CN102284288B - Technology for completely removing formaldehyde at room temperature by high-efficiency cold catalyst - Google Patents
Technology for completely removing formaldehyde at room temperature by high-efficiency cold catalyst Download PDFInfo
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- CN102284288B CN102284288B CN201010202956.1A CN201010202956A CN102284288B CN 102284288 B CN102284288 B CN 102284288B CN 201010202956 A CN201010202956 A CN 201010202956A CN 102284288 B CN102284288 B CN 102284288B
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Abstract
The invention provides a high-efficiency humidity-resistance room-temperature formaldehyde removing catalyst technology, and relates to the field of catalyst and environmental protection. The technology is characterized in that: honeycomb ceramic adopted as a carrier first loads channel gold-doped hollandite type crystal structured manganese dioxide (MnO2) to serve as a substrate, and then loads platinum (Pt) as an active component, wherein the doped hollandite type MnO2 substrate is characterized in that: chemical general formula of the substrate can be shown as Aux(A)y[MzMn8-z]O16 (M is Mg2+ and Zn2+, A is K+ and H+, x is less than or equal to 2, y is less than or equal to 2, and z is less than or equal to 3, [MzMn8-z]O16 represents the framework composition of the hollandite type MnO2, and Aux(A)y represents the channel composition of MnO2; and the weight ratio of Pt to doped MnO2 is between 0 and 10 percent. The integral catalyst can effectively, stably and completely remove the formaldehyde in the air in a room-temperature constant-humidity real environment, has no adverse side effect to a human body, and thus can be widely applied to the preparation of various air purifiers to remove formaldehyde.
Description
Technical field
The present invention is the catalyst technology that a kind of Effective Anti moist chamber temperature is removed formaldehyde, relates to the fields such as environmental protection, air pollutants improvement and environmental protection.It is characterized in that adopting ceramic honey comb is carrier, with the first load duct golden manganese dioxide (MnO that adulterates
2) be matrix, later Supported Pt Nanoparticles (Pt) is active component.The catalyzer contact agent of the technology of the present invention can be removed efficiently and stably airborne formaldehyde in the true environment of ambient temperature and moisture.
The invention still further relates to above-mentioned preparation method of nano material.
The invention still further relates to above-mentioned Application of micron administers in the various environmental protection of preparation and air pollutants.
Background technology
Along with steadily improving of China's rapid development of economy and living standards of the people, the repairs profession being driven by real estate and building industry has obtained unprecedented development.But, by fitting up or ornament materials and the indoor formaldehyde pollution problem that causes is very serious, caused that the whole world pays close attention to greatly.International cancer research institution of the World Health Organization (IARC) tissue is pointed out: formaldehyde can cause the mankind carcinogenic.Research shows that formaldehyde is the material that a kind of toxicity is higher, and short term contact formaldehyde can stimulate eyes, nasal cavity and respiratory tract and cause allergic reaction; Long Term Contact low dosage formaldehyde can increase nasopharyngeal carcinoma, leukaemia and dead possibility.Therefore, the sanitary standard (maximum permissible concentration) of China's regulation formaldehyde in indoor air in the < < IAQ standard > > (GB/T18883-2002) promulgating for 2002 is respectively 0.10mg/m
3.Therefore the formaldehyde of, removing in room air is extremely urgent.
The purification method that absorption method, plasma technique, chemical reaction method, photocatalyst oxidizing process and hot catalyst oxidizing process are formaldehyde.Wherein absorption method, chemical reaction method and photocatalyst method are the methods of the removal formaldehyde in indoor air pollutant commonly used.The porous material that in absorption method, conventional adsorbent is high-ratio surface is as active carbon, molecular sieve etc.Because the boiling point of formaldehyde lower (20 ℃) and molecule have stronger polarity, so at room temperature gaseous formaldehyde surface be nonpolar or the material such as low pole active carbon on absorption generally a little less than, therefore conventionally need to carry out modification to these porous masses in actual applications, to improve its adsorption capacity.Yet physical absorption or chemisorbed all can not obtain satisfied effect, because when adsorption and desorption reaches balance when saturated (adsorb), adsorbent will lose efficacy maybe to be needed to regenerate.In photocatalyst oxidation of formaldehyde technology, conventional catalyzer contact agent is TiO
2yet, in the lower formaldehyde removal efficiency of full-scale condition, limited photocatalyst and applied widely.Also have, by make the migration of its electronics occur in the problems such as visible region to the modification of photocatalyst agent, remain problem demanding prompt solution in photocatalyst degradation of formaldehyde and even whole photocatalyst field.
