CN102188983B - Fibrous nano porous V2O5-K2SO4 / composite carrier catalyst and application thereof - Google Patents

Fibrous nano porous V2O5-K2SO4 / composite carrier catalyst and application thereof Download PDF

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CN102188983B
CN102188983B CN 201110084434 CN201110084434A CN102188983B CN 102188983 B CN102188983 B CN 102188983B CN 201110084434 CN201110084434 CN 201110084434 CN 201110084434 A CN201110084434 A CN 201110084434A CN 102188983 B CN102188983 B CN 102188983B
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fiber
matrix material
catalyst
ordered structure
nano porous
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CN102188983A (en
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吴强
吴江
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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Shanghai University of Electric Power
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Abstract

The invention discloses a fibrous nano porous V2O5-K2SO4 / composite carrier catalyst and a preparation method thereof. According to a nano carbon fiber template technology, fibrous nano porous metallic oxides can be first solidified on orderly structured macroscopic matrix materials to obtain composite carriers; then composite carrier coatings are loaded with corresponding active ingredients V2O5-K2SO4, so finally the fibrous nano porous V2O5-K2SO4 / composite carrier catalyst is obtained. The fibrous nano porous V2O5-K2SO4 / composite carrier catalyst of the present invention has strong adsorption and catalysis performance, and can overcome various abuses, such as pressure drop, heat transfer, low contact efficiency and difficulty in separating catalyst, caused by using a traditional nano powder catalyst in a catalytic reaction, so as to more efficiently reduce soot particle discharged from diesel vehicle tail gas.

