CN102838168A - Mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously - Google Patents
Mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously Download PDFInfo
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- CN102838168A CN102838168A CN2011101743008A CN201110174300A CN102838168A CN 102838168 A CN102838168 A CN 102838168A CN 2011101743008 A CN2011101743008 A CN 2011101743008A CN 201110174300 A CN201110174300 A CN 201110174300A CN 102838168 A CN102838168 A CN 102838168A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously, which relates to the field of catalysis and environmental protection. The mesoporous manganese oxide nanometer material is characterized by adopting honeycomb ceramics as a carrier, and carrying mesoporous manganese oxide as a substrate. The mesoporous manganese oxide is characterized in that: the aperture of a mesopore is 0.5-3nm. The monolithic catalyst provided by the invention can be used for completely and simultaneously removing the formaldehyde and the ozone in the air in realistic environment with room temperature and normal atmospheric humidity, and has high effect, stability and no side effect.
Description
Technical field
The present invention is the mesoporous manganese oxide nano material that a kind of while room temperature is removed ozone and formaldehyde in the air, relates to catalysis and field of environment protection.It is characterized in that adopting ceramic honey comb is carrier, is matrix with the mesoporous manganese of first load oxidation.The mesoporous manganese oxide matrix is characterised in that mesoporous aperture is 0.5-3nm.Integral catalyst of the present invention can be removed the formaldehyde and the ozone of air fully simultaneously in the often wet true environment of room temperature, and has efficient, stability and have no side effect.
The invention still further relates to above-mentioned mesoporous material preparation method.
The invention still further relates to above-mentioned mesoporous material and be applied to the improvement of various environmental protection and air ozone and formaldehyde.
Background technology
International cancer research institution of the World Health Organization (IARC) tissue is pointed out: formaldehyde can cause human carcinogenic.Research shows that formaldehyde is the higher material of a kind of toxicity, 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, white blood disease and dead possibility.Therefore, China " IAQ standard " (GB/T18883-2002) in the regulation formaldehyde in indoor air hygienic standard (maximum permissible concentration) be respectively 0.10mg/m
3Simultaneously, along with steadily improving of China's rapid development of economy and living standards of the people, the repairs profession that is driven by real estate and construction industry has obtained unprecedented development.Therefore, the air formaldehyde pollution problem that is caused by finishing or finishing material is very serious, has caused that the whole world pays close attention to greatly, and the formaldehyde of removing in the room air is extremely urgent.
The method that purifies formaldehyde comprises absorption method, chemical reaction method, photocatalytic oxidation and heat catalytic oxidation method.The short-term effective means is a chemical reaction method at present; Promptly through chemical reagent and formolite reaction to reach the purpose of removing formaldehyde in the air; Its main drawback is that chemical reagent is sometimes dangerous, cost is high, can only once uses, and may cause secondary pollution etc.Common chemical reaction method: formaldehyde generates water and carbonic acid gas after being loaded in the strainer that aluminum oxide or activated carbon make through the potassium permanganate load.But in case the potassium permanganate completely consumed, strainer will lose efficacy.Spray chemical reagent in the air or polluted air is fed chemical reagent solution, generate other chemical substance by chemical reagent (like organic amine etc.) and formaldehyde complexing.Except the cost height, more very be that the material itself that it generated has certain toxicity, usually with the form suspended of aerosol particle in air, can directly get into human respiratory tract and lung, bigger to human harm.
Absorption method and photocatalytic method also are the methods of the removal formaldehyde in indoor air pollutent used always.Sorbent material commonly used is porous material such as gac, the molecular sieve etc. of high-ratio surface in the absorption method.Because boiling point of formaldehyde lower (20 ℃) and molecule have stronger polarity; So at room temperature gaseous formaldehyde the surface be nonpolar or material such as low-pole gac on absorption generally a little less than; Therefore in practical application, need carry out modification to these porous masses usually, to improve its adsorptive power.Yet physical adsorption still is that chemisorption all can not obtain satisfied effect, because when absorption and desorption reach balance when saturated (adsorb), sorbent material will lose efficacy maybe to be needed to regenerate.Catalyzer commonly used in the photochemical catalytic oxidation formaldehyde technology is TiO
2Yet, the lower formaldehyde of full-scale condition remove efficiency limitations, among others photochemical catalysis use widely.Also have, make the migration of its electronics occur in problem such as visible region through modification and remain problem demanding prompt solution in photocatalytic degradation formaldehyde and even the overall optical catalytic field photocatalyst.
