1) is washing, drying, and cooling earlier can be filtered earlier after the washing and be carried out drying again before washing.
The concrete preparation method of described nanometer carbon tube tungsten carbide catalyzer that recommends carries out according to following steps:
(1) the carbon pipe being scattered in mass concentration is in 67% the concentrated nitric acid solution, 95～150 ℃ of following backflow purifying 2～10 hours, and the carbon pipe after supercooling, washing, filtration, drying obtain purifying;
(2) the carbon pipe behind the purifying is distributed in the tungsten aqueous metal salt,, reactant liquor is imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma 80～120 ℃ of stirring reactions 4～10 hours; Described tungsten slaine is sulfo-ammonium tungstate or six carboxyl tungsten, and the mass ratio of described carbon pipe and tungsten slaine is 1:1～20; Described spray-dired condition is: the inlet flow velocity is 20mL/min, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃.
(3) be that carbon monoxide and the carbon dioxide mix gas of 8～12:1 is reduction and carbonization atmosphere with volume ratio; described gaseous mixture flow velocity is 0.25～0.55m/S; with the resulting tungsten slaine of step (2)/carbon tube particle presoma in 450 ℃ of reduction and carbonization atmosphere, carry out calcination 1～3 hour, carried out reduction and carbonization 9～10 hours at 700～800 ℃ again; question response finishes; under the protection of inert gas, product is cooled to room temperature, obtains described nanometer carbon tube tungsten carbide catalyzer.
The present invention compared with prior art optimizes reaction condition, is mainly reflected in following several respects:
1) the tungsten slaine of Shi Yonging substitutes traditional ammonium metatungstate with sulfo-ammonium tungstate or six carboxyl tungsten, experimental result shows, carbon pipe sulfur loaded can be by the chemical bond combination between them for ammonium tungstate or six carboxyl tungsten, the tungsten ion group of load can evenly distribute at the carbon tube-surface, has improved load efficiency greatly.
2) use CO/CO
2Replaced C H
4/ H
2As reduction and carbonization atmosphere.CO has double action, is presoma is reduced, and cracking simultaneously produces carbon, for carburizing reagent provides carbon source.Utilize the temperature of CO carburizing to reduce greatly in the experiment than methane; CO
2Existence be to be used for balance CO disproportionated reaction, can reduce the carbon distribution of catalyst surface greatly, the surface that catalyst is kept clean.
3) utilize spray-drying that the CNT outer surface is arrived in the grafting of tungsten ion group, realize the control to mixing, drying, pattern and the structure of presoma, mixing and pattern control are more convenient, more effective.
Because the optimization of above-mentioned reaction condition, the catalytic performance of the feasible nanometer carbon tube tungsten carbide catalyzer that makes has had large increase than prior art, its technique effect is mainly reflected in: the carbon pipe for preparing carries nanometer WC catalyst and not only demonstrates fully the small-size effect that nanoparticle has, particular performances such as skin effect and quantum size effect, also utilized the superior Electronic Performance of CNT fully, thereby will prolong combining in conjunction with life-span and the constant bit rate transmission that increases the interface electronics again of charge carrier, increase substantially the electrocatalysis characteristic of material.Experimental result shows that the nanometer carbon tube tungsten carbide catalyzer for preparing is much better more than precious metals pt and carrier carbon pipe to the electrocatalysis characteristic of p-nitrophenol.To sum up, the nanometer carbon tube tungsten carbide catalyzer for preparing all has a wide range of applications in chemical catalysis, electro-catalysis field.
(4) description of drawings
Fig. 1 is the transmission electron microscope picture of the carbon pipe behind embodiment 1 purifying, and resolution ratio is 200nm.
Fig. 2 is the XRD figure of the carbon pipe supported nanometer WC sample of embodiment 4 preparations.
Fig. 3 is the carbon pipe supported nanometer WC transmission electron microscope figure of embodiment 4 preparations, and wherein the resolution ratio of a is 100nm, and the resolution ratio of b is 5nm.
