CN102247842A - High-efficiency catalyst for removing formaldehyde at room temperature - Google Patents
High-efficiency catalyst for removing formaldehyde at room temperature Download PDFInfo
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- CN102247842A CN102247842A CN201010177901XA CN201010177901A CN102247842A CN 102247842 A CN102247842 A CN 102247842A CN 201010177901X A CN201010177901X A CN 201010177901XA CN 201010177901 A CN201010177901 A CN 201010177901A CN 102247842 A CN102247842 A CN 102247842A
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Abstract
The invention relates to a high-efficiency catalyst for oxidizing low-concentration formaldehyde in indoor air into carbon dioxide and water at room temperature and normal humidity and a preparation method of the catalyst. The catalyst is characterized in that: cordierite honeycomb ceramic coated with TiO2-SnO2 composite oxide is taken as a carrier, and 0 to 5 percent of Pt is taken as an active ingredient. The catalyst has the advantages that: energy such as light, heat, electricity and the like and a chemical reagent are not required to be added, the formaldehyde removing efficiency is far higher than that of a photocatalysis technology and a plasma technology under the conditions of large air quantity, high humidity and the like, byproducts are not generated, and the catalyst is suitable for efficiently removing formaldehyde in closed or semi-closed spaces such as artificial board production workshops, living rooms, automobiles and the like.
Description
Technical field
The present invention relates to eliminating formaldehyde at room temperature effective catalyst and preparation method thereof; promptly relate to and a kind ofly under room temperature, high humidity, airborne formaldehyde gas is completely oxidized to harmless carbon dioxide and water; the formaldehyde that is applicable to sealings such as removing Wood-based Panel Production workshop, room, building materials furniture market, hemi-closure space pollutes, and belongs to catalysis material, environmental catalysis and environmental protection technical field.
Background technology
The formaldehyde pollution problem of closed system and closed system has caused that various circles of society pay close attention to greatly.Studies show that formaldehyde can stimulate eyes, nasal cavity and respiratory tract and cause allergic reaction the possibility of long-term contact meeting increase trouble cancer in short term contact as a kind of highly toxic material.For this reason, formaldehyde is defined as carcinogenic and teratogenesis shape material by the World Health Organization." the closed system air quality standard " of China's promulgation (GB/T18883-2002) stipulates that formaldehyde sanitary standard (maximum permissible concentration) is 0.10mg/m in the closed system air
3, at room temperature be about 0.08ppm.Yet, according to investigations, the content overproof of formaldehyde in the Chinese most city half family air, and also the modern has time of 80～90% to spend at closed system approximately.Therefore, it is imperative to remove the such formaldehyde of closed system.
Absorption method and photocatalytic method are the methods of formaldehyde pollutant in the degraded closed system air of using always at present.Yet, for absorption method, taking off when reaching balance when the absorption of formaldehyde and holder, adsorbent will lose efficacy or need regeneration.The degradation efficiency of photocatalysis PARA FORMALDEHYDE PRILLS(91,95) is low also have been limited it and has used widely.The catalytic oxidation airborne formaldehyde of degrading is a kind of long-acting method.Chinese patent CN1698932A can obtain effect preferably with the rare earth oxide or the absorption composite oxide catalysts of load gold under 80-100 ℃ of temperature, still, the input of high humility and heat energy is the biggest obstacle of this catalyst extensive use.U.S. Pat 5585083 has been invented a kind of Pt/SnO
2Catalyst is removed the method for formaldehyde in the air, and catalyst is not having under extra energy input and-5～25 ℃ of conditions, is that oxidant will perfect and be degraded into carbon dioxide and water fully with airborne oxygen.But Pt content (12%) high in the catalyst causes costing an arm and a leg of catalyst, and therefore this catalyst can only be used special occasions such as some military projects or aerospace.
