CN105060861B - There is the porous ceramicss class catalyst carrier in two-dimensional nano duct and preparation method thereof - Google Patents
There is the porous ceramicss class catalyst carrier in two-dimensional nano duct and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of have the porous ceramicss class catalyst carrier in two-dimensional nano duct and preparation method thereof.The Main Ingredients and Appearance of this catalyst carrier is Al2O3、SiO2Or TiO2In one of which, with the Bacterial cellulose modified through acrylic surface as pore creating material, the porosity is 5% 65%, and aperture is 50nm 300nm, and specific surface area is 20m2/g‑130m2/g.The porous ceramicss class catalyst carrier that the present invention has two-dimensional nano duct takes following steps to prepare：Main inclusion stock is processed, Bacterial cellulose is modified, idiosome sintering, idiosome modification Four processes；The present invention has inside the porous ceramicss class catalyst carrier in two-dimensional nano duct containing both ends open, two dimension nanoscale pore passage structure；The preparation method that the present invention has the porous ceramicss class catalyst carrier in two-dimensional nano duct is simple, and pore creating material is natural nanoscale Organic substance, will not produce noxious substance, meet environmental requirement during production and use.
Description
Technical field
The invention belongs to technical field of inorganic non-metal material preparation, specifically, it is to be related to one kind with Al2O3、SiO2Or
Person TiO2For primary raw material, with the Bacterial cellulose modified through acrylic surface as pore creating material, there is two-dimensional nano duct
Porous ceramicss class catalyst carrier and preparation method thereof.
Background technology
Catalyst carrier can support active component in catalytic reaction process, makes catalyst have specific physical aspect,
But carrier itself does not have catalysis activity.Traditional catalyst carrier mainly includes natural ore species, adsorbent class, glass
Class, high molecular polymerization species etc., and porous ceramicss class catalyst carrier due to have high-specific surface area, high temperature resistant, heat shock resistance,
Corrosion-resistant the advantages of, become the catalyst carrier type receiving significant attention in recent years.
Porous ceramicss class catalyst carrier species is more, is wherein had relatively using the porous ceramicss that organic foam prepares
High open-cell porosity, is one of catalyst carrier species of being most widely used, but its pore-size is larger, typically up to
100 μm of -5mm, and a large amount of toxic gas pollution environment can be produced in preparation process, do not meet environmental requirement
[Maldonado-Hodar F. J., Morales-Torres S., Ribeiro F. Development of carbon
coatings for cordierite foams: an alternative to cordierite honeycombs,
Langmuir, 2008, 24(7);He Xiulan, Yang Yitian, Yang Yue, royal power peak, Qi Haonan, rushes pleasure. Polymeric sponge method
Preparation Al2O3Porous ceramicss and its performance study, Chinese pottery, 2014,7；Shang Jingli, Dai Binyu, Vera Wang. organic foam soaks
Stain method prepares ZrO2Foamed ceramics sintering Process, silicate is circulated a notice of, and 2011,1；Strict and impartial, Chen Yanlin, Peng Shaoxian, Jiang Jiuxin,
Chang Ying. Foam dipping method prepares porous Ti2The method of AIN pottery, publication number：CN102372499A].
By adding the porous ceramicss that the pore creating materials such as coal dust, graphite, starch, carbamide, sodium carboxymethyl cellulose are fired
Can also use as catalyst carrier, but be affected by the impact of pore creating material particle size and profile, it prepares gained porous pottery
The pore of porcelain is mostly held one's breath hole, and aperture is usually 5 μm of -1mm, and the uniformity of gas cell distribution is also poor simultaneously, limits the type
Range of application [Ogiwara T., Noda Y., the Kimura O. Fabrication of high of catalyst carrier
density cordierite ceramics using a coal fly, Journal of the Ceramic Society
of Japan, 2010, 118(1375)；Woods star pump, Wu Renping, Yu Yan, Zeng Zhaowang. the preparation of cordierite porous ceramicss and
Performance study, Chinese pottery, 2012,48 (2)；Sandoval M. L., Talou M. H., Souto P. M.,
Kiminami R. H. G. A., Camerucci M. A. Microwave sintering of cordierite
precursor green bodies prepared by starch consolidation, Ceramics
International, 2011, 37(4);Zeng Yuping, Cao Jianwu. a kind of preparation method of poruos material in micro-nano magnitude, public
The number of opening：CN1686949A].