Fig. 4 is that the powder microelectrode of embodiment 8, embodiment 9 and comparative example 1 preparation is at 1mol/LH
2SO
4Cyclic voltammetry curve in the+0.002mol/L p-nitrophenyl phenol solution.Wherein a is the platinum microdisk electrode, and b is the CNT powder microelectrode, and c is a carbon pipe supported nanometer WC end microelectrode.
(5) specific embodiment
Further set forth technical scheme of the present invention with specific embodiment below, but protection scope of the present invention is not limited thereto:
Embodiment 1
With the 8.85g caliber is that the carbon pipe of 40～60nm and the red fuming nitric acid (RFNA) of 88.5g67% mix in the there-necked flask of the 500ml that packs into, be warming up to 150 ℃, stirring and refluxing 5 hours, question response finishes, cooled product, behind the washing filtering, be positioned in the infrared drying oven dry 2 hours, obtain the carbon pipe 8.65g behind the purifying.
Fig. 1 has shown the transmission electron microscope picture with the carbon pipe behind this law purifying.Can clearly be seen that from photo through after the nitrated processing, the discreteness of carbon pipe is better, the opening phenomenon has appearred in part carbon pipe, helps the load of later stage tungsten ion.
Embodiment 2
With the 6.95g caliber is that the carbon pipe of 10～20nm and the red fuming nitric acid (RFNA) of 69.5g67% mix in the there-necked flask of the 500ml that packs into, be warming up to 95 ℃, stirring and refluxing 10 hours, question response finishes, cooled product, behind the washing filtering, be positioned in the infrared drying oven dry 2 hours, obtain the carbon pipe 6.73g behind the purifying.
Embodiment 3
With the 5.15g caliber is that the carbon pipe of 60～100nm and the red fuming nitric acid (RFNA) of 51.5g67% mix in the there-necked flask of the 500ml that packs into, be warming up to 120 ℃, stirring and refluxing 2 hours, question response finishes, cooled product, behind the washing filtering, be positioned in the infrared drying oven dry 2 hours, obtain the carbon pipe 4.90g behind the purifying.
Embodiment 4
Take by weighing carbon pipe and 22.2g sulfo-ammonium tungstate behind 2.22g embodiment 1 purifying, be dissolved in 150ml distilled water, water-bath adds thermal agitation, and the control reaction temperature was reacted 8 hours at 90 ℃, reactant liquor imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma, spray-dired condition is: the inlet flow velocity is 20mL/min, and the air intake flow velocity is 600L/h, the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace; feed carbon monoxide and carbon dioxide gas mixture; the mass ratio of carbon monoxide and carbon dioxide mix is 10:1; gas flow rate is 0.45m/S; 450 ℃ carry out calcination 3 hours, carried out reduction and carbonization 10 hours at 750 ℃ again; question response finishes, and under the protection of inert gas product is cooled to room temperature, obtains nanometer carbon tube tungsten carbide catalyzer.The sample that obtains detects (as shown in Figure 2) through XRD, and as can be seen from the figure, sample is mainly by the tungsten oxide W of three phase compositions: WC, CNT and non-stoichiometric
18O
49, the crystallization degree of WC is higher in the sample, and (003) face diffraction maximum only appears in the diffraction maximum of CNT, and the diffraction maximum of other crystal face is not obvious, W
18O
49Also based on (100) face, other diffraction maximum is not obvious for diffraction maximum.The HRTEM of carbon pipe supported nanometer WC sample can find that from Fig. 3 a the WC particle in the sample is distributed in the outer surface of CNT equably as shown in Figure 3, and the WC particle size is about 30nm, and combines closely with CNT, shown in Fig. 3 b.
Take by weighing carbon pipe and 2.12g sulfo-ammonium tungstate behind 2.12g embodiment 1 purifying, be dissolved in 150ml distilled water, water-bath adds thermal agitation, and the control reaction temperature was reacted 4 hours at 80 ℃, reactant liquor imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma, spray-dired condition is: the inlet flow velocity is 40mL/min, and the air intake flow velocity is 800L/h, the inlet nozzle temperature of hot air nozzle is 250 ℃, and tail gas exit temperature is 120 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace; feed carbon monoxide and carbon dioxide gas mixture; the mass ratio of carbon monoxide and carbon dioxide mix is 7:1; gas flow rate is 0.25m/S; 400 ℃ carry out calcination 4 hours, carried out reduction and carbonization 15 hours at 700 ℃ again; question response finishes, and under the protection of inert gas product is cooled to room temperature, obtains nanometer carbon tube tungsten carbide catalyzer.
