CN106563430A - Honeycomb ceramic monolithic photocatalyst as well as preparation method and application of honeycomb ceramic monolithic photocatalyst - Google Patents

Honeycomb ceramic monolithic photocatalyst as well as preparation method and application of honeycomb ceramic monolithic photocatalyst Download PDF

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Publication number
CN106563430A
CN106563430A CN201610978890.2A CN201610978890A CN106563430A CN 106563430 A CN106563430 A CN 106563430A CN 201610978890 A CN201610978890 A CN 201610978890A CN 106563430 A CN106563430 A CN 106563430A
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China
Prior art keywords
active
monoblock type
honey comb
honeycomb ceramic
type photocatalyst
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CN201610978890.2A
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Chinese (zh)
Inventor
何丹农
赵昆峰
袁静
蔡婷
高振源
杨玲
张涛
金彩虹
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16Clays or other mineral silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8678Removing components of undefined structure
    • B01D53/8687Organic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708Volatile organic compounds V.O.C.'s

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a honeycomb ceramic monolithic photocatalyst as well as a preparation method and application of the honeycomb ceramic monolithic photocatalyst. TiO2 is immobilized on cordierite honeycomb ceramic with an activated aluminum oxide coating by using a dip-coating method, and due to the adoption of the pre-coated activated aluminum oxide coating, the acting force between activated slurry and a carrier is enhanced, the shedding rate of the monolithic catalyst is reduced, meanwhile, the usage amount of a binder used in the coating process is reduced, and the activity of the catalyst is improved because activated ingredients are more easily exposed on the surface of the catalyst. The catalyst prepared by using the preparation method has the characteristics of large specific surface area, good light transparency, low shedding rate, high mechanical strength and the like and overcomes defects of the traditional monolithic photocatalyst.