Chemical reaction method, by chemical reagent and formolite reaction, reaches the object of removing formaldehyde in air, and its major defect is that chemical reagent is dangerous, cost is high, can only once uses, and the refuse producing can cause secondary pollution etc.Common chemical reaction method: formaldehyde generates water and carbon dioxide after being loaded in by potassium permanganate load the filter that aluminium oxide or activated carbon make.But once potassium permanganate consumes completely, filter will lose efficacy.In air, spray chemical reagent or contaminated air is passed into chemical reagent solution, by chemical reagent (as organic amine etc.) and formaldehyde complexing, generated other chemical substance.Except cost height, be more very that its material generating itself has certain toxicity, the form with aerosol particle is suspended in air conventionally, can directly enter human respiratory tract and lung, larger to harm.
The catalyst oxidizing process airborne formaldehyde of degrading is a kind of long-acting method.US Patent No. 5585083 has been invented a kind of Pt/SnO
2catalyzer contact agent is removed the method for formaldehyde in air, and catalyzer contact agent, not having under extra energy input and-5～25 ℃ of conditions, is that oxidant will perfect degradable one-tenth carbon dioxide and water with airborne oxygen.But Pt content (12%) high in catalyzer contact agent causes the expensive of catalyzer contact agent, therefore this catalyzer contact agent can only be applied the special occasions such as some military projects or aerospace.Rare earth oxide or the absorption composite oxides catalyzer contact agent of gold-supported for Chinese patent CN1698932A can obtain good effect at 80-100 ℃ of temperature, and still, the input of high humility and heat energy is the biggest obstacle of this catalyzer contact agent extensive use.
The object of this invention is to provide a kind of straight way cellular type ceramic honey comb catalyst material of efficiently removing formaldehyde under the condition of room temperature, high humility and Wind Volume, be about to airborne formaldehyde and be completely oxidized to H
2o and CO
2, be applicable to the removal of the formaldehyde pollutants of sealing, hemi-closure space.Formaldehyde in catalyst oxidation removal room air has caused the attention in the world, because catalyzer contact agent does not need extra light or electric energy just airborne formaldehyde can be converted into harmless carbon dioxide (CO
2) and water (H
2o), its advantage is: process formaldehyde efficiency high, there is no secondary pollution and do not adsorb the problems such as saturated, the formaldehyde of particularly processing low concentration is very effective.
Summary of the invention
Object 1 of the present invention: provide a kind of Effective Anti moist chamber temperature to remove the catalyst technology of formaldehyde.
Object 2 of the present invention: provide a kind of Effective Anti moist chamber temperature to remove the preparation method of the catalyst technology of formaldehyde.
Object 3 of the present invention: relate to above-mentioned technology and be applied to prepare various environmental protection and air pollutants improvement product.
The object of the invention is to be achieved through the following technical solutions:
Efficient room temperature provided by the invention is removed formaldehyde, adopts following methods synthetic:
1. skeleton doping hollandite type MnO
2two kinds of preparation methods
(1) roasting method key step: by powder MnO
2or soluble manganese salt, M salt (M=Zn
2+or Mg
2+), template and organic solvent be according to a certain amount of mixing, vigorous stirring mixes, at 100～150 ℃ of dry 1～24h, then at 800～1300 ℃ of roasting 1～36h, cooling rear washing, is dried and obtains skeleton doping hollandite type MnO at 200～500 ℃ of roasting 1～36h
2matrix.
(2) ion-exchange key step: by the skeleton doping hollandite type MnO of above-mentioned preparation
2matrix adds a certain amount of red fuming nitric acid (RFNA) ammonium (NH
4nO
3) forming suspension in the aqueous solution, ion-exchange 1～48h, filters, at 100～150 ℃ of dry 1～24h, then at 200～400 ℃ of roasting 1～36h, as required, ion exchange procedure can repeat, and obtains the skeleton doping hollandite type MnO that in duct, part K+ is replaced by H+
2matrix.
2. duct Au doping hollandite type MnO
2the preparation method of matrix.
(1) by the hollandite type MnO of skeleton doping
2matrix adds in a certain amount of aqueous solution and forms suspension.