Embodiment 6
Take by weighing carbon pipe behind 2.03g embodiment 1 purifying and 10.15g six carboxyl tungsten by, be dissolved in 150ml distilled water, water-bath adds thermal agitation, and the control reaction temperature was reacted 6 hours at 120 ℃, reactant liquor imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma, spray-dired condition is: the inlet flow velocity is 5mL/min, and the air intake flow velocity is 400L/h, the inlet nozzle temperature of hot air nozzle is 160 ℃, and tail gas exit temperature is 80 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace; feed carbon monoxide and carbon dioxide gas mixture; the mass ratio of carbon monoxide and carbon dioxide mix is 12:1; gas flow rate is 0.35m/S; 450 ℃ carry out calcination 1 hour, carried out reduction and carbonization 5 hours at 1000 ℃ again; question response finishes, and under the protection of inert gas product is cooled to room temperature, obtains nanometer carbon tube tungsten carbide catalyzer.
Embodiment 7
Take by weighing carbon pipe and 33.0g six carboxyl tungsten behind 1.65g embodiment 1 purifying, be dissolved in 150ml distilled water, water-bath adds thermal agitation, and the control reaction temperature was reacted 10 hours at 90 ℃, reactant liquor imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma, spray-dired condition is: the inlet flow velocity is 20mL/min, and the air intake flow velocity is 600L/h, the inlet nozzle temperature of hot air nozzle is 120 ℃, and tail gas exit temperature is 100 ℃; The dried presoma quartz boat of packing into is positioned in the tube type resistance furnace; feed carbon monoxide and carbon dioxide gas mixture; the mass ratio of carbon monoxide and carbon dioxide mix is 15:1; gas flow rate is 0.55m/S; 500 ℃ carry out calcination 0.5 hour, carried out reduction and carbonization 9 hours at 800 ℃ again; question response finishes, and under the protection of inert gas product is cooled to room temperature, obtains nanometer carbon tube tungsten carbide catalyzer.
Embodiment 8
The nanometer carbon tube tungsten carbide catalyzer that embodiment 7 is made is prepared into powder microelectrode, adopts cyclic voltammetry that carbon pipe supported nanometer WC powder microelectrode is carried out the test of electroreduction catalytic activity, the results are shown in Figure the 4c curve.Used instrument is a microcomputer control CHI660B electrochemical analyser, and three electrode test systems are adopted in experiment, and electrolyte is 1mol/L H
2SO
4+ 0.002mol/L p-nitrophenol, reference electrode are saturated calomel electrode, are the Pt sheet to electrode, and experimental temperature is 25 ℃, and sweep speed is 0.02V/S.
Embodiment 9
CNT preparing carriers powdered microelectrode behind the purifying that embodiment 1 is made repeats embodiment 8 described testing procedures, the results are shown in Figure the 4b curve.
Comparative Examples 1
Utilize the Pt microdisk electrode, repeat embodiment 8 described testing procedures, the results are shown in Figure the 4a curve.
Can find to have higher reduction current absolute value from Fig. 4 with carbon pipe supported nanometer WC powder microelectrode.Under identical condition, the Pt microdisk electrode does not have other reduction current peak except the liberation of hydrogen peak; The reduction peak current of carbon pipe supported nanometer WC powder microelectrode is 4 times of CNT powder microelectrode, and spike potential about 0.1V that shuffles.This explanation carbon pipe supported nanometer WC sample obviously is better than CNT sample behind Pt microdisk electrode and the purifying to the p-nitrophenol electrocatalysis. and this has reflected that its electrocatalysis characteristic has obtained tangible enhancing with behind the carbon pipe loaded with nano WC.