The purpose of this invention is to provide and a kind ofly under room temperature, high humidity, airborne formaldehyde gas is oxidized to harmless H
2O and CO
2Catalyst efficiently, it is skeleton that catalyst adopts the ceramic honey comb of straight way cellular type, during use, the very little efficient of windage is very high, is applicable to the removal of the formaldehyde pollution of sealings such as removing Wood-based Panel Production workshop, room, building materials furniture market and automotive interior, hemi-closure space.
Summary of the invention
The object of the present invention is to provide a kind of catalyst that under room temperature and high humidity, formaldehyde in the closed system air can be completely oxidized to carbon dioxide and water.
Another object of the present invention provides a kind of method for preparing above-mentioned catalyst.
The objective of the invention is to be achieved through the following technical solutions:
Catalyst provided by the invention is prepared by following method:
1. titaniferous presoma and stanniferous presoma are dissolved in respectively in two-(2-ethylhexyl) sodium sulfosuccinate (AOT)/ethanol/deionized water solution; According to suitable Ti-Sn mol ratio, above-mentioned three kinds of solution are mixed, and under intense agitation, drip an amount of H
2O
2, H
2O
2The mol ratio that belongs to ion with GOLD FROM PLATING SOLUTION is 1～5: 1; Toward an amount of concentration of mixed solution and dripping is the ammoniacal liquor of 0.05～0.23mol/l, and its pH value finally is adjusted to 7～9; Gained colloidal liquid mixture is through ultrasonic processing 0.5～2h; After sediment in the colloidal liquid mixture washed through centrifugation, deionized water, 110 ℃ of dry 24h obtained the composite oxides presoma, obtain required Ti-Sn composite oxides in 400 ℃ of roasting 2h subsequently in air.
2. take by weighing a certain amount of Ti-Sn composite oxides, add a certain proportion of aqueous solution of silica gel, high-speed stirred 3 hours obtains certain density Ti-Sn composite oxides slurries; The cordierite honeycomb ceramic sample (400 hole/inch) of anticipating is immersed in the Ti-Sn composite oxides slurries that prepare, flood after 2 minutes and take out, blow the raffinate in the most duct, the back 110 ℃ of dryings of drying in the shade in air 2 hours, roasting obtained scribbling the cordierite honeycomb ceramic carrier of Ti-Sn composite oxides in 2 hours under 400-600 ℃ of air.Wherein composite oxides account for the 10-20% of vehicle weight, the back 110 ℃ of dryings of in air, drying in the shade 2 hours, and the cordierite honeycomb ceramic carrier that roasting got in 2 hours under 400-600 ℃ of air,
3. the cordierite honeycomb ceramic carrier that step 2 is obtained is immersed in Pt (NH
3)
2(NO
2)
2Or Pt (NO
3)
2In the aqueous solution, wherein the concentration of Pt is 0.001～0.05mol/l.The taking-up back 110 ℃ of dryings of drying in the shade in air obtained the supporting Pt presoma in 2 hours.Repeat to make for 1-6 time the content of Pt to account for the 0-5% of composite oxides total amount.
4. the supporting Pt presoma of step 3 is handled the catalyst that obtained pre-oxidation, prereduction in 1-10 hour respectively in 200-600 ℃ in air (purity oxygen) or pure hydrogen.
The technology of the present invention effect
Advantage of the present invention: need not to add light, heat, electric equal energy source and chemical reagent, the formaldehyde under conditions such as room temperature, high humility is removed efficient far above photocatalysis and plasma technique, and does not have any accessory substance; It is skeleton that catalyst adopts the ceramic honey comb of straight way cellular type, and the pressure reduction during use before and after the catalyst is very little, therefore under big air speed condition the harmful formaldehyde gas in the contaminated air is oxidized to also harmless H
2O and CO
2Be applicable to the removal of the formaldehyde pollution of sealings such as removing Wood-based Panel Production workshop, room, building materials furniture market and automobile inner air, hemi-closure space.
Description of drawings
Fig. 1 is the stability test of the Pt/Ti-Sn catalyst of the present invention's preparation.
Test condition: 0.8 mg/m
3Formaldehyde, 2.5m/s wind speed, relative humidity 80%, 20 ℃ of temperature, air.