(2) ammoniacal liquor of finite concentration (≤25wt.%) is added to nitric acid gold solution (AuNO
3) the middle golden ammonia (Au (NH that forms
3)
2 +) solution.
(3) under fierce stirring, by the hydrogen peroxide (H of finite concentration (≤30wt.%)
2o
2) and Au (NH
3)
2 +solution is added dropwise to respectively above-mentioned skeleton doping hollandite type MnO simultaneously
2matrix suspension, aging 1～12h, then filters, washs, and at 100～150 ℃ of dry 1～24h, then at 200～800 ℃ of roasting 1～36h, obtains duct containing monatomic gold doping hollandite type MnO
2matrix.
3. honeycomb ceramic carrier load Au
x(A)
y[M
zmn
8-z] O
16preparation method
(1) take the Au of a certain amount of doping
x(A)
y[M
zmn
8-z] O
16matrix, adds a certain proportion of deionized water and adhesive.According to the requirement of viscosity and particle diameter, by the Au of adhesive and doping
x(A)
y[M
zmn
8-z] O
16matrix mixing suspended emulsion high-speed stirred 1～24h, obtains the Au of certain density doping
x(A)
y[M
zmn
8-z] O
16matrix slurries.
(2) adopt vacuum-negative pressure extraction technique by the Au of above-mentioned doping
x(A)
y[M
zmn
8-z] O
16matrix slurries are coated on the ceramic honey comb of anticipating, and at 200～800 ℃ of roasting 1～36h, obtain carried with doped Au
x(A)
y[M
zmn
8-z] O
16matrix material.
4. Au adulterates
x(A)
ym
zmn
8-z] O
16the method of matrix supporting Pt, is characterized in that adopting gas phase reduction process or liquid phase reduction preparation:
(1) gas phase reduction process: by above-mentioned load Au
x(A)
y[M
zmn
8-z] O
16monolithic devices material (claim 6 preparation) is immersed in nitroso diamines and closes platinum (Pt (NH
3)
2(NO
2)
2) or chloroplatinic acid (H
2ptCl
6) in mixed solution, dry after at 200～400 ℃ of roasting 1～36h, then in H2 atmosphere at 200～400 ℃ of reduction 1～36h, or adopt the UV of certain wavelength and light intensity to irradiate 1～72h.
(2) liquid phase reduction: by load Au
x(A)
ym
zmn
8-z] O
16monolithic devices material is immersed in finite concentration Pt (NH
3)
2(NO
2)
2or H
2ptCl
6in mixed solution, then add reducing agent, as NaBH
4, formaldehyde, ethylene glycol, glucose or there is the organic matter of reducing property, react at a certain temperature 1～6h, dry after at 200～400 ℃ of roasting 1～36h.
The technology of the present invention effect
Technique effect of the present invention is the feature that a kind of room temperature can thoroughly be removed airborne formaldehyde technology: under unglazed existence, room temperature is often 0.010～50mg/m by concentration in oxidation air under wet condition
3formaldehyde change into nontoxic carbon dioxide and water.
Advantage of the present invention
1. high efficiency and broad spectrum activity
Efficient room temperature of the present invention is removed formaldehyde catalyst technology, adopts the method for catalyst, and PARA FORMALDEHYDE PRILLS(91,95) has outstanding removal ability.
2. high stability and long-lasting
Anti-biotic material of the present invention has been abandoned adsorption technology, adopts catalyst activation oxygen mechanism, and when formaldehyde is removed, catalyzer contact agent does not consume, and has well long-lasting, very high stability and good economy, and to human body without any adverse side effect.
3. non-toxic and have no side effect
Efficient room temperature of the present invention is removed the catalyst technology of formaldehyde, and when being applied to air clearing product, nontoxicity, does not have accessory substance carbon monoxide and formic acid and produce.
The specific embodiment
Embodiment mono-
Duct is containing golden hollandite type MnO
2matrix (Au
x(A)
ym
zmn
8-z] O
16, A=K
+, M=Zn
2+or Mg
2+) preparation.
By powder MnO
2(P25), M salt (Zn (NO
3)
2or Mg (NO
3)
2), template potassium nitrate (KNO
3) and organic matter P123 according to a certain amount of mixing, vigorous stirring mixes, at 100～150 ℃ of dry 1～24h, then at 900 ℃ of roasting 36h, cooling rear washing, dry and obtain skeleton doping hollandite type MnO at 500 ℃ of roasting 24h
2matrix.