Claims (8)
1. nanometer carbon tube tungsten carbide catalyzer, it is characterized in that described nanometer carbon tube tungsten carbide catalyzer comprises nano silicon carbide tungsten particle and CNT, described nanometer tungsten carbide uniform particles is distributed in the outer surface of CNT, the mass ratio of carrier carbon pipe and tungsten carbide is 1:1～15 in the described nanometer carbon tube tungsten carbide catalyzer, the caliber of described carbon pipe is 10～100nm, the particle diameter of described tungsten carbide particle is 3～30nm, the preparation method of described nanometer carbon tube tungsten carbide catalyzer is: the carbon pipe is scattered in the purifying that refluxes in the concentrated nitric acid solution, and the process post processing obtains the carbon pipe behind the purifying; Carbon pipe behind the purifying is distributed to stirring reaction in the tungsten aqueous metal salt, reactant liquor is imported carry out spray-drying in the spray dryer again, obtain tungsten slaine/carbon tube particle presoma; Then with the tungsten slaine/carbon tube particle presoma of gained at CO/CO
2Carry out calcination, reduction and carbonization reaction in the reduction and carbonization atmosphere, question response finishes, and under the protection of inert gas product is cooled to room temperature, obtains described nanometer carbon tube tungsten carbide catalyzer; Described tungsten slaine is sulfo-ammonium tungstate or six carboxyl tungsten.
2. a method for preparing nanometer carbon tube tungsten carbide catalyzer as claimed in claim 1 is characterized in that described preparation method comprises the steps:
(1) the carbon pipe is scattered in the concentrated nitric acid solution,, obtains carbon pipe behind the purifying through post processing 95～150 ℃ of following backflow purifying 2～10 hours;
(2) the carbon pipe behind the purifying is distributed in the tungsten aqueous metal salt,, reactant liquor is imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma 80～120 ℃ of stirring reactions 4～10 hours; Described tungsten slaine is sulfo-ammonium tungstate or six carboxyl tungsten, and the mass ratio of described carbon pipe and tungsten slaine is 1:1～20;
(3) be reduction and carbonization atmosphere with carbon monoxide and carbon dioxide mix gas; the resulting tungsten slaine of step (2)/carbon tube particle presoma is carried out calcination, reduction and carbonization reaction; question response finishes; under the protection of inert gas, product is cooled to room temperature, obtains described nanometer carbon tube tungsten carbide catalyzer.
3. the preparation method of nanometer carbon tube tungsten carbide catalyzer as claimed in claim 2, it is characterized in that the described spray-dired condition of step (2) is: the inlet flow velocity is 5～40mL/min, the air intake flow velocity is 400～800L/h, the inlet nozzle temperature of hot air nozzle is 160～250 ℃, and tail gas exit temperature is 80～120 ℃.
4. the preparation method of nanometer carbon tube tungsten carbide catalyzer as claimed in claim 2, the volume ratio that it is characterized in that described carbon monoxide of step (3) and carbon dioxide is 7～15:1, the gaseous mixture flow velocity is 0.25～0.55m/S.
5. the preparation method of nanometer carbon tube tungsten carbide catalyzer as claimed in claim 4 is characterized in that the described calcination temperature of step (3) is 400～500 ℃, and the calcination time is 0.5～4 hour.
6. the preparation method of nanometer carbon tube tungsten carbide catalyzer as claimed in claim 5 is characterized in that the described reduction and carbonization reaction temperature of step (3) is 700～1000 ℃, and the reduction and carbonization reaction time is 5～15 hours.
7, the preparation method of nanometer carbon tube tungsten carbide catalyzer as claimed in claim 2 is characterized in that the carbon pipe described in the step (1) is scattered in the concentrated nitric acid solution behind the backflow purifying, and post processing obtains the carbon pipe behind the purifying for washing, drying.