Description

A kind of ceramic honey comb monoblock type photocatalyst and its preparation method and application
Technical field
The present invention relates to nanocatalyst technical field, more particularly, to a kind of ceramic honey comb monoblock type photocatalyst and its Preparation method and application.
Background technology
Volatile organic matter(VOC)It is a kind of widely distributed, miscellaneous atmosphere pollution, it participates in photochemical fog Reaction, the secondary particulate participated in air is formed, while major part VOC itself has toxicity and carcinogenecity, to ecological environment Serious harm is caused with human health.Therefore, a kind of efficient, energy-conservation of urgent needss, the VOC purification techniques of green.
At present, conventional VOC purification techniques mainly has absorption method, heat-accumulation combustion, catalysis burning, photocatalysis etc..Absorption is net Change method, material adsorption capacity is limited, and easily generation desorption causes secondary pollution.Heat-accumulation combustion and catalysis burning etc. are general in high temperature Lower reaction, expends substantial amounts of energy.Photocatalysis method can under mild conditions realize the efficient degradation of VOC using luminous energy, Simultaneously secondary pollution is not produced, with good application prospect.
The integral catalyzer obtained after photocatalyst is immobilized, changes powder photocatalyst pressure drop greatly, is difficult back The shortcomings of receipts, be to realize through engineering approaches application foundation.Conventional metal mesh carrier or the network structure of foam nickel carrier, determine it Under conditions of light transmission is met, mechanical strength is not suitable for large-scale application than relatively low.Meanwhile, immobilized process is more multiple Miscellaneous, immobilized rear expulsion rate is difficult to control to.
The content of the invention
For the deficiencies in the prior art, the present invention discloses a kind of ceramic honey comb monoblock type photocatalyst and preparation method thereof With.Light can be entered by the duct of ceramic honey comb, and the catalyst surface inside duct meets photocatalysis and light transmission is wanted Ask, and high mechanical strength.
By TiO2Photocatalyst, using on the immobilized cordierite honeycomb ceramic to active aluminum oxide coating layer of dip coating, Prepare ceramic honey comb monoblock type photocatalyst.The active oxidation aluminized coating of pre-coated, enhances the effect of active slurry and carrier Power, reduces the expulsion rate of integral catalyzer.Simultaneously the active oxidation aluminized coating of pre-coated, reduces in coating process and bonds The usage amount of agent, makes active component be easier exposed to catalyst surface, improves catalyst activity.
Gained catalyst of the invention has that specific surface area is big, light transmission is good, expulsion rate is low, high mechanical strength the features such as, change It has been apt to the deficiency of traditional monoblock type photocatalyst.The technology of the present invention was not reported in pertinent literature and patent.
The technical scheme is that:
A kind of preparation method of ceramic honey comb monoblock type photocatalyst, it is characterised in that using dip coating by TiO2It is immobilized to tool On the cordierite honeycomb ceramic of active aluminum oxide coating layer, the active oxidation aluminized coating of pre-coated enhances active slurry and carries The active force of body, reduces the expulsion rate of integral catalyzer, while the active oxidation aluminized coating of pre-coated, reduces coated The usage amount of binding agent in journey, makes active component be easier exposed to catalyst surface, improves catalyst activity, methods described Comprise the following steps:
The first step, by a certain amount of TiO2It is scattered in a certain amount of deionized water with boehmite, under stirring condition, Deca Concentrated nitric acid to pH is 3-4, continues to stir 30min, obtains active slurry;
Second step, the cordierite honeycomb ceramic carrier of active aluminum oxide coating layer vertically impregnated in above-mentioned slurry to carrier Mid-height position, takes out after 5-10s, is inversely blown out additional size using air compressor machine purging, overturns carrier, will be untreated Half vertically impregnated in above-mentioned slurry, take out after 5-10s, and additional size is inversely blown out;
3rd step, by gained ceramic honey comb monoblock type photocatalyst, stands a few hours under room temperature, 50 DEG C of drying, 400-550 DEG C of roasting 4h is burnt, ceramic honey comb monoblock type photocatalyst is obtained.
Cordierite carrier is impregnated in the alumina sol of solid content 28% and take out after 5-10s, blown using air compressor Go out additional size, 50 DEG C of dryings, 550 DEG C of roastings.
TiO described in the first step2It is 1 with the mass ratio of boehmite:20~1:10;Solid content is 35% ~ 50%, and solid is accounted for Mass ratio in total dispersion liquid.
A kind of ceramic honey comb monoblock type photocatalyst, it is characterised in that prepared according to methods described.