Utilize sol-gel technology can also prepare porous ceramicss class carrier for supported catalyst, but the method life
Product efficiency is low, process conditions are wayward it is impossible to efficient preparation has the porous ceramicss class catalyst in even level aperture
Carrier [Zhao Yueqing, Zhao Hailei, beam quintessence, Jia Qianyi, Shen Yi, Zhang Bobo. Cuo (CoO, MnO)/SiO2Nano combined airsetting
The preparation of glue catalyst carrier and its application in diphenyl carbonate synthesis, silicate journal, 2009,11；Zhang Lili, Zhang Yong
Bright. porous ceramicss load TiO2Photocatalyst for degrading methylene blue, Chinese pottery, 2011,12；Gong Cairong, peaceful Yunlong, Liu Jia
Outstanding person, Fan Guo. fibrous template method preparation SiOC porous ceramicss load La0.9Sr0.1CoO3Nano-particle catalyst, publication number：
CN102836732A].
In addition, extrusion moulding is also the common methods preparing porous ceramicss class catalyst carrier, not only pore opening can
Control, and can continuously produce, but because mould difficulty of processing is big, is unsuitable for producing that specific surface area is larger, have two wieners
Metre hole road carrier material [Gong Guoli, Liu Lili, Wang Na. a kind of preparation method of the porous ceramicss of the fixing slime bacteria of absorption,
Publication number：CN103030420A；Fu Weifeng, Tang Zhuxing, Wang Jixuan. the performance of extrusion molding porous ceramicss and application, modern skill
Art pottery, 2007,1；Shi Limin, Zhao Hongsheng, Yan Yinghui, Tang Chun and. open-pored porous pottery technology of preparing, material engineering,
2005,12； Shamshuddin S. Z. M., Sundar M. S., Thimmaraju N. Synthesis,
characterization and catalytic activity studies on cordierite honeycomb
coated with ZrO2based solid super acids, Comptes rendus chimie, 2012, 15
(9)].
Content of the invention
The technical problem to be solved is for the existing porous ceramicss class catalysis with two-dimensional nano duct
Difficulty is larger for agent carrier preparation, under low production efficiency the problems such as, provide a kind of porous ceramicss class with two-dimensional nano duct to urge
Agent carrier and preparation method thereof.The porous ceramicss class catalyst carrier with two-dimensional nano duct of the present invention is with Al2O3、
SiO2Or TiO2In one of which be primary raw material, be pore creating material using the Bacterial cellulose modified through acrylic surface
And be prepared from through silane coupler modified.Bacterial cellulose is to be interweaved by the fibre bundle of diameter 40nm-50nm to form
And there is network structure, uniform moisture can be formed with ceramic powder, dispersant and sintering aid after surface modification and dissipate
System, can be internally formed open cell type two-dimensional nano duct structure in catalyst carrier after high-temperature process.Using party's legal system
Standby go out the advantage of the porous ceramicss class catalyst carrier with two-dimensional nano duct mainly include that aperture is little, uniform pore diameter, open
Porosity height etc..
For solving above-mentioned technical problem, the present invention employs the following technical solutions：
The porous ceramicss class catalyst carrier with two-dimensional nano duct is with ceramic powder（Al2O3、SiO2Or TiO2
In one of which）For primary raw material, with the Bacterial cellulose modified through acrylic surface as pore creating material, at 600 DEG C -800
Sinter at a temperature of DEG C and form through silane coupler modified, obtain the porous ceramicss class catalyst with two-dimensional nano duct
The porosity of carrier is 5%-65%, and aperture is 50nm-300nm, and specific surface area is 20m2/g-130m2/ g, wherein open pore account for
The ratio of total pore reaches more than 80%.