Description

Fibrous nano porous V 2O 5-K 2SO 4/ composite carried catalyst and application thereof
Technical field
This invention relates to the fibrous nano porous V of carbon black granules in a kind of high-performance catalytic oxidation exhaust gas from diesel vehicle 2O 5-K 2SO 4/ composite carried catalyst belongs to inorganic catalysis material field.
Background technology
Carbon nano-fiber not only has low-density, high specific strength, high conduction and thermal conductivity, strong corrosion resistant and the performance such as high temperature resistant, have also simultaneously that defects count is few concurrently, specific area is large and the advantage such as compact structure, thereby be with a wide range of applications at catalyst and catalyst carrier, high-efficiency adsorbent, prepare composite.In recent years, template is widely used on the preparations of nanomaterials because it has the plurality of advantages such as pattern, structure, size orientation of easy, economic, the repeated height of method and product be controlled, and carbon nano-fiber is a kind of mould material with potential application foreground, and it can be by standby the obtaining of technique chemical vapor deposition (CVD) legal system simple, with low cost.
Carbon black granules is one of major pollutants of emission of diesel engine, oneself has caused very large threat to urban atmosphere and public health, and the day by day quickening along with motor vehicle diesel, this trend will be more outstanding, and therefore the discharging tool of control and elimination exhaust gas from diesel vehicle carbon black granules is of great significance.Scientific research shows adopts oxidation catalyst that carbon black granules is oxidized to CO 2It is the major measure that effectively solves at present exhaust gas from diesel vehicle carbon black granules exhaust emission.
V 2O 5-K 2SO 4Series catalysts has eutectic point and runny characteristic because of it, be easy to realize the close contact of carbon black granules and catalyst, thereby have the reactivity worth of excellent catalytic oxidation carbon black granules, but this catalyst can not be in a large number and equably coating load on the macroscopical matrix material that possesses ordered structure such as vermiculite, hydrotalcite, rod-like fibre, honeycomb ceramic body and porous anodic alumina films (AAO).Therefore, actively to develop and develop new technology with high-quality and high-performance sample and new technology be that researchers are insistent always pursues a goal.
Adopt the carbon nano-fiber mould plate technique fibrous nano porous metal oxide to be solidificated on macroscopical matrix material of ordered structure first, obtain composite with this, after with composite as the corresponding active component V of carrier coating load 2O 5-K 2SO 4, and then obtain fibrous nano porous V 2O 5-K 2SO 4/ composite carried catalyst.By optimizing preparation condition, finally can obtain the compound porous material of high-quality ordered structure macroscopic view matrix and microscopic particles, such material will have very strong absorption and catalytic performance, can overcome in the catalytic reaction the various drawbacks of using traditional nanometer powder catalyst to bring (being difficult to separate etc. with catalyst as Pressure Drop and hot problem of transmission and contacting efficiency are low), can more effectively reduce the discharging of carbon black granules in the exhaust gas from diesel vehicle, thereby have potential application prospect, have not yet to see the report of relevant this respect work.
Summary of the invention
One of purpose of this invention is to provide a kind of fibrous nano porous V in order to solve the variety of issue that brings in above-mentioned existing traditional nanometer powder catalyst use procedure 2O 5-K 2SO 4/ composite carried catalyst.
Two of purpose of the present invention is a kind of fibrous nano porous V of providing above-mentioned 2O 5-K 2SO 4The preparation method of/composite carried catalyst and the application in the discharging of carbon black granules in reducing exhaust gas from diesel vehicle thereof.
Fibrous nano porous V 2O 5-K 2SO 4/ composite carried catalyst, it is by being prepared as follows the method preparation:
(1), synthesize nano carbon fiber on ordered structure macroscopic view matrix material
Adopt chemical vapour deposition technique synthesize nano carbon fiber on macroscopical matrix material of ordered structure;
Namely make the catalyst activity component with metals such as Ni, Co, Fe, take macroscopical matrix material of ordered structure as carrier, CH 4, C 2H 4, the gas such as CO is as carbon source, the control gas flow is at 20-30 mL/min, temperature is at 550-600 ℃, reaction 2-3 h namely obtains being solidificated in the carbon nano-fiber on the ordered structure macroscopic view matrix material under the normal pressure;
Catalyst amount is 1% of macroscopical matrix material;
Macroscopical matrix material of described ordered structure is rod-like fibre, vermiculite, hydrotalcite, honeycomb ceramic body or porous anodic alumina films (AAO);
Macroscopical matrix material of preferred ordered structure is rod-like fibre;
Described rod-like fibre is preferably SiO 2Fiber or Al 2O 3Fiber;
(2), the preparation of complex carrier
Be solidificated in carbon nano-fiber on the ordered structure macroscopic view matrix material as template synthesis of metal oxide on macroscopical matrix material of ordered structure, to obtain complex carrier take step (1) gained;
Described metal oxide is Al 2O 3, TiO 2Or SiO 2
Being about to be solidificated in carbon nano-fiber template on the ordered structure macroscopic view matrix material, to be immersed in concentration be 5min in the corresponding slaine precursor liquid of 0.2-0.4moL/L, then suction filtration is in order to remove its surface excess solution, by 300 ℃ of dry 1h, repeat said process 3～4 times; In air, be higher than again 600 ℃ of lower roasting 6h and finally obtain complex carrier to remove the carbon nano-fiber template;
The complex carrier that is final gained is Al 2O 3/ ordered structure macroscopic view matrix material, TiO 2/ ordered structure macroscopic view matrix material or SiO 2/ ordered structure macroscopic view matrix material;
Described slaine precursor liquid is Al (NO 3) 3, Ti (OBu) 4, Si (OC 2H 5) 4
(3), V 2O 5-K 2SO 4The preparation of/composite carried catalyst
A certain amount of active component V of complex carrier coating load that step (2) is obtained 2O 5-K 2SO 4, and then obtain V 2O 5-K 2SO 4/ composite carried catalyst;
Namely under 80 ℃ of water-baths and stirring condition with a certain amount of NH 4VO 3Be dissolved in the deionized water with oxalic acid, then continue in solution, slowly to add a certain amount of K 2SO 4, after the stirring and dissolving until obtain dark blue solution;
NH wherein 4VO 3, oxalic acid, K 2SO 4Press NH with the proportioning of deionized water 4VO 3: oxalic acid: K 2SO 4: deionized water 3.2mol:3.2mol:1.6mol:1L calculates;
The Al that step (2) is obtained 2O 3/ SiO 2Fibre composite carrier is immersed in 1-2 h in the dark blue solution of above-mentioned gained, sample is dried 5-6h under 120 ℃ of conditions in baking oven subsequently, then take out and be positioned in the Muffle furnace, cool to room temperature obtained fibrous nano porous V after Muffle furnace rose to 350 ℃ of roasting 24 h with the heating rate of 8-10 ℃/min by room temperature 2O 5-K 2SO 4/ composite carried catalyst.
Beneficial effect of the present invention
Nano-porous fiber shape complex carrier/V of the present invention 2O 5-K 2SO 4Catalyst, a kind of macroscopical matrix porous material mutually compound with microscopic particulate, have very strong absorption and catalytic performance, can overcome the various drawbacks of using traditional nanometer powder catalyst to bring in the catalytic reaction, with hot problem of transmission and contacting efficiency is low is difficult to separate etc. with catalyst, can more effectively reduce the discharging of carbon black granules in the exhaust gas from diesel vehicle such as Pressure Drop.The present invention adopts chemical vapour deposition technique (CVD) synthesize nano carbon fibrous template, and its preparation technology is simple, with low cost and repeated high, can effectively regulate and control the formation of carbon nano-fiber template by the condition of control chemical vapour deposition (CVD); The nano-porous fiber shape complex carrier/V that the present invention relates to 2O 5-K 2SO 4The preparation technology of catalyst is simple, selected raw material wide material sources, with low cost, so decrease its production cost.By optimizing preparation process condition, finally can obtain the compound porous material of high-quality ordered structure macroscopic view matrix and microscopic particles, such material can reduce the discharging of carbon black granules in the exhaust gas from diesel vehicle effectively, has potential application prospect.