8. the preparation method of nanometer carbon tube tungsten carbide catalyzer as claimed in claim 2 is characterized in that described preparation method comprises the steps:
(1) the carbon pipe being scattered in mass concentration is in 67% the concentrated nitric acid solution, 95～150 ℃ of following backflow purifying 2～10 hours, and the carbon pipe after supercooling, washing, filtration, drying obtain purifying;
(2) the carbon pipe behind the purifying is distributed in the tungsten aqueous metal salt,, reactant liquor is imported carry out spray-drying in the spray dryer, obtain tungsten slaine/carbon tube particle presoma 80～120 ℃ of stirring reactions 4～10 hours; Described tungsten slaine is sulfo-ammonium tungstate or six carboxyl tungsten, and the mass ratio of described carbon pipe and tungsten slaine is 1:1～20; Described spray-dired condition is: the inlet flow velocity is 20mL/min, and the air intake flow velocity is 600L/h, and the inlet nozzle temperature of hot air nozzle is 200 ℃, and tail gas exit temperature is 100 ℃.
(3) be that carbon monoxide and the carbon dioxide mix gas of 8～12:1 is reduction and carbonization atmosphere with volume ratio; described gaseous mixture flow velocity is 0.25～0.55m/S; with the resulting tungsten slaine of step (2)/carbon tube particle presoma in 450 ℃ of reduction and carbonization atmosphere, carry out calcination 1～3 hour, carried out reduction and carbonization 9～10 hours at 700～800 ℃ again; question response finishes; under the protection of inert gas, product is cooled to room temperature, obtains described nanometer carbon tube tungsten carbide catalyzer.
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| CN103056377B (en) * | 2013-01-04 | 2015-07-01 | 湖南顶立科技有限公司 | Method for manufacturing nanometer tungsten/cobalt carbide composite powder |
| CN103785377B (en) * | 2013-11-15 | 2016-05-18 | 浙江工业大学 | A kind of tungsten carbide montmorillonite composite catalyst and preparation method thereof |
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| CN111326749B (en) * | 2018-12-14 | 2021-06-18 | 中国科学院福建物质结构研究所 | Co-supported carbon nano catalytic material with tungsten carbide |
| CN109603813B (en) * | 2019-01-03 | 2021-09-07 | 江西理工大学 | Preparation method of micro/nano spherical tungsten oxide high-efficiency photocatalyst |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1628903A (en) * | 2004-10-13 | 2005-06-22 | 浙江工业大学 | Tungsten carbide catalyst and its preparation method and special retort |
| WO2005124916A2 (en) * | 2004-06-10 | 2005-12-29 | California Institute Of Technology | Processing techniques for the fabrication of solid acid fuel cell membrane electrode assemblies |
| CN1772970A (en) * | 2005-11-03 | 2006-05-17 | 武汉化工学院 | Process for producing metal-base nano-composite cladding material |
| CN1785898A (en) * | 2005-11-03 | 2006-06-14 | 武汉化工学院 | Preparation method of nano-carbon tube-nano tungston carbide composite powder |
| JP2006240957A (en) * | 2005-03-07 | 2006-09-14 | Showa Denko Kk | Conductive silicon carbide ceramic and its manufacturing method |
-
2007
- 2007-09-30 CN CNB2007101562222A patent/CN100493709C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005124916A2 (en) * | 2004-06-10 | 2005-12-29 | California Institute Of Technology | Processing techniques for the fabrication of solid acid fuel cell membrane electrode assemblies |
| CN1628903A (en) * | 2004-10-13 | 2005-06-22 | 浙江工业大学 | Tungsten carbide catalyst and its preparation method and special retort |
| JP2006240957A (en) * | 2005-03-07 | 2006-09-14 | Showa Denko Kk | Conductive silicon carbide ceramic and its manufacturing method |
| CN1772970A (en) * | 2005-11-03 | 2006-05-17 | 武汉化工学院 | Process for producing metal-base nano-composite cladding material |
| CN1785898A (en) * | 2005-11-03 | 2006-06-14 | 武汉化工学院 | Preparation method of nano-carbon tube-nano tungston carbide composite powder |
Non-Patent Citations (2)
| Title |
|---|
| WC/CNT纳米复合材料制备及其对甲醇氧化的电催化性能. 李国华等.物理化学学报，第23卷第9期. 2007 * |
| WC/纳米碳管复合材料制备及其电化学性能. 马淳安等.化学学报，第64卷第20期. 2006 * |
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