By above-mentioned hollandite type MnO
2matrix adds in a certain amount of aqueous solution and forms suspension.The ammoniacal liquor of finite concentration (≤25wt.%) is added to nitric acid gold solution (AuNO
3) the middle golden ammonia (Au (NH that forms
3)
2 +) solution.Under fierce stirring, by the hydrogen peroxide (H of finite concentration (≤30wt.%)
2o
2) and golden ammonia (Au (NH
3)
2 +) solution is added dropwise to respectively above-mentioned hollandite type MnO simultaneously
2matrix suspension, stirs aging 12h, then filters, washs, and at 110 ℃ of dry 24h, at 500 ℃ of roasting 6h, obtains Au
x(A)
ym
zmn
8-z] O
16(x≤2; Y≤2; Z≤3).
XRD and HRTEM analytical proof Au enter Hollandite type MnO
2the duct of matrix.
The performance test of catalyzer contact agent is carried out on the fixed bed reactors of continuous-flow.Before catalyzer contact agent performance test, catalyzer contact agent is not done to any processing, powder catalyst agent, through compressing tablet, is pulverized the granular of making 0.25～0.50mm, then 0.5g granular is loaded in a glass tube, under the condition that is 50% in room temperature (20 ℃) and relative humidity, pass into containing 5.0mg/m
3the air of formaldehyde, wind speed is 1.5m/s.Reactor outlet gas detects with FMNR infrared spectrum analyser, trace gas analysis mass spectrograph and Aulient7890A gas chromatographicanalyzer simultaneously simultaneously.The results are shown in Table 1.
Embodiment bis-
Au (K)
0.3[Zn
2mn
6] O
16the preparation of monolithic devices catalyst material.Take a certain amount of Au (K)
0.3[Zn
2mn
6] O
16, adding a certain proportion of deionized water and 30% silica adhesive, high-speed stirred 10h, obtains the Au (K) of certain density doping
0.3[Zn
2mn
6] O
16slurries.Adopt vacuum-negative pressure extraction technique by the Au (K) of doping
0.3[Zn
2mn
6] O
16slurries are coated on the ceramic honey comb of anticipating, and at 500 ℃ of roasting 12h, Au (K) obtains adulterating
0.3[Zn
2mn
6] O
16monolithic devices catalyst material.Be designated as " monolithic devices Au (K)
0.3[Zn
2mn
6] O
16".
The formaldehyde performance test of monolithic devices catalyst material is carried out on fixed bed.The three-dimensional of monolithic devices catalyzer contact agent is 150*150*40mm
3, then pack in glass tube, under the condition that is 50% in room temperature (20 ℃) and relative humidity, pass into containing 5.0mg/m
3the air of formaldehyde, wind speed is 1.5m/s.Air purifier detects the concentration of exit gas simultaneously simultaneously with FMNR infrared spectrum analyser, trace gas analysis mass spectrograph and Aulient7890A gas chromatographicanalyzer.The results are shown in Table 1.
Embodiment tri-
Doping Au (K)
0.3[Zn
2mn
6] O
16matrix supporting Pt is prepared by gas phase reduction process: by above-mentioned load Au (K)
0.3[Zn
2mn
6] O
16monolithic devices material (claim 6 preparation) is immersed in nitroso diamines and closes platinum (Pt (NH
3)
2(NO
2)
2) or chloroplatinic acid (H
2ptCl
6) in mixed solution, dry after at 300 ℃ of roasting 4h, then at H
2in atmosphere, at 300 ℃ of reduction 4h, or adopt the UV of certain 254nm to irradiate 36h.By liquid phase reduction, prepared: by load Au (K)
0.3[Zn
2mn
6] O
16monolithic devices material is immersed in finite concentration AuNO
3and Pt (NH
3)
2(NO
2)
2or H
2ptCl
6in mixed solution, then add reducing agent NaBH
4, at room temperature react 4h, after being dried, at 300 ℃ of roasting 4h, remembering " Pt/Au (K)
0.3[Zn
2mn
6] O
16".The content process icp analysis of metal, wherein Pt and doping Au (K)
0.3[Zn
2mn
6] O
16matrix ratio is 0～10%.
The formaldehyde performance test of monolithic devices catalyzer contact agent is with embodiment bis-.Result shows, preparation method is little on experimental result impact, in Table 2.