Description of drawings
Fig. 1, SiO 2The ESEM of carbon nano-fiber diagram on the fiber
Fig. 2, Al 2O 3The ESEM of carbon nano-fiber diagram on the fiber
Fig. 3, Al 2O 3/ SiO 2The ESEM diagram of fibre composite carrier
Fig. 4, Al 2O 3/ Al 2O 3The ESEM diagram of fibre composite carrier
Fig. 5, V 2O 5-K 2The ESEM diagram of SO4/ composite carried catalyst
The catalytic oxidation performance the effects of Fig. 6, carbon black granules.
The specific embodiment
Purify below by embodiment and the emission of diesel engine carbon black granules that by reference to the accompanying drawings this invention provided and to use fibrous nano porous V 2O 5-K 2SO 4/ composite carried catalyst is described further, but does not limit the present invention.
The TG-DTA analyzer that the present invention is used, model TG8120, Rigaku Co., Ltd.;
The field emission electron flying-spot microscope that the present invention is used, model JSM-7400, Japanese JEOL;
It is pure that the used various reagent of the present invention are reagent, is Japanese Taihei, and Sangyo provides.
Embodiment 1
(1), synthesize nano carbon fiber on ordered structure macroscopic view matrix material
1., SiO 2Synthesize nano carbon fibrous template on the fiber
Make the catalyst activity component with metal Ni, with SiO 2Fiber is carrier, with CH 4Gas is as carbon source, and the control gas flow is at 20 mL/min, and temperature is at 550 ℃, and reaction 2h obtains being solidificated in SiO under the normal pressure 2Carbon nano-fiber on the fiber;
Gained be solidificated in SiO 2The scanning electron microscope (SEM) photograph of the carbon nano-fiber on the fiber as shown in Figure 1, carbon nano-fiber is a large amount of and be solidificated in uniformly SiO as can be seen from Figure 1 2On the fiber, its diameter distributes between 40-70nm;
2., Al 2O 3Synthesize nano carbon fibrous template on the fiber
According to above-mentioned SiO 2The method of synthesize nano carbon fibrous template is at Al on the fiber 2O 3Synthesize nano carbon fibrous template on the fiber;
Gained be solidificated in Al 2O 3The scanning electron microscope (SEM) photograph of the carbon nano-fiber on the fiber as shown in Figure 2, carbon nano-fiber is a large amount of and be solidificated in uniformly Al as can be seen from Figure 2 2O 3On the fiber, its diameter distributes between 60-100nm;
(2), the preparation of complex carrier
1., Al 2O 3/ SiO 2The preparation of fibre composite carrier
Make solvent with ethanol, prepare the Al (NO of 0.3 moL/L 3) 3.9H 2O solution is with the above-mentioned SiO that is solidificated in 2Carbon nano-fiber on the fiber is immersed in institute and joins in the solution, then through suction filtration and 300 ℃ of dry processing, repeat again above operation 3 times after being cooled to room temperature, at last products therefrom is positioned in the Muffle furnace, Muffle furnace rises to 650 ℃ with the heating rate of 10 ℃/min by room temperature, and insulation and roasting 5 h finally obtain Al in order to burn the carbon nano-fiber template 2O 3/ SiO 2Fibre composite carrier;
The Al of gained 2O 3/ SiO 2The scanning electron microscope (SEM) photograph of fibre composite carrier can be found out fibrous nano Al from Fig. 3 as shown in Figure 3 2O 3A large amount of and uniform coating load is at SiO 2On the fiber, obtain macroscopical matrix porous material mutually compound with microscopic particulate;
2., Al 2O 3/ Al 2O 3The preparation of fibre composite carrier
According to above-mentioned Al 2O 3/ SiO 2The preparation method of fibre composite carrier prepares Al 2O 3/ Al 2O 3Fibre composite carrier;