There is the preparation method of the porous ceramicss class catalyst carrier in two-dimensional nano duct, step is as follows：
(1) ceramic powder, dispersant and sintering aid are weighed rear mix homogeneously according to weight proportion and obtain stock, its
The weight proportion of middle ceramic powder, dispersant and sintering aid is：
Ceramic powder 85wt%-95wt%
Dispersant 1.0wt%-5.0wt%
Sintering aid 4.0wt%-10wt%
(2) by the stock obtaining and carry out ball-milling treatment, thus the size by ceramic powder, dispersant and sintering aid
It is down to micro/nano level；
(3) using ultrasonic Treatment, Bacterial cellulose is dispersed in the aqueous solution of ethanol, then Deca acrylic acid
Bacterial cellulose is carried out with surface modification, modified Bacterial cellulose absolute ethanol washing and dry under the conditions of 45 DEG C to
Moisture content is less than 1.0%；
(4) utilize mechanical agitation, micro/nano level ceramic powder that modified Bacterial cellulose and step (2) are obtained,
Dispersant and sintering aid mix homogeneously simultaneously add distilled water and make aqueous dispersion；
(5) then filter cake is dried to moisture content under the conditions of 60 DEG C by vacuum filtration step (4) gained aqueous dispersion
Less than 1.0%, obtain idiosome；
(6) dried idiosome is put into sintering in Muffle furnace, sintering temperature is 600 DEG C -800 DEG C, and temperature retention time is
1h-3h；
(7) pH value with hydrochloric acid regulation ethanol is that 3-4 obtains ethanol-hydrogen chloride system at normal temperatures, then will be silane coupled
Agent is added to the mixed solution obtaining silane coupler and ethanol-hydrogen chloride in ethanol-hydrogen chloride system, and wherein silane coupler is in second
It is hydrolyzed in alcohol-hydrochloric acid system and obtains silanol, hydrolysis is thoroughly masked as the mixing of silane coupler and ethanol-hydrogen chloride system
Solution clear；
(8) idiosome after the sintering obtaining step (6) immerses silane coupler and the ethanol-hydrogen chloride that step (7) obtains
Carry out surface modification, modified sintering idiosome absolute ethanol washing in the mixed solution of system；
(9) the sintering idiosome after washing is dried under the conditions of 75 DEG C and is less than 1.0% to moisture content, be obtained and there are two wieners
The porous ceramicss class catalyst carrier in metre hole road.
In described step (1), ceramic powder is Al2O3、SiO2Or TiO2In one of which, dispersant be polypropylene
One of which in acid, ammonium polyacrylate, sodium polyacrylate or polyacrylic acid potassium, sintering aid is starch.
In described step (2), rotational speed of ball-mill is 300r/min, ceramic powder after ball-milling treatment, dispersant and sintering
The particle diameter of auxiliary agent is 500nm-1 μm.
In described step (3), by Bacterial cellulose, under conditions of power is for 300w, ultrasonic Treatment 120s makes it uniform
It is scattered in the ethanol-water solution that mass fraction is 75%；Often modified 1.0g Bacterial cellulose needs 50mL ethanol-water solution and drips
Plus 4 ~ 7mL acrylic acid, the reaction temperature of described surface modification is 60 DEG C, the response time is 3h, mechanical agitation rotating speed is 60r/
Min, the chemical equation of surface modification is as follows：
.
In described step (4), churned mechanically rotating speed is 120r/min, and the time is 300s；Every 100g micro/nano level ceramics
Body, dispersant and sintering aid can add modified bacteria cellulose 1.0g-20.0g, distilled water 100-300mL.
The heating rate of described step (6) sintering process is 5 DEG C/min, and wherein the temperature retention time at 105 DEG C is 30min.
Described step (7) silane coupler is 1 with the volume ratio of ethanol-hydrogen chloride system:9, the hydrolysis of silane coupler is anti-
Answer equation as follows：
；
In formula：X is hydrophobic group, for example, can be 3- (2,3- glycidoxy), 3- methacryloxy etc..
In described step (8), often the idiosome after modified 1.0g sintering, needs 10mL silane coupler and ethanol-hydrogen chloride
Mixed solution, reaction temperature during surface modification is 60 DEG C, and the response time is 2h, and mechanical agitation rotating speed is 60r/min, and surface changes
Property reaction equation is as follows：
；
Wherein：X is hydrophobic group, for example, can be 3- (2,3- glycidoxy), 3- methacryloxy etc., Y
For Al2O3、SiO2Or TiO2In one of which.