Simultaneously, room temperature or low-temperature catalyzed method ozone decomposition are a kind of long lasting methods.Chinese patent CN90106857 adopts manganese, copper oxide to come ozone decomposition as active ingredient.CN1259398A, CN117167674A and CN1357348A adopt manganese, copper, nickel and ferriferous oxide as active ingredient, load on ozone decomposition on the activated carbon.CN1785507A adopt various Mn oxides as catalyzer at normal temperatures ozone decomposition obtained effect preferably.In Chinese patent CN1812835A employing manganese and zirconium or the iron one or both obtain the effect of ozone decomposition preferably as catalyzer at 150 ℃, need extra energy supplement.It is thus clear that manganese oxide is a kind of good ozone remover, the manganese oxide of different crystal structure has very big difference to the decomposability of ozone.Simultaneously, the humidity-proof ability of manganese oxide and low temperature active all await improving.
The catalytic oxidation airborne formaldehyde of degrading is a kind of long lasting method, and the most key is catalyzer.U.S. Pat 5585083 has been invented a kind of Pt/SnO
2Catalyzer is removed the method for formaldehyde in the air, and catalyzer uses airborne oxygen will perfect as oxygenant and is degraded into carbonic acid gas and water fully under extra energy input and-5～25 ℃ of conditions not having.But Pt content (12%) high in the catalyzer causes costing an arm and a leg of catalyzer, and therefore this catalyzer can only be used special occasions such as some military projects or aerospace.Chinese patent CN1698932A perhaps adsorbs composite oxide catalysts with the rare earth oxide of load gold, under 80-100 ℃ of temperature, can obtain effect preferably, but the input of high humidity and heat energy is the biggest obstacle of this catalyzer widespread use.
The purpose of this invention is to provide a kind of honeycomb ceramic catalyze material of under the condition of room temperature and high humidity, efficiently removing formaldehyde, be about to airborne formaldehyde and be completely oxidized to carbonic acid gas (CO
2) and water (H
2O), be applicable to the removal of airborne formaldehyde pollutent.The airborne formaldehyde of environment protection catalytic oxidation removal has caused the attention in the world, because catalyzer does not need extra light or electric energy just can airborne formaldehyde be converted into harmless H
2O and CO
2, can stably decompose ozone to oxygen simultaneously simultaneously.Its advantage is: it is high to handle formaldehyde efficient, does not have secondary pollution and do not exist to adsorb problems such as saturated.
Summary of the invention
The object of the invention 1: provide a kind of while room temperature to remove the mesoporous manganese oxide nano material of ozone and formaldehyde in the air.
The object of the invention 2: provide a kind of while room temperature to remove the mesoporous manganese oxide preparation of nanomaterials of ozone and formaldehyde in the air.
The objective of the invention is to realize through following scheme:
The mesoporous manganese oxide nano material of ozone and formaldehyde in the while room temperature removal air provided by the invention, adopt following scheme implementation:
1. the preparation of mesoporous manganese oxide nano material
A certain amount of PVP is added the NaMnO that contains 0.01mol
4, KMnO
4Perhaps in the 250ml aqueous solution of soluble manganese salt; Constantly adding the 40ml trioctylamine under the agitation condition; Obtain colloidal sol, will seal then and behind 50 ℃ of crystallization 24h, colloidal sol is transferred to has in the teflon-lined still; In 100 ℃ of following hydro-thermal 24h; Products therefrom is put into the electric vacunm drying case in 100 ℃ of following vacuum-drying 24h behind deionized water and ethanol repetitive scrubbing: put into retort furnace at last in 200-500 ℃ of calcining 6h removed template method down, the gained powder is the mesoporous manganese oxide sample.