The Al of gained 2O 3/ Al 2O 3The scanning electron microscope (SEM) photograph of fibre composite carrier as shown in Figure 4, fibrous nano Al as can be seen from Figure 4 2O 3A large amount of and uniform coating load is at Al 2O 3On the fiber, obtain macroscopical matrix porous material mutually compound with microscopic particulate.
(3),V 2O 5-K 2SO 4The preparation of/composite carried catalyst
Under 80 ℃ of water-baths and the stirring condition with 9.3 g NH 4VO 3Be dissolved in the 25 mL deionized waters with 7.2 g oxalic acid, then continue in solution, slowly to add 6.96 g K 2SO 4After the stirring and dissolving until obtain dark blue solution.With the 1. resulting Al in the above-mentioned steps (2) 2O 3/ SiO 2Fibre composite carrier is immersed in institute and joins 1 h in the solution, sample is dried 6 h under 120 ℃ of conditions in baking oven subsequently, then taking-up is positioned in the Muffle furnace, and Muffle furnace rises to 350 ℃ with the heating rate of 10 ℃/min by room temperature, and cool to room temperature obtains V behind insulation and roasting 24 h 2O 5-K 2SO 4/ composite carried catalyst;
The V of gained 2O 5-K 2The scanning electron microscope (SEM) photograph of SO4/ composite carried catalyst as shown in Figure 5, fibrous nano V as can be seen from Fig. 2O 5-K 2SO 4A large amount of and uniform coating load is at Al 2O 3/ SiO 2On the fibre composite carrier, obtain macroscopical matrix porous material mutually compound with microscopic particulate.
Embodiment 2
V 2O 5-K 2SO 4The experiment of/composite carried catalyst catalytic oxidation carbon black granules
The experiment of the catalytic oxidation performance of carbon black granules is undertaken by the TG-DTA analyzer, and its operation is as follows: the V that embodiment 1 is finally prepared 2O 5-K 2SO 4/ complex carrier (Al 2O 3/ SiO 2Fibre composite carrier) catalyst and carbon black granules maintenance weight ratio is 1:10, behind mixed grinding, be positioned in the crucible of TG-DTA analyzer, reaction system rises to 700 ℃ of variations of observing thermogravimetric curve with the heating rate of 10 ℃/min by room temperature, continue to pass into air in this process as oxidant, flow control is 30 mL/min.Other gets the α-Al of identical weight ratio 2O 3Compare experiment with the carbon black granules mixture, other condition is consistent.
Experimental result as shown in Figure 6, α-Al as can be seen from Figure 6 2O 3On, the initiation temperature of carbon black granules is near 510 ℃, and V 2O 5-K 2SO 4/ complex carrier (Al 2O 3/ SiO 2Fibre composite carrier) on the catalyst, the initiation temperature of carbon black granules is 310 ℃, so V 2O 5-K 2SO 4/ composite carried catalyst can obviously reduce the initiation temperature of carbon black granules.Because V 2O 5-K 2SO 4/ composite carried catalyst is the compound porous material of a kind of macroscopical matrix and microscopic particles, the various drawbacks of using traditional nanometer powder catalyst to bring (being difficult to separate etc. with catalyst as Pressure Drop and hot problem of transmission and contacting efficiency are low) can be evaded in the catalytic reaction, thereby the discharging of carbon black granules in the exhaust gas from diesel vehicle can be effectively reduced.
In sum, adopt the carbon nano-fiber mould plate technique fibrous nano porous metal oxide to be solidificated on macroscopical matrix material of ordered structure first, and then obtain composite, then can be with fibrous nano V by infusion process 2O 5-K 2SO 4Coating load is on above-mentioned composite.By optimizing preparation condition, finally can obtain the compound porous material of high-quality ordered structure macroscopic view matrix and microscopic particles, such material will have very strong absorption and catalytic performance, can effectively overcome the various drawbacks of using traditional nanometer powder catalyst to bring in the catalytic reaction, thereby can more effectively reduce the discharging of carbon black granules in the exhaust gas from diesel vehicle, have potential application prospect.This invention equipment is simple, operating condition is easy to control, repeatability is high, with low cost, economic results in society are remarkable, is conducive to it and applies.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (7)