A kind of ceramic honey comb monoblock type photocatalyst photodegradative applications of THC at room temperature.
Using dip coating by TiO2On the immobilized cordierite honeycomb ceramic to active aluminum oxide coating layer of photocatalyst.In advance The active oxidation aluminized coating of coating, enhances the active force of active slurry and carrier, reduces the expulsion rate of integral catalyzer. Simultaneously the active oxidation aluminized coating of pre-coated, reduces the usage amount of binding agent in coating process, is easier active component sudden and violent Catalyst surface is exposed to, catalyst activity is improve.Gained catalyst of the invention has that specific surface area is big, light transmission is good, comes off Rate is low, high mechanical strength the features such as, improve the deficiency of traditional monoblock type photocatalyst.
The present invention has advantages below:
(1)Ceramic honey comb is used as carrier of photocatalyst, high mechanical strength.
(2)By the carrier of catalyst coated to active aluminum oxide coating layer, adhesiveness is good, and expulsion rate is low.
(3)Raw material is easy to get, low cost, prepares simply, reproducible.
Specific embodiment
Embodiments of the invention are elaborated below:The present embodiment is carried out under premised on technical solution of the present invention Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following enforcements Example.
Embodiment 1:
By 175g TiO2It is scattered in 200ml deionized waters with 25g boehmites, under stirring condition, Deca concentrated nitric acid to pH For 3-4, continue to stir 30min, obtain active slurry.
The cordierite honeycomb ceramic carrier of the active aluminum oxide coating layer of 10 cm*10 cm*5 cm vertically impregnated in To carrier height half position in above-mentioned slurry, take out after 5-10s, inversely blown out additional size using air compressor machine purging.Turn over Rotaring carrier, untreated half vertically impregnated in above-mentioned slurry, take out after 5-10s, and additional size is inversely blown out.Room temperature Lower standing a few hours, 50 DEG C of drying, 550 DEG C of roasting 4h.
Gained catalyst TiO2Loading is 18%, expulsion rate < 1%, and THC the disposal efficiencies are 55% under room temperature.
Embodiment 2
By 165g TiO2It is scattered in 200ml deionized waters with 35g boehmites, under stirring condition, Deca concentrated nitric acid to pH For 3-4, continue to stir 30min, obtain active slurry.
The cordierite honeycomb ceramic carrier of the active aluminum oxide coating layer of 10 cm*10 cm*5 cm vertically impregnated in To carrier height half position in above-mentioned slurry, take out after 5-10s, inversely blown out additional size using air compressor machine purging.Turn over Rotaring carrier, untreated half vertically impregnated in above-mentioned slurry, take out after 5-10s, and additional size is inversely blown out.Room temperature Lower standing a few hours, 50 DEG C of drying, 550 DEG C of roasting 4h.
Gained catalyst TiO2Loading is 17%, expulsion rate < 1%, and THC the disposal efficiencies are 45% under room temperature.
Embodiment 3
By 185g TiO2It is scattered in 200ml deionized waters with 15g boehmites, under stirring condition, Deca concentrated nitric acid to pH For 3-4, continue to stir 30min, obtain active slurry.
The cordierite honeycomb ceramic carrier of the active aluminum oxide coating layer of 10 cm*10 cm*5 cm vertically impregnated in To carrier height half position in above-mentioned slurry, take out after 5-10s, inversely blown out additional size using air compressor machine purging.Turn over Rotaring carrier, untreated half vertically impregnated in above-mentioned slurry, take out after 5-10s, and additional size is inversely blown out.Room temperature Lower standing a few hours, 50 DEG C of drying, 550 DEG C of roasting 4h.
Gained catalyst TiO2Loading is 19%, expulsion rate < 1%, and THC the disposal efficiencies are 70% under room temperature.
Embodiment 4
By 185g TiO2It is scattered in 200ml deionized waters with 15g boehmites, under stirring condition, Deca concentrated nitric acid to pH For 3-4, continue to stir 30min, obtain active slurry.
The cordierite honeycomb ceramic carrier of 10 cm*10 cm*5 cm vertically impregnated in above-mentioned slurry to carrier height Half position, takes out after 5-10s, is inversely blown out additional size using air compressor machine purging.Upset carrier, by untreated half In vertically impregnated in above-mentioned slurry, take out after 5-10s, additional size is inversely blown out.A few hours are stood under room temperature, 50 DEG C of bakings It is dry, 550 DEG C of roasting 4h.
Gained catalyst TiO2Loading is 19%, expulsion rate 2%, and THC the disposal efficiencies are 64% under room temperature.
Embodiment 5:
By 70g γ-Al2O3It is scattered in 200ml deionized waters with 10g boehmites, under stirring condition, Deca concentrated nitric acid It is 3-4 to pH, continues to stir 30min, obtains active slurry.
The cordierite honeycomb ceramic carrier of 10 cm*10 cm*5 cm vertically impregnated in above-mentioned slurry, take after 5-10s Go out, inversely blown out additional size using air compressor machine purging.A few hours are stood under room temperature, 50 DEG C of drying, 550 DEG C of roasting 4h, Obtain the cordierite honeycomb ceramic carrier of active aluminum oxide coating layer.