2. the preparation of honeycomb ceramic carrier loaded mesoporous manganese oxide nano material
(1) takes by weighing a certain amount of mesoporous manganese oxide nano material, add a certain proportion of deionized water and tackiness agent.According to the requirement of viscosity and particle diameter, tackiness agent is mixed suspended emulsion high-speed stirring 1～24h with the mesoporous manganese oxide nano material, obtain certain density mesoporous manganese oxide nano material slurries.
(2) adopt the vacuum-negative pressure extraction technique that above-mentioned mesoporous manganese oxide nano material slurries are coated on the ceramic honey comb of anticipating,, obtain the loaded mesoporous manganese oxide nano material at 200～800 ℃ of roasting 1～36h.
Technique effect of the present invention
Technique effect of the present invention is the characteristic that a kind of room temperature can thoroughly be removed airborne formaldehyde and ozone nanometer material simultaneously: under the often wet condition of room temperature, can be 0.010～50mg/m with concentration in the air simultaneously in the presence of unglazed
3Formaldehyde and 0.010～50mg/m
3Ozone change into nontoxic carbonic acid gas, water and oxygen.
Advantage of the present invention
1. high efficiency and broad spectrum
Efficient room temperature of the present invention is removed formaldehyde and ozone nanometer material simultaneously, adopts catalytic method, and PARA FORMALDEHYDE PRILLS(91,95) and ozone all have good removal ability.
2. high stability and long-lasting
Nano material of the present invention has been abandoned adsorption technology, adopts catalytic activation oxygen mechanism, and catalyzer did not consume when formaldehyde and ozone were removed, and has well long-lasting, very high stability and good economy, and human body is not had any adverse side effect.
Nontoxicity with have no side effect
Efficient room temperature of the present invention is removed the catalytic material of formaldehyde and ozone simultaneously, and when being applied to air clearing product, nontoxicity does not have by product carbon monoxide (CO) and formic acid and produces.
Embodiment
Embodiment one
The preparation of mesoporous manganese oxide nano material.A certain amount of PVP is added the NaMnO that contains 0.01mol
4, KMnO
4Perhaps in the 250ml aqueous solution of soluble manganese salt; Constantly adding the 40ml trioctylamine under the agitation condition; Obtain colloidal sol, will seal then and behind 50 ℃ of crystallization 24h, colloidal sol is transferred to has in the teflon-lined still; In 100 ℃ of following hydro-thermal 24h; Products therefrom is put into the electric vacunm drying case in 100 ℃ of following vacuum-drying 24h behind deionized water and ethanol repetitive scrubbing: put into retort furnace at last in 200-500 ℃ of calcining 6h removed template method down, the gained powder is the mesoporous manganese oxide sample.
The preparation of honeycomb ceramic carrier loaded mesoporous manganese oxide nano material.Take by weighing a certain amount of mesoporous manganese oxide nano material, add a certain proportion of deionized water and tackiness agent.According to the requirement of viscosity and particle diameter, tackiness agent is mixed suspended emulsion high-speed stirring 1～24h with the mesoporous manganese oxide nano material, obtain certain density mesoporous manganese oxide nano material slurries.Adopt the vacuum-negative pressure extraction technique that above-mentioned mesoporous manganese oxide nano material slurries are coated on the ceramic honey comb of anticipating,, obtain the loaded mesoporous manganese oxide nano material at 200～800 ℃ of roasting 1～36h.
The performance test of catalyzer is carried out on the fixed-bed reactor of continuous flow.Before the catalyst performance test, catalyzer is not done any processing; Fine catalyst is pulverized the granular of processing 0.25～0.50mm through compressing tablet, then the 0.2g granular is loaded in the Glass tubing; Be under 50% the condition in room temperature (20 ℃) and relative humidity, feed and contain 0.01-50mg/m
3The air of formaldehyde, wind speed are 2.5m/s.Reactor outlet gas detects with FTIR infrared spectrum analyser, trace gas analysis mass spectrograph and Aglient 7890A gas chromatographicanalyzer simultaneously simultaneously.The result sees table 1.