The beneficial effects of the present invention is：(1) the invention provides a kind of obtain even level two by low-temperature sintering
The effective way of dimension pore passage structure；(2) the invention provides one kind has nano-scale two-dimensional duct, high apparent porosity and big
The porous ceramicss class catalyst carrier of the construction featuress such as specific surface area；(3) present invention is carried out to Bacterial cellulose using acrylic acid
Surface modification, it is possible to reduce the formation of hydrogen bond between due to surface hydroxyl and the Bacterial cellulose that leads to are reunited and improved it in pottery
Dispersibility in matrix；(4) present invention, with acrylic acid modified Bacterial cellulose as pore creating material, not only obtains in ceramic matrix
Equally distributed nano-scale two-dimensional duct, it also avoid the harmful gass producing in conventional pore creating material combustion process simultaneously；(5)
The present invention is modified to catalyst carrier using silane coupler to improve its crystallized ability to catalyst such as silver；(6) originally
The preparation method that invention has the porous ceramicss class catalyst carrier in two-dimensional nano duct is simple, is easily combined with prior art, can
Realize industrialized production.
Specific embodiment
Describe technical scheme in detail with reference to embodiment, but protection domain is not limited thereto.
Embodiment 1
The preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct of the present embodiment is as follows：
（1）Take the Al of 85.0g2O3As ceramic powder, 5.0g sodium polyacrylate as dispersant, 10.0g starch
As sintering aid, these three raw material mix homogeneously are obtained 100.0g stock；
（2）Mixing gained 100.0g stock is carried out with the ball-milling treatment of 24 hours, drum's speed of rotation is 300r/min, passes through
Al after process2O3, the particle diameter of sodium polyacrylate and starch be averagely down to 600nm-800nm, take 80.0g through the embryo of ball-milling treatment
Material is standby；
（3）In take 20.0g Bacterial cellulose to be positioned over ethanol-water solution that 1000mL mass fraction is 75%, using power
Ultrasonic Treatment 120s for 300w makes Bacterial cellulose dispersed, then this solution is placed in 60 DEG C of water-baths and heats and drip
Plus 80mL acrylic acid carries out 3h surface modification to Bacterial cellulose, in modifying process, need the mechanical agitation that rotating speed is 60r/min,
Modified Bacterial cellulose absolute ethanol washing 3 times is simultaneously dried to moisture content less than 1.0%, altogether under the conditions of 45 DEG C
20.7g；
（4）Take the acrylic acid modified Bacterial cellulose of 16.0g and step（2）Gained 80.0g mixes through the stock of ball milling
After be placed in 240mL distilled water, and carry out rotating speed be 120r/min, the time be 300s mechanical agitation, make Bacterial cellulose equal
Even it is distributed in stock；
（5）Vacuum filtration is carried out to the stock stirring, then drying is little to moisture content under the conditions of 60 DEG C by filter cake
In 1.0%, prepare 96.5g idiosome；
（6）Dried idiosome is put in Muffle furnace and is sintered, maximum temperature is 800 DEG C, temperature retention time is 1h, rises
Warm curve is：Heating rate is 5 DEG C/min, and wherein the temperature retention time at 105 DEG C is 30min, and after sintering, idiosome is 63.5g；
（7）PH value with hydrochloric acid regulation ethanol is that 3-4 obtains ethanol-hydrogen chloride system at normal temperatures, then by the 3- of 100mL
Methacryloxypropyl trimethoxy silane is added in the ethanol-hydrogen chloride system of 900mL and obtains 3- methacryloxypropyl
Base propyl trimethoxy silicane and the mixed solution of ethanol-hydrogen chloride, wherein 3- methacryloxypropyl trimethoxy silane
Ethanol-hydrogen chloride system is hydrolyzed and obtains silanol, hydrolysis is thoroughly masked as 3- methacryloxypropyl trimethoxy
Base silane and the mixed solution clear of ethanol-hydrogen chloride system；
（8）Take 635mL hydrolysis thoroughly 3- methacryloxypropyl trimethoxy silane and ethanol-hydrogen chloride system
Mixed solution, by step（6）In the 63.5g idiosome immersion mixed solution of sintering, using heating in water bath, reaction temperature is controlled to
60 DEG C, the response time is 2h, and mechanical agitation rotating speed is 60r/min, modification terminate after with absolute ethanol washing 3 times；
（9）Modified idiosome after absolute ethanol washing is dried under the conditions of 75 DEG C and is less than 1.0% to moisture content, be obtained
63.6g has the porous ceramicss class catalyst carrier in two-dimensional nano duct.