The specific embodiment
Embodiment one
Apply the preparation of Ti-Sn composite oxides cordierite honeycomb ceramic carrier: will contain titanium tetrachloride and butter of tin and be dissolved in (wherein AOT, ethanol, water mol ratio were at 2: 20: 40) in two-(2-ethylhexyl) sodium sulfosuccinate (AOT)/ethanol/deionized water solution respectively, according to suitable Ti-Sn mol ratio (seeing Table 1), above-mentioned three kinds of solution are mixed, and under intense agitation, drip an amount of H
2O
2, H
2O
2The mol ratio that belongs to ion with GOLD FROM PLATING SOLUTION is 1: 1; Toward an amount of concentration of mixed solution and dripping is the ammoniacal liquor of 0.20mol/l, and its pH value finally is adjusted to 7～9; Gained colloidal liquid mixture is through ultrasonic processing 1h; After sediment in the colloidal liquid mixture washed through centrifugation, deionized water, 110 ℃ of dry 24h obtained the composite oxides presoma, obtain required Ti-Sn composite oxides in 400 ℃ of roasting 2h subsequently in air.
Take by weighing the Ti-Sn composite oxides of a certain amount of above-mentioned different content, add a certain proportion of aqueous solution of silica gel, high-speed stirred 3 hours obtains certain density Ti-Sn composite oxides slurries; With cylindrical cordierite honeycomb ceramic sample (the high 23mm that anticipates, diameter 20mm, 400 hole/inches) be immersed in the Ti-Sn composite oxides slurries that prepare, flood after 2 minutes and take out, blow the raffinate in the most duct, the back 110 ℃ of dryings of drying in the shade in air 2 hours, roasting obtained scribbling the cordierite honeycomb ceramic carrier (seeing Table 1) of Ti-Sn composite oxides in 2 hours under 500 ℃ of air.Wherein composite oxides account for 20% of vehicle weight.
The performance test of catalyst is carried out on the fixed bed reactors of continuous-flow.Cylindrical iolite honeycomb ceramic catalyst (high 23mm, diameter 20mm, 400 hole/inches) loads in the glass tube, is that feeding contains 0.8mg/m under 80% the condition in room temperature (18-25 ℃) and relative humidity
3The air of formaldehyde, wind speed are 2.5m/s.Reactor outlet gas uses Innova1312 gas concentration detector and trace gas analysis mass spectrograph (PTR-MS) to analyze simultaneously.Experiment shows: formaldehyde is resolved into harmless water and carbon dioxide fully, does not have accessory substances such as formic acid, carbon monoxide and methyl formate.The results are shown in Table 1.
Embodiment two
Preparation of catalysts: the Ti-Sn composite oxides cordierite honeycomb ceramic carrier that scribbles that embodiment 1 is obtained is immersed in Pt (NH
3)
2(NO
2)
2In the aqueous solution, wherein the concentration of Pt is 0.01mol/l.The taking-up back 110 ℃ of dryings of drying in the shade in air obtained the supporting Pt presoma in 2 hours, then the supporting Pt presoma were handled 2 hours in pure hydrogen in 200 ℃.The content of Pt accounts for 1.0% of composite oxides.
The performance test of catalyst is with embodiment one, and experiment shows: formaldehyde is resolved into harmless water and carbon dioxide fully, does not have accessory substances such as formic acid, carbon monoxide and methyl formate.The results are shown in table 1.
Embodiment three
The Preparation of catalysts of different Pt content: the Ti-Sn composite oxides cordierite honeycomb ceramic carrier that scribbles that embodiment 1 is obtained is immersed in Pt (NH
3)
2(NO
2)
2In the aqueous solution, the concentration of Pt is to make the content of Pt in the finished catalyst account for the 0-5% of composite oxides in the regulator solution.The taking-up back 110 ℃ of dryings of drying in the shade in air obtained the supporting Pt presoma in 2 hours, then the supporting Pt presoma were handled 2 hours in pure hydrogen in 200 ℃.