The test result of table 1. mesoporous manganese oxide nano material.
Embodiment two
The preparation of mesoporous manganese oxide nano material is with embodiment one
Before the catalyst performance test, catalyzer is not done any processing; Fine catalyst is pulverized the granular of processing 0.25～0.50mm through compressing tablet, then the 0.2g granular is loaded in the Glass tubing; Be under 50% the condition in room temperature (20 ℃) and relative humidity, feed and contain 0.001-50mg/m
3The air of ozone, wind speed are 2.5m/s.Reactor outlet ozone detects with ozone analyzer.。The result sees table 2.
The test result of table 2. catalytic elimination ozone.
Execute example three
The preparation of mesoporous manganese oxide nano material is with embodiment one
Before the catalyst performance test, catalyzer is not done any processing; Fine catalyst is pulverized the granular of processing 0.25～0.50mm through compressing tablet, then the 0.2g granular is loaded in the Glass tubing; Be under 50% the condition in room temperature (20 ℃) and relative humidity, feed and contain 0.001-50mg/m
3The air of ozone, wind speed are 2.5m/s.Reactor outlet ozone detects with ozone analyzer; Reactor outlet formaldehyde detects with FTIR infrared spectrum analyser, trace gas analysis mass spectrograph and Aglient 7890A gas chromatographicanalyzer simultaneously simultaneously.。The result sees table 3.
The test result of table 3. catalytic elimination ozone.
Claims (8)
1. the present invention is the mesoporous manganese oxide nano material that a kind of while room temperature is removed ozone and formaldehyde in the air, and the aperture of its characteristic mesoporous manganese oxide is 3nm, and the content of titanium is 0-50%.
2. room temperature is removed the mesoporous manganese oxide nano material of ozone and formaldehyde in the air in the time of in the claim 1, and its characteristic nano material is that it prepares as follows:
(1) preparation of mesoporous manganese oxide nano material.
(2) preparation of the loaded mesoporous manganese nano material of honeycomb ceramic carrier.
3. mesoporous manganese oxide preparation of nanomaterials in the claim 2 (1) is characterized in that adopting hydrothermal method synthetic:
A certain amount of PVP is added the NaMnO that contains 0.01mol
4, KMnO
4Perhaps in the 250ml aqueous solution of soluble manganese salt; Constantly adding the 40ml trioctylamine under the agitation condition; Obtain colloidal sol, will seal then and behind 50 ℃ of crystallization 24h, colloidal sol is transferred to has in the teflon-lined still; In 100 ℃ of following hydro-thermal 24h; Products therefrom is put into the electric vacunm drying case in 100 ℃ of following vacuum-drying 24h behind deionized water and ethanol repetitive scrubbing: put into retort furnace at last in 200-500 ℃ of calcining 6h removed template method down, the gained powder is the mesoporous manganese oxide sample.
4. the preparation of claim 2 (2) honeycomb ceramic carrier loaded mesoporous manganese oxide nano material is characterized in that the condition for preparing is following:
(1) takes by weighing a certain amount of mesoporous manganese oxide nano material, add a certain proportion of deionized water and tackiness agent.According to the requirement of viscosity and particle diameter, tackiness agent is mixed suspended emulsion high-speed stirring 1～24h with the mesoporous manganese oxide nano material, obtain certain density mesoporous manganese oxide nano material slurries.
(2) adopt the vacuum-negative pressure extraction technique that above-mentioned mesoporous manganese oxide nano material slurries are coated on the ceramic honey comb of anticipating,, obtain the loaded mesoporous manganese oxide nano material at 200～800 ℃ of roasting 1～36h.