The porosity of the porous ceramicss class catalyst carrier with two-dimensional nano duct that the present embodiment is obtained is：62.5%,
Aperture is：50nm-150nm, specific surface area is 117 m2/g.
Embodiment 2
The preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct of the present embodiment is as follows：
（1）Take the SiO of 90.0g2As ceramic powder, 5.0g ammonium polyacrylate as dispersant, 5.0g starch make
For sintering aid, these three raw material mix homogeneously are obtained 100.0g stock；
（2）Mixing gained 100.0g stock is carried out with the ball-milling treatment of 36 hours, drum's speed of rotation is 300r/min, passes through
SiO after process2, the particle diameter of ammonium polyacrylate and starch be averagely down to 500nm-600nm, take 60.0g through the embryo of ball-milling treatment
Material is standby；
（3）In take 10.0g Bacterial cellulose to be positioned over ethanol-water solution that 500mL mass fraction is 75%, using power
Ultrasonic Treatment 120s for 300w makes Bacterial cellulose dispersed, then this solution is placed in 60 DEG C of water-baths and heats and drip
Plus 60mL acrylic acid carries out 3h surface modification to Bacterial cellulose, in modifying process, need the mechanical agitation that rotating speed is 60r/min,
Modified Bacterial cellulose absolute ethanol washing 3 times is simultaneously dried to moisture content less than 1.0%, altogether under the conditions of 45 DEG C
10.3g；
（4）Take the acrylic acid modified Bacterial cellulose of 6.0g and step（2）Gained 60.0g is after the stock of ball milling mixes
Be placed in 120mL distilled water, and carry out rotating speed be 120r/min, the time be 300s mechanical agitation, make Bacterial cellulose uniform
It is distributed in stock；
（5）Vacuum filtration is carried out to the stock stirring, then drying is little to moisture content under the conditions of 60 DEG C by filter cake
In 1.0%, prepare 65.9g idiosome；
（6）Dried idiosome is put in Muffle furnace and is sintered, maximum temperature is 600 DEG C, temperature retention time is 2h, rises
Warm curve is：Heating rate is 5 DEG C/min, and wherein the temperature retention time at 105 DEG C is 30min, and after sintering, idiosome is 51.8g；
（7）PH value with hydrochloric acid regulation ethanol is that 3-4 obtains ethanol-hydrogen chloride system at normal temperatures, then by the 3- of 100mL
（2,3- epoxy third oxygen）Propyl trimethoxy silicane is added in the ethanol-hydrogen chloride system of 900mL and obtains 3-（2,3- epoxy third
Oxygen）Propyl trimethoxy silicane and the mixed solution of ethanol-hydrogen chloride, wherein 3-（2,3- epoxy third oxygen）Propyl trimethoxy silicane
Ethanol-hydrogen chloride system is hydrolyzed and obtains silanol, hydrolysis is thoroughly masked as 3-（2,3- epoxy third oxygen）Propyl group trimethoxy
Base silane and the mixed solution clear of ethanol-hydrogen chloride system；
（8）Take 518mL hydrolysis thoroughly 3-（2,3- epoxy third oxygen）Propyl trimethoxy silicane and ethanol-hydrogen chloride system
Mixed solution, by step（6）In the 51.8g idiosome immersion mixed solution of sintering, using heating in water bath, reaction temperature is controlled to
60 DEG C, the response time is 2h, and mechanical agitation rotating speed is 60r/min, modification terminate after with absolute ethanol washing 3 times；
（9）Modified idiosome after absolute ethanol washing is dried under the conditions of 75 DEG C and is less than 1.0% to moisture content, be obtained
52.1g has the porous ceramicss class catalyst carrier in two-dimensional nano duct.
The porosity of a kind of porous ceramicss class catalyst carrier with two-dimensional nano duct that the present embodiment is obtained is：
37.2%, aperture is：200nm-300nm, specific surface area is 53 m2/g.