Embodiment tetra-
Pt/Au (K)
0.3[Zn
2mn
6] O
16the preparation of catalyst material (Pt/Au=3/7) is identical with embodiment tri-.
The performance test of catalyzer contact agent stability experiment is with embodiment bis-, and 200 days follow-on test time, the formaldehyde of entrance is 10mg/m
3, formaldehyde exit concentration is respectively 0.003mg/m
3.
Table 1. duct is containing the Hollandite type MnO of Au
2matrix (Au
x(A)
ym
zmn
8-z] O
16) test result.
Table 2.Pt/Au (K)
0.3[Zn
2mn
6] O
16test result.
Claims (10)
1. room temperature is removed a catalyst for formaldehyde, and it is characterized in that adopting ceramic honey comb is carrier, the hollandite type crystal structure manganese dioxide (MnO of first load duct gold doping
2), back loading platinum (Pt), duct gold doping hollandite type MnO
2chemical formulation be Au
x(A)
y[M
zmn
8-z] O
16, M=Zn wherein
2+, Mg
2+; A=K
+, H
+; X≤2; Y≤2; Z≤3, [M
zmn
8-z] O
16represent hollandite type MnO
2skeleton form, Au
x(A)
yrepresent MnO
2duct form, Pt and the duct gold hollandite type MnO that adulterates
2weight ratio is 0～10%, does not wherein comprise 0.
2. room temperature is removed the catalyst of formaldehyde as described in claim 1, it is characterized in that preparation method is as follows:
(1) first prepare skeleton doping hollandite type MnO
2, then carry out duct gold doping, obtain Au
x(A)
y[M
zmn
8-z] O
16;
(2) above-mentioned (1) is prepared to Au
x(A)
y[M
zmn
8-z] O
16be coated on honeycomb ceramic carrier 80～150 ℃ of oven dry, 200～800 ℃ of roasting 1～36h;
(3) by above-mentioned (2) preparation doping hollandite type MnO
2outer surface supporting Pt cluster or the nano particle of matrix.
3. room temperature is removed the catalyst of formaldehyde as described in claim 2, it is characterized in that skeleton doping hollandite type MnO
2preparation method adopt roasting method synthetic:
Soluble manganese salt, zinc salt or magnesium salts, template and organic solvent are according to a certain amount of mixing, vigorous stirring mixes, at 100～150 ℃ of dry 1～24h, then at 800～1300 ℃ of roasting 1～36h, cooling rear washing, is dried and obtains skeleton doping hollandite type MnO at 200～500 ℃ of roasting 1～36h
2matrix.
4. room temperature is removed the catalyst of formaldehyde as described in claim 3, it is characterized in that skeleton doping hollandite type MnO
2the condition of preparation is as follows:
Soluble manganese salt is that manganous salt is manganese acetate (Mn (CH
3cOO)
2), manganous chloride (MnCl
2), manganese nitrate (Mn (NO
3)
2) or manganese sulfate (MnSO
4) in one or more; The concentration of zinc salt or magnesium salts is 0.1～5.0mol/L, and soluble zinc salt is zinc nitrate (Zn (NO
3)
2), zinc chloride (ZnCl
2) and zinc acetate (Zn (CH
3cOO)
2) in one or more; Solubility magnesium salts is magnesium nitrate (Mg (NO
3)
2), magnesium chloride (MgCl
2) and magnesium acetate (Mg (CH
3cOO)
2) in one or more, wherein the mol ratio of zinc salt or magnesium salts and manganese ion is between 0～0.4, does not wherein comprise 0; Template is sylvite, and the mol ratio of template and total metal ion is between 1: 1 to 20: 1.
5. room temperature is removed the catalyst of formaldehyde as described in claim 1, it is characterized in that duct gold doping hollandite type MnO
2preparation method as follows:
By hollandite type MnO
2add in a certain amount of aqueous solution and form suspension, the ammoniacal liquor that is 25wt.% by concentration adds nitric acid gold solution (AuNO
3) in, under fierce stirring, the hydrogen peroxide (H that is 30wt.% by concentration
2o
2) and Au (NH
3)
2 +solution is added dropwise to respectively above-mentioned skeleton doping hollandite type MnO simultaneously
2suspension, aging 1～12h, then filters, washs, and at 100～150 ℃ of dry 1～24h, then at 200～800 ℃ of roasting 1～36h, obtains duct gold doping hollandite type MnO
2.