1. fibrous nano porous V 2O 5-K 2SO 4/ composite carried catalyst is characterized in that it passes through such as the below
Legal system is standby:
(1), synthesize nano carbon fiber on ordered structure macroscopic view matrix material
Make the catalyst activity component with Ni, Co or Fe metal, take macroscopical matrix material of ordered structure as carrier, with CH 4, C 2H 4Or CO gas is as carbon source, and the control gas flow is at 20-30 mL/min, and temperature is at 550-600 ℃, and reaction 2-3h can obtain being solidificated in the carbon nano-fiber on the ordered structure macroscopic view matrix material under the normal pressure;
Amount of metal catalyst is 1% of macroscopical matrix material;
Macroscopical matrix material of described ordered structure is rod-like fibre, vermiculite, hydrotalcite, honeycomb ceramic body or porous anodic alumina films (AAO);
Described rod-like fibre is SiO 2Fiber or Al 2O 3Fiber;
(2), the preparation of complex carrier
Take step (1) gained be solidificated in carbon nano-fiber on the ordered structure macroscopic view matrix material as template synthesis of metal oxide on macroscopical matrix material of ordered structure, obtain complex carrier;
Described metal oxide is Al 2O 3, TiO 2Or SiO 2
(3), V 2O 5-K 2SO 4The preparation of/composite carried catalyst
Under 80 ℃ of water-baths and stirring condition with a certain amount of NH 4VO 3Be dissolved in the deionized water with oxalic acid, then continue in solution, slowly to add a certain amount of K 2SO 4, after the stirring and dissolving until obtain dark blue solution;
NH wherein 4VO 3, oxalic acid, K 2SO 4Press NH with the proportioning of deionized water 4VO 3: oxalic acid: K 2SO 4: deionized water 3.2mol:3.2mol:1.6mol:1L calculates;
The complex carrier that step (2) is obtained is immersed in 1-2h in the dark blue solution of above-mentioned gained, sample is dried 5-6h under 120 ℃ of conditions in baking oven subsequently, then take out and be positioned in the Muffle furnace, Muffle furnace rises to cool to room temperature behind 350 ℃ of roasting 24h with the heating rate of 8-10 ℃/min by room temperature, finally obtains fibrous nano porous V 2O 5-K 2SO 4/ composite carried catalyst.
2. a kind of fibrous nano porous V as claimed in claim 1 2O 5-K 2SO 4/ composite carried catalyst, it is characterized in that the preparation of described complex carrier, being about to the carbon nano-fiber on the ordered structure macroscopic view matrix material of being solidificated in of step (1) gained, to be immersed in concentration be 5min in the corresponding slaine precursor liquid of 0.2-0.4mol/L, then suction filtration is in order to remove its surface excess solution, by 300 ℃ of dry 1h, repeat said process 3～4 times; In air, be higher than again 600 ℃ of lower roasting 6h and finally obtain complex carrier to remove the carbon nano-fiber template;
Described slaine precursor liquid is Al (NO 3) 3, Ti (OBu) 4Or Si (OC 2H 5) 4
3. a kind of fibrous nano porous V as claimed in claim 1 or 2 2O 5-K 2SO 4/ composite carried catalyst,
It is characterized in that described complex carrier is Al 2O 3/ ordered structure macroscopic view matrix material, TiO 2/ tie in order
Structure macroscopic view matrix material or SiO 2/ ordered structure macroscopic view matrix material.
4. a kind of fibrous nano porous V as claimed in claim 3 2O 5-K 2SO 4/ composite carried catalyst is characterized in that macroscopical matrix material of the ordered structure in the described complex carrier is preferably rod-like fibre.
5. a kind of fibrous nano porous V as claimed in claim 4 2O 5-K 2SO 4/ composite carried catalyst is characterized in that described rod-like fibre is preferably SiO 2Fiber or Al 2O 3Fiber.
6. a kind of fibrous nano porous V as claimed in claim 1 or 2 2O 5-K 2SO 4/ composite carried catalyst is used
The discharging of carbon black granules in reducing exhaust gas from diesel vehicle.
7. a kind of fibrous nano porous V as claimed in claim 5 2O 5-K 2SO 4/ composite carried catalyst is used
The discharging of carbon black granules in reducing exhaust gas from diesel vehicle.
CN 201110084434 2011-04-06 2011-04-06 Fibrous nano porous V2O5-K2SO4 / composite carrier catalyst and application thereof Expired - Fee Related CN102188983B (en)

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CN102716738B (en) * 2012-06-21 2014-06-25 上海电力学院 Fibrous nano-porous catalyst, preparation method thereof and application
CN102874875A (en) * 2012-10-08 2013-01-16 上海电力学院 Nano-porous WO3 with ordered macroscopic structure and preparation method thereof
CN109395528B (en) * 2017-08-15 2021-05-11 中国石油化工股份有限公司 Active agent, preparation method and application thereof

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN101462066A (en) * 2008-03-11 2009-06-24 郑州大学 Catalyst for preparing naphthaquinone and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462066A (en) * 2008-03-11 2009-06-24 郑州大学 Catalyst for preparing naphthaquinone and preparation method thereof

Non-Patent Citations (1)

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Title
A.Kaszonyi et al.,.Changes in properties of V2O5-K2SO4-SiO2 catalysts in air, hydrogen and toluene vapors.《Applied Catalysis A：General》.1999,第184卷103-113. *

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