Embodiment 3
The preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct of the present embodiment is as follows：
（1）Take the TiO of 95.0g2As ceramic powder, 1.0g polyacrylic acid as dispersant, 4.0g starch conduct
Sintering aid, these three raw material mix homogeneously are obtained 100.0g stock；
（2）Mixing gained 100.0g stock is carried out with the ball-milling treatment of 18 hours, drum's speed of rotation is 300r/min, passes through
Al after process2O3, the particle diameter of sodium polyacrylate and starch be averagely down to 800nm-1 μm, take 80.0g through the stock of ball-milling treatment
Standby；
（3）In take 6.0g Bacterial cellulose to be positioned over ethanol-water solution that 300mL mass fraction is 75%, using power it is
Ultrasonic Treatment 120s of 300w makes Bacterial cellulose dispersed, then this solution is placed in 60 DEG C of water-bath heating Deca
42mL acrylic acid carries out 3h surface modification to Bacterial cellulose, the mechanical agitation needing rotating speed to be 60r/min in modifying process, changes
Property after Bacterial cellulose absolute ethanol washing 3 times and dry under the conditions of 45 DEG C to moisture content be less than 1.0%, 6.1g altogether；
（4）Take the acrylic acid modified Bacterial cellulose of 4.0g and step（2）Gained 80.0g is after the stock of ball milling mixes
Be placed in 80mL distilled water, and carry out rotating speed be 120r/min, the time be 300s mechanical agitation, so that Bacterial cellulose is uniformly divided
Cloth is in stock；
（5）Vacuum filtration is carried out to the stock stirring, then drying is little to moisture content under the conditions of 60 DEG C by filter cake
In 1.0%, prepare 84.2g idiosome；
（6）Dried idiosome is put in Muffle furnace and is sintered, maximum temperature is 650 DEG C, temperature retention time is 3h, rises
Warm curve is：Heating rate is 5 DEG C/min, and wherein the temperature retention time at 105 DEG C is 30min, and after sintering, idiosome is 71.9g；
（7）PH value with hydrochloric acid regulation ethanol is that 3-4 obtains ethanol-hydrogen chloride system at normal temperatures, then by the 3- of 100mL
(2,3- epoxy third oxygen) propyl trimethoxy silicane is added in the ethanol-hydrogen chloride system of 900mL and obtains 3- (2,3- epoxy third
Oxygen) propyl trimethoxy silicane and ethanol-hydrogen chloride mixed solution, wherein 3- (2,3- epoxy the third oxygen) propyl trimethoxy silicane
Ethanol-hydrogen chloride system is hydrolyzed and obtains silanol, hydrolysis is thoroughly masked as 3- (2,3- epoxy the third oxygen) propyl group trimethoxy
Base silane and the mixed solution clear of ethanol-hydrogen chloride system；
（8）Take 719mL hydrolysis thoroughly 3- (2,3- epoxy third oxygen) propyl trimethoxy silicane and ethanol-hydrogen chloride system
Mixed solution, by step（6）In the 71.9g idiosome immersion mixed solution of sintering, using heating in water bath, reaction temperature is controlled to
60 DEG C, the response time is 2h, and mechanical agitation rotating speed is 60r/min, modification terminate after with absolute ethanol washing 3 times；
（9）Modified idiosome after absolute ethanol washing is dried under the conditions of 75 DEG C and is less than 1.0% to moisture content, be obtained
71.5g has the porous ceramicss class catalyst carrier in two-dimensional nano duct.
The porosity of a kind of porous ceramicss class catalyst carrier with two-dimensional nano duct that the present embodiment is obtained is：
17.6%, aperture is：150nm-300nm, specific surface area is 25.2 m2/g.
Claims (10)
1. there is the porous ceramicss class catalyst carrier in two-dimensional nano duct it is characterised in that：Described have two-dimensional nano duct
Porous ceramicss class catalyst carrier be with ceramic powder as primary raw material, with the Bacterial cellulose modified through acrylic surface
For pore creating material, sinter at a temperature of 600 DEG C -800 DEG C and form through silane coupler modified, prepared has two-dimensional nano
The porosity of the porous ceramicss class catalyst carrier in duct is 5%-65%, and aperture is 50nm-300nm, and specific surface area is 20m2/g-
130m2The ratio that/g, wherein open pore account for total pore reaches more than 80%.
2. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct described in claim 1, its feature
It is to take following steps：
(1) ceramic powder, dispersant and sintering aid are weighed rear mix homogeneously according to weight proportion and obtain stock, wherein make pottery
The weight proportion of porcelain powder body, dispersant and sintering aid is：
Ceramic powder 85wt%-95wt%
Dispersant 1.0wt%-5.0wt%
Sintering aid 4.0wt%-10wt%
(2) stock obtaining is carried out ball-milling treatment, thus the particle diameter of ceramic powder, dispersant and sintering aid is down to micro-
Nanoscale；
(3) using ultrasonic Treatment, Bacterial cellulose is dispersed in the aqueous solution of ethanol, then Deca acrylic acid is to thin
Fungin carries out surface modification, and modified Bacterial cellulose absolute ethanol washing is simultaneously dried to aqueous under the conditions of 45 DEG C
Rate is less than 1.0%；
(4) utilize mechanical agitation, micro/nano level ceramic powder that modified Bacterial cellulose and step (2) are obtained, dispersion
Agent and sintering aid mix homogeneously simultaneously add distilled water and make aqueous dispersion；
(5) then filter cake is dried under the conditions of 60 DEG C and is less than to moisture content by vacuum filtration step (4) gained aqueous dispersion
1.0%, obtain idiosome；
(6) dried idiosome is put into sintering in Muffle furnace, sintering temperature is 600 DEG C -800 DEG C, temperature retention time is 1h-3h；
(7) adjusting the pH value of ethanol with hydrochloric acid at normal temperatures is that 3-4 obtains ethanol-hydrogen chloride system, then by silane coupler plus
Enter to obtain the mixed solution of silane coupler and ethanol-hydrogen chloride in ethanol-hydrogen chloride system, wherein silane coupler ethanol-
It is hydrolyzed in hydrochloric acid system and obtains silanol, it is molten with the mixing of ethanol-hydrogen chloride system that hydrolysis is thoroughly masked as silane coupler
Liquid clear；
(8) idiosome after the sintering obtaining step (6) immerses silane coupler and the ethanol-hydrogen chloride system that step (7) obtains
Mixed solution in carry out surface modification, modified sintering idiosome absolute ethanol washing；
(9) the sintering idiosome after washing is dried under the conditions of 75 DEG C and is less than 1.0% to moisture content, be obtained and there is two-dimensional nanopore
The porous ceramicss class catalyst carrier in road.
3. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：Ceramic powder in described step (1) is Al2O3、SiO2Or TiO2In one of which, dispersant be polypropylene
One of which in acid, ammonium polyacrylate, sodium polyacrylate or polyacrylic acid potassium, sintering aid is starch.
4. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：Rotational speed of ball-mill in described step (2) is 300r/min, ceramic powder after ball-milling treatment, dispersant and
The particle diameter of sintering aid is 500nm-1 μm.
5. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：In described step (3), by Bacterial cellulose, under conditions of power is for 300w, ultrasonic Treatment 120s makes it uniform
It is scattered in the ethanol-water solution that mass fraction is 75%；Often modified 1.0g Bacterial cellulose needs 50mL ethanol-water solution and drips
Plus 4 ~ 7mL acrylic acid, surface modification is reaction 3h, the reaction of surface modification under 60 DEG C, the mechanical agitation of 60r/min
Equation is as follows：
.
6. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：In described step (4), churned mechanically rotating speed is 120r/min, and the time is 300s；Every 100g micro/nano level pottery
Powder body, dispersant and sintering aid add modified bacteria cellulose 1.0g-20.0g, distilled water 100-300mL.
7. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：The heating rate of described step (6) sintering process is 5 DEG C/min, is incubated 30min wherein when 105 DEG C.
8. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：Described step (7) silane coupler is 1 with the volume ratio of ethanol-hydrogen chloride system:9, the hydrolysis of silane coupler is anti-
Answer equation as follows：
；
In formula：X is hydrophobic group.
9. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct according to claim 2, its
It is characterised by：In described step (8), often the idiosome after modified 1.0g sintering, needs 10mL silane coupler and ethanol-hydrogen chloride
Mixed solution, reaction temperature during surface modification is 60 DEG C, and the response time is 2h, and mechanical agitation rotating speed is 60r/min, and surface changes
Property reaction equation is as follows：
；
In formula：X is hydrophobic group, and Y is Al2O3、SiO2Or TiO2In one of which.
10. the preparation method of the porous ceramicss class catalyst carrier with two-dimensional nano duct described in claim 8 or 9, its
It is characterised by：Described X is 3- (2,3- glycidoxy) or 3- methacryloxy.
Priority Applications (1)
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