Claims (5)

1. a kind of preparation method of ceramic honey comb monoblock type photocatalyst, it is characterised in that using dip coating by TiO2It is immobilized to tool On the cordierite honeycomb ceramic of active aluminum oxide coating layer, the active oxidation aluminized coating of pre-coated enhances active slurry and carries The active force of body, reduces the expulsion rate of integral catalyzer, while the active oxidation aluminized coating of pre-coated, reduces coated The usage amount of binding agent in journey, makes active component be easier exposed to catalyst surface, improves catalyst activity, methods described Comprise the following steps:
The first step, by a certain amount of TiO2It is scattered in a certain amount of deionized water with boehmite, under stirring condition, Deca Concentrated nitric acid to pH is 3-4, continues to stir 30min, obtains active slurry;
Second step, the cordierite honeycomb ceramic carrier of active aluminum oxide coating layer vertically impregnated in above-mentioned slurry to carrier Mid-height position, takes out after 5-10s, is inversely blown out additional size using air compressor machine purging, overturns carrier, will be untreated Half vertically impregnated in above-mentioned slurry, take out after 5-10s, and additional size is inversely blown out;
3rd step, by gained ceramic honey comb monoblock type photocatalyst, stands a few hours under room temperature, 50 DEG C of drying, 400-550 DEG C of roasting 4h is burnt, ceramic honey comb monoblock type photocatalyst is obtained.
2. the preparation method of ceramic honey comb monoblock type photocatalyst according to claim 1, it is characterised in that carry cordierite Body impregnates in the alumina sol of solid content 28% and taken out after 5-10s, and using air compressor additional size is blown out, and 50 DEG C are done It is dry, 550 DEG C of roastings.
3. the preparation method of ceramic honey comb monoblock type photocatalyst according to claim 1, it is characterised in that described in the first step TiO2It is 1 with the mass ratio of boehmite:20~1:10;Solid content is 35% ~ 50%, the quality that solid is accounted in total dispersion liquid Than.
4. a kind of ceramic honey comb monoblock type photocatalyst, it is characterised in that be prepared into according to the arbitrary methods described of claim 1-3 Arrive.
5. the ceramic honey comb monoblock type photocatalyst photodegradative applications of THC at room temperature according to claim 4.
CN201610978890.2A 2016-11-08 2016-11-08 Honeycomb ceramic monolithic photocatalyst as well as preparation method and application of honeycomb ceramic monolithic photocatalyst Pending CN106563430A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012756A (en) * 2018-09-17 2018-12-18 南京景铄新材料科技有限公司 A kind of catalysis material and preparation method thereof with high stability
CN110662605A (en) * 2017-05-30 2020-01-07 先技精工(日本)有限公司 Method for producing catalyst or adsorbent carrier, and catalyst or adsorbent carrier
CN113318719A (en) * 2020-02-28 2021-08-31 广东粤能净环保科技有限公司 Photocatalytic unit and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064739A1 (en) * 1998-06-12 1999-12-16 Guiterrez, Richard, N. Method for a reduction of emissions in combustion processes
CN1384152A (en) * 2001-04-28 2002-12-11 中国科学院化学研究所 Titania nano-paint for photocatalytic decomposition of organic matter and its prepn
CN2533415Y (en) * 2002-03-08 2003-01-29 戴各生 Air cleaning device
JP2005254128A (en) * 2004-03-11 2005-09-22 Toshiba Ceramics Co Ltd Photocatalyst particle and method of immobilizing it, and photocatalytic member
CN102180705A (en) * 2011-02-28 2011-09-14 武汉大方机电有限公司 Preparation method for titanium dioxide thin layer loaded on surface of inorganic ceramic matrix
CN104998697A (en) * 2015-07-10 2015-10-28 上海纳米技术及应用国家工程研究中心有限公司 Application method for integral catalyst active coating

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064739A1 (en) * 1998-06-12 1999-12-16 Guiterrez, Richard, N. Method for a reduction of emissions in combustion processes
CN1384152A (en) * 2001-04-28 2002-12-11 中国科学院化学研究所 Titania nano-paint for photocatalytic decomposition of organic matter and its prepn
CN2533415Y (en) * 2002-03-08 2003-01-29 戴各生 Air cleaning device
JP2005254128A (en) * 2004-03-11 2005-09-22 Toshiba Ceramics Co Ltd Photocatalyst particle and method of immobilizing it, and photocatalytic member
CN102180705A (en) * 2011-02-28 2011-09-14 武汉大方机电有限公司 Preparation method for titanium dioxide thin layer loaded on surface of inorganic ceramic matrix
CN104998697A (en) * 2015-07-10 2015-10-28 上海纳米技术及应用国家工程研究中心有限公司 Application method for integral catalyst active coating

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110662605A (en) * 2017-05-30 2020-01-07 先技精工(日本)有限公司 Method for producing catalyst or adsorbent carrier, and catalyst or adsorbent carrier
CN109012756A (en) * 2018-09-17 2018-12-18 南京景铄新材料科技有限公司 A kind of catalysis material and preparation method thereof with high stability
CN113318719A (en) * 2020-02-28 2021-08-31 广东粤能净环保科技有限公司 Photocatalytic unit and application thereof

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