5. the tackiness agent described in the claim 4 (1) is inorganic adhesives such as silicate, aluminum oxide or zirconium carbonate ammonium, and the weight ratio of tackiness agent and mesoporous manganese oxide nano material is between 1～50%.
6. the mesoporous material of purification ozone and formaldehyde simultaneously in the long-acting air at room temperature in the claim 1, the aperture that it is characterized in that is 0.5-3nm.
7. a kind of efficient moisture-resistant room temperature described in the claim 1 is removed the characteristic of ozone and formaldehyde catalyst simultaneously: in the presence of unglazed under the often wet condition of room temperature with oxidation air in concentration be 0.01～50mg/m
3Formaldehyde change into nontoxic carbonic acid gas and water.
8. a kind of efficient moisture-resistant room temperature described in the claim 1 is removed the characteristic of ozone and formaldehyde catalyst simultaneously: under the often wet condition of room temperature, can be 0.01～50mg/m with concentration in the air simultaneously in the presence of unglazed
3Formaldehyde and 0.001～50mg/m
3Ozone change into nontoxic carbonic acid gas, water and oxygen.
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| CN2011101743008A CN102838168A (en) | 2011-06-24 | 2011-06-24 | Mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously |
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| CN2011101743008A CN102838168A (en) | 2011-06-24 | 2011-06-24 | Mesoporous manganese oxide nanometer material capable of removing ozone and formaldehyde in air at room temperature simultaneously |
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| CN104338528A (en) * | 2013-07-30 | 2015-02-11 | 江苏瑞丰科技实业有限公司 | Preparation of room temperature formaldehyde catalyst |
| CN105148836A (en) * | 2015-07-08 | 2015-12-16 | 深圳市中纺滤材无纺布有限公司 | Catalytic decomposition type air purification material and preparation method thereof |
| CN106732573A (en) * | 2016-11-23 | 2017-05-31 | 北京易净优智环境科技有限公司 | For often wet catalyst for eliminating ozone of room temperature and preparation method thereof |
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN107376931A (en) * | 2017-03-22 | 2017-11-24 | 傅国琳 | A kind of solid catalyst and preparation method and purposes |
| CN107413328A (en) * | 2017-04-13 | 2017-12-01 | 湛江市斯格特环境科技有限公司 | A kind of area load type material for air purification and preparation method thereof |
| WO2018176779A1 (en) * | 2017-03-31 | 2018-10-04 | 南京大学 | Mesoporous ozone oxidation catalyst and preparation and usage method therefor |
| CN108772057A (en) * | 2018-06-28 | 2018-11-09 | 广东工业大学 | A kind of low-temperature SCR manganese oxide catalyst and its preparation method and application |
| CN109045959A (en) * | 2018-09-18 | 2018-12-21 | 南京大学射阳高新技术研究院 | A kind of reagent and method removing formaldehyde |
| CN109529613A (en) * | 2018-12-26 | 2019-03-29 | 深圳市中建南方环境股份有限公司 | A kind of method and purification system of the formaldehyde of mineralising at room temperature |
| CN110433868A (en) * | 2019-07-19 | 2019-11-12 | 淮阴工学院 | A kind of aerogel composite and preparation method thereof for formaldehyde catalytic decomposition |
| CN110482609A (en) * | 2019-08-05 | 2019-11-22 | 广东美的白色家电技术创新中心有限公司 | A kind of big table specific area ε-MnO of high-purity2Hydrothermal synthesis method |
| CN111013376A (en) * | 2018-10-09 | 2020-04-17 | 深圳市寒暑科技新能源有限公司 | Portable high-efficient formaldehyde air purification device that removes |
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| CN113976183A (en) * | 2020-07-08 | 2022-01-28 | 河南净好运医疗科技有限公司 | VOCS catalyst for normal temperature sterilization and disinfection treatment of formaldehyde and the like and preparation method thereof |