The performance test of catalyst is with embodiment one, and experiment shows: formaldehyde is resolved into harmless water and carbon dioxide fully, does not have accessory substances such as formic acid, carbon monoxide and methyl formate.The results are shown in table 1.
Embodiment four
The preliminary treatment of Pt/Ti-Sn catalyst: the cordierite honeycomb ceramic carrier that scribbles the Ti-Sn composite oxides that embodiment 1 is obtained is immersed in Pt (NH
3)
2(NO
2)
2In the aqueous solution, the concentration of Pt makes that the content of Pt accounts for 1.0% of composite oxides in the finished catalyst in the regulator solution.The taking-up back 110 ℃ of dryings of drying in the shade in air obtained the supporting Pt presoma in 2 hours, then the supporting Pt presoma were handled 2 hours in purity oxygen or pure hydrogen in 200 ℃.The catalyst of preparation is designated as the Pt/Ti-Sn and the reduction of oxidation processes respectively and handles Pt/Ti-Sn.
The performance test of catalyst is with embodiment one, and experiment shows: formaldehyde is resolved into harmless water and carbon dioxide fully, does not have accessory substances such as formic acid, carbon monoxide and methyl formate.The results are shown in Fig. 1.
The influence that the composition of table 1.Pt/Ti-Sn catalyst and PARA FORMALDEHYDE PRILLS(91,95) thereof are eliminated efficient.
Claims (10)
1. the present invention relates to a kind of room temperature formaldehyde and remove catalyst, it is characterized in that adopting the cordierite honeycomb ceramic that scribbles the Ti-Sn composite oxides as carrier, with Pt as active component.
2. the oxidation of formaldehyde catalyst in the claim 1, its feature is meeting following preparation flow:
(1) at first prepares Ti-Sn composite oxides (or its presoma).
(2) the Ti-Sn composite oxides are coated on the cordierite honeycomb ceramic as carrier 110 ℃ of oven dry, 400-600 ℃ of roasting 2h.
(3) supporting Pt presoma, 110 ℃ of oven dry, 400-600 ℃ of roasting 2h, and carry out preliminary treatment.
3. the Ti-Sn composite oxides described in the claim 2 is characterized in that wherein the content of Ti is 0-100%.
4. Ti-Sn composite oxides described in the claim 2 is characterized in that its preparation method is as follows:
(1) titaniferous presoma and stanniferous presoma are dissolved in respectively in two-(2-ethylhexyl) sodium sulfosuccinate (AOT)/ethanol/deionized water solution.
(2), above-mentioned three kinds of solution are mixed, and under intense agitation, drip an amount of H according to suitable Ti-Sn mol ratio
2O
2, H
2O
2The mol ratio that belongs to ion with GOLD FROM PLATING SOLUTION is 1～5: 1.
(3) be the ammoniacal liquor of 0.05～0.23mol/l toward an amount of concentration of mixed solution and dripping, and its pH value finally is adjusted to 7～9.
(4) after the sediment in the colloidal liquid mixture washed through centrifugation, deionized water, 110 ℃ of dry 24h obtained the composite oxides presoma.
(5) the complex carrier presoma obtains required Ti-Sn composite oxides in 400-800 ℃ of roasting 2h in air.
5. the titaniferous presoma in the claim 4 is a kind of in titanium sulfate, titanium tetrachloride or the tetrabutyl titanium, and titanium concentration is 0.1～1.2mol/l in its solution.Stanniferous presoma in the claim 4 is a kind of in tin oxalate, stannic chloride or the nitric acid tin, and tin concentration is 0.2～1.9mol/l in its solution.
6. two described in the claim 4-(2-ethylhexyl) sodium sulfosuccinate (AOT)/ethanol/deionized water solution is characterized in that AOT, ethanol, water mol ratio are 1～8: 20～60: 50～90.
7. the Pt active component described in the claim 1 is characterized in that its quality percentage composition is 0～5%, and with Pt (NH
3)
2(NO
2)
2Or Pt (NO
3)
2In a kind of be presoma, Pt concentration is 0.001～0.05mol/l in the used precursor water solution.