6. room temperature is removed the catalyst of formaldehyde as described in claim 1, it is characterized in that Supported Honeycomb Ceramics duct gold doping hollandite type MnO
2preparation method be:
(1) take a certain amount of duct gold doping hollandite type MnO
2, add a certain proportion of deionized water and adhesive, according to the requirement of viscosity and particle diameter, by adhesive and duct gold doping hollandite type MnO
2mix suspended emulsion high-speed stirred 1～24h, obtain finite concentration duct gold doping hollandite type MnO
2slurries;
(2) adopt vacuum-negative pressure extraction technique by duct gold doping hollandite type MnO
2slurries are coated on the ceramic honey comb of anticipating, at 200～800 ℃ of roasting 1～36h.
7. room temperature is removed the catalyst of formaldehyde as described in claim 1, it is characterized in that Pt carrying method adopts gas phase reduction process or liquid phase reduction preparation:
(1) gas phase reduction process: by Supported Honeycomb Ceramics duct gold doping hollandite type MnO
2be immersed in nitroso diamines and close platinum (Pt (NH
3)
2(NO
2)
2) or chloroplatinic acid (H
2ptCl
6) in solution, dry after at 200～400 ℃ of roasting 1～36h, then at H
2in atmosphere, at 200～400 ℃ of reduction 1～36h, or adopt the UV of certain wavelength and light intensity to irradiate 1～72h;
(2) liquid phase reduction: by Supported Honeycomb Ceramics duct gold doping hollandite type MnO
2be immersed in finite concentration Pt (NH
3)
2(NO
2)
2or H
2ptCl
6in solution, then add NaBH
4, formaldehyde, ethylene glycol or glucose, react at a certain temperature 1～6h, dry after at 200～400 ℃ of roasting 1～36h.
8. room temperature is removed the catalyst of formaldehyde as described in claim 6, and the adhesive adopting while it is characterized in that preparing is silicate, aluminium oxide or zirconium carbonate ammonium, the hollandite type MnO that adhesive and duct are adulterated golden
2weight ratio between 1～50%.
9. room temperature is removed the catalyst of formaldehyde as described in claim 1, it is characterized in that Hollandite duct contains monatomic nanowires of gold, is mainly Au
0; Pt is cluster or nano particle.
10. room temperature is removed the catalyst of formaldehyde as described in claim 1, it is characterized in that: in unglazed, room temperature, by concentration in air, be often 0.010～50mg/m under wet condition
3formaldehyde change into carbon dioxide and water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9908098B2 (en) | 2014-10-06 | 2018-03-06 | Corning Incorporated | Honeycomb filter article and methods thereof |
| US10046264B2 (en) | 2014-10-06 | 2018-08-14 | Corning Incorporated | Non-extruded activated carbon honeycomb structures |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI481444B (en) * | 2013-06-18 | 2015-04-21 | Univ Nat Taiwan Science Tech | Method of modifying photocatalyst, manganese-modified photocatalyst, photocatalytic filter, method of fabricating and utilizing the same |
| CN110639551A (en) * | 2019-09-26 | 2020-01-03 | 复旦大学 | Monolithic catalyst for removing benzene series at low temperature and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5585083A (en) * | 1995-03-30 | 1996-12-17 | The United States As Represented By The Administrator Of The National Aeronautics And Space Administration | Catalytic process for formaldehyde oxidation |
| CN101357331A (en) * | 2007-07-31 | 2009-02-04 | 上海大今实业有限公司 | Room-temperature decomposition ozone catalysis material and preparation method thereof |
-
2010
- 2010-06-18 CN CN201010202956.1A patent/CN102284288B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5585083A (en) * | 1995-03-30 | 1996-12-17 | The United States As Represented By The Administrator Of The National Aeronautics And Space Administration | Catalytic process for formaldehyde oxidation |
| CN101357331A (en) * | 2007-07-31 | 2009-02-04 | 上海大今实业有限公司 | Room-temperature decomposition ozone catalysis material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9908098B2 (en) | 2014-10-06 | 2018-03-06 | Corning Incorporated | Honeycomb filter article and methods thereof |
| US10046264B2 (en) | 2014-10-06 | 2018-08-14 | Corning Incorporated | Non-extruded activated carbon honeycomb structures |
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| Publication number | Publication date |
|---|---|
| CN102284288A (en) | 2011-12-21 |
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