| CN115124332A (en) * | 2022-08-31 | 2022-09-30 | 广东简一(集团)陶瓷有限公司 | Ceramic tile with aldehyde-removing and humidity-adjusting functions and preparation method thereof |
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| CN104338528A (en) * | 2013-07-30 | 2015-02-11 | 江苏瑞丰科技实业有限公司 | Preparation of room temperature formaldehyde catalyst |
| CN105148836A (en) * | 2015-07-08 | 2015-12-16 | 深圳市中纺滤材无纺布有限公司 | Catalytic decomposition type air purification material and preparation method thereof |
| CN106732573A (en) * | 2016-11-23 | 2017-05-31 | 北京易净优智环境科技有限公司 | For often wet catalyst for eliminating ozone of room temperature and preparation method thereof |
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN106865618B (en) * | 2017-02-23 | 2018-05-04 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN107376931A (en) * | 2017-03-22 | 2017-11-24 | 傅国琳 | A kind of solid catalyst and preparation method and purposes |
| WO2018176779A1 (en) * | 2017-03-31 | 2018-10-04 | 南京大学 | Mesoporous ozone oxidation catalyst and preparation and usage method therefor |
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| CN108772057A (en) * | 2018-06-28 | 2018-11-09 | 广东工业大学 | A kind of low-temperature SCR manganese oxide catalyst and its preparation method and application |
| CN108772057B (en) * | 2018-06-28 | 2020-12-08 | 广东工业大学 | Low-temperature SCR manganese oxide catalyst and preparation method and application thereof |
| CN109045959A (en) * | 2018-09-18 | 2018-12-21 | 南京大学射阳高新技术研究院 | A kind of reagent and method removing formaldehyde |
| CN111013376A (en) * | 2018-10-09 | 2020-04-17 | 深圳市寒暑科技新能源有限公司 | Portable high-efficient formaldehyde air purification device that removes |
| CN109529613A (en) * | 2018-12-26 | 2019-03-29 | 深圳市中建南方环境股份有限公司 | A kind of method and purification system of the formaldehyde of mineralising at room temperature |
| CN109529613B (en) * | 2018-12-26 | 2020-09-25 | 深圳市中建南方环境股份有限公司 | Method for mineralizing formaldehyde at room temperature and purification system |
| CN110433868A (en) * | 2019-07-19 | 2019-11-12 | 淮阴工学院 | A kind of aerogel composite and preparation method thereof for formaldehyde catalytic decomposition |
| CN110482609A (en) * | 2019-08-05 | 2019-11-22 | 广东美的白色家电技术创新中心有限公司 | A kind of big table specific area ε-MnO of high-purity2Hydrothermal synthesis method |
| CN110482609B (en) * | 2019-08-05 | 2022-03-15 | 广东美的白色家电技术创新中心有限公司 | High-purity epsilon-MnO with large surface specific area2Hydrothermal synthesis method |
| CN111545193A (en) * | 2020-05-30 | 2020-08-18 | 西安交通大学 | Hollow core-shell structure catalyst for catalytic oxidation of nitrogen oxide and preparation method thereof |
| CN111545193B (en) * | 2020-05-30 | 2021-07-09 | 西安交通大学 | Hollow core-shell structure catalyst for catalytic oxidation of nitrogen oxide and preparation method thereof |
| CN113976183A (en) * | 2020-07-08 | 2022-01-28 | 河南净好运医疗科技有限公司 | VOCS catalyst for normal temperature sterilization and disinfection treatment of formaldehyde and the like and preparation method thereof |
| CN115124332A (en) * | 2022-08-31 | 2022-09-30 | 广东简一(集团)陶瓷有限公司 | Ceramic tile with aldehyde-removing and humidity-adjusting functions and preparation method thereof |
| CN116984026A (en) * | 2023-07-31 | 2023-11-03 | 嘉兴富瑞邦新材料科技有限公司 | Aldehyde-removing deodorizing catalyst and preparation method and application thereof |
| CN116984026B (en) * | 2023-07-31 | 2024-05-31 | 华阳新材料科技集团有限公司 | Aldehyde-removing deodorizing catalyst and preparation method and application thereof |
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Application publication date: 20121226 |