8. the cordierite honeycomb ceramic carrier that scribbles the Ti-Sn composite oxides described in the claim 2; , it is characterized in that its preparation method is as follows:
(1) preparation of Ti-Sn composite oxides slurries
Take by weighing a certain amount of Ti-Sn composite oxides, add a certain proportion of aqueous solution of silica gel, high-speed stirred 0-10 hour, obtain certain density Ti-Sn composite oxides slurries.
(2) coating of Ti-Sn composite oxides
The cordierite honeycomb ceramic sample of anticipating is immersed in the Ti-Sn composite oxides slurries that prepare, flood after 2 minutes and take out, blow the raffinate in the most duct, the back 110 ℃ of dryings of in air, drying in the shade 2 hours, roasting is 2 hours under 200-800 ℃ of air.
9. the prereduction in the claim 2 is characterized in that reducing gas is a hydrogen, and reduction temperature is 200～600 ℃, and the recovery time is 1～6h, and purpose is to make Pt to be in metallic state.Pre-oxidation in the claim 2 is characterized in that oxidizing gas adopts air or pure oxygen, and the pre-oxidation temperature is at 200～600 ℃, and preoxidation time is 1～6h, and purpose is Pt is partly placed oxidation state.
10. the integral catalyst described in the claim 1 is applicable to the removal of formaldehyde in the air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010177901XA CN102247842A (en) | 2010-05-18 | 2010-05-18 | High-efficiency catalyst for removing formaldehyde at room temperature |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010177901XA CN102247842A (en) | 2010-05-18 | 2010-05-18 | High-efficiency catalyst for removing formaldehyde at room temperature |
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| CN102247842A true CN102247842A (en) | 2011-11-23 |
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ID=44975621
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|---|---|---|---|
| CN201010177901XA Pending CN102247842A (en) | 2010-05-18 | 2010-05-18 | High-efficiency catalyst for removing formaldehyde at room temperature |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103962128A (en) * | 2014-03-27 | 2014-08-06 | 青岛道一空优科技有限公司 | Photocatalytic glass ball for removing formaldehyde |
| CN106040230A (en) * | 2016-06-02 | 2016-10-26 | 华东理工大学 | Method for preparing integrated catalyst for low-temperature catalytic oxidation of formaldehyde |
| CN111437814A (en) * | 2020-05-08 | 2020-07-24 | 清华大学盐城环境工程技术研发中心 | Tin-doped platinum-titanium catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3894965A (en) * | 1972-04-12 | 1975-07-15 | Corning Glass Works | Process for depositing noble metal catalysts |
| CN101274281A (en) * | 2007-03-16 | 2008-10-01 | 北京安泽汶科技发展有限公司 | Room temperature catalyst for removing formaldehyde in air and method of preparing the same |
-
2010
- 2010-05-18 CN CN201010177901XA patent/CN102247842A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3894965A (en) * | 1972-04-12 | 1975-07-15 | Corning Glass Works | Process for depositing noble metal catalysts |
| CN101274281A (en) * | 2007-03-16 | 2008-10-01 | 北京安泽汶科技发展有限公司 | Room temperature catalyst for removing formaldehyde in air and method of preparing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103962128A (en) * | 2014-03-27 | 2014-08-06 | 青岛道一空优科技有限公司 | Photocatalytic glass ball for removing formaldehyde |
| CN106040230A (en) * | 2016-06-02 | 2016-10-26 | 华东理工大学 | Method for preparing integrated catalyst for low-temperature catalytic oxidation of formaldehyde |
| CN106040230B (en) * | 2016-06-02 | 2019-01-18 | 上海华明高技术（集团）有限公司 | A kind of preparation method of the integrated catalyst for formaldehyde low-temperature catalytic oxidation |
| CN111437814A (en) * | 2020-05-08 | 2020-07-24 | 清华大学盐城环境工程技术研发中心 | Tin-doped platinum-titanium catalyst and preparation method and application thereof |
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Application publication date: 20111123 |