CN102909031A - Catalyst used for catalyzing and eliminating toluene in air and preparation method of catalyst - Google Patents
Catalyst used for catalyzing and eliminating toluene in air and preparation method of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst used for catalyzing and eliminating toluene in the air and a preparation method of the catalyst. An active component of the catalyst is a composite oxide of Fe and Mn, and the composite oxide of Fe and Mn is in a mesoporous structure. The preparation method of the catalyst comprises the steps of: primary dipping, primary roasting, secondary dipping, secondary roasting, removing a template, washing, drying and the like. The catalyst disclosed by the invention adopts composite oxide which is in the mesoporous structure and is formed by base metal Fe and Mn as the active components, thereby greatly reducing the cost of the catalyst. Moreover, the catalyst disclosed by the invention can present favorable catalytic combustion activity of the toluene at the high reaction space velocity (66,000mL.h<-1>.g<-1>) and low reaction temperature (523K), and has favorable low temperature toluene catalytic combustion activity.
Description
Technical field
The present invention relates to a kind of benzene homologues catalyst for catalytic combustion, be specifically related to a kind of Catalysts and its preparation method for the elimination of air toluene catalytically.
Background technology
In today that environment for human survival goes from bad to worse, environmental pollution has been subject to common people's great attention, and atmospheric environment is as one of important living environment of the mankind, and its pollution situation is paid much attention to equally.(Volatile Organic Fempounds-VOCs) is the important component part of atmosphere pollution to volatile organic matter, and VOCs is of a great variety, and complicated component has great harm to health and environment.Benzene homologues (as, benzene, toluene and dimethylbenzene etc.) be the important component part of VOCs, be widely used as initiation material or the solvent of industrial chemical, but they has the effect of strong carcinogenicity and murder by poisoning central nervous system, have caused the great attention of countries in the world.World many countries has been formulated the atomosphere quality standard of benzene homologues, carries out since on December 1st, 2000 such as European Union that the average annual concentration limit of benzene is 5 μ g/m in the atmosphere
3, rising on January 1st, 2006 is 1 μ g/m
3The per day exposure concentration limit value of toluene is 8.21 μ g/m in the World Health Organization (WHO) the regulation atmosphere
3Benzene homologues also has close ties with Atmospheric Photochemical Smog, aerocolloidal formation, generates the larger photochemical fog of toxicity.Processing method for benzene homologues can be divided into two large classes usually: a class is that non-destructive technology is absorption method; One class is destructive technology, namely make benzene homologues be converted into the inorganic matter that carbon dioxide, water and hydrogen chloride etc. are nontoxic or toxicity is little by chemistry or biological technology, these class methods comprise the common technique such as direct burning, catalytic combustion, biodegradation, plasma oxidation, photocatalytic oxidation.Wherein, catalytic combustion can be processed the benzene homologues gas of low concentration under far below direct ignition temperature condition, has that purification efficiency is high, a non-secondary pollution, characteristics that energy consumption is low, is to process benzene homologues to use one of the most effective processing method.
The researcher has carried out a large amount of correlative studys to catalyst for catalytic combustion both at home and abroad, and the purification treatment technology of benzene series substances in atmosphere has become a study hotspot in environmental catalysis field, and the key problem of correlative study is still the problem of the design and development of catalysis material.At present, used benzene homologues catalyst for catalytic combustion mainly contains noble metal catalyst, comprises containing Pt, Pd, Ru and Au etc., because active high, selective good, long service life, and have the good advantages such as antitoxin performance, caused researcher's very big interest.Although noble metal catalyst has lot of advantages, limited the application of noble metal catalyst in benzene homologues is eliminated owing to it is expensive.Therefore, cheap catalyst of transition metal oxide has caused people's broad interest in recent years.Research for catalyst of transition metal oxide is found, composite oxide catalysts shows superior catalytic activity and stability, even can reach the catalytic effect of noble metal catalyst, and has very large advantage on the price, and easily obtain, therefore have broad application prospects.
In addition, there are the defectives such as specific area is little, hole is undeveloped, pore-size distribution is irregular in conventional metal oxide, and this has limited the performance of its catalytic performance greatly.In the last few years, the research of mesoporous material has obtained huge development, develop into non-silica-base material by silica-base material, wherein mesoporous metallic oxide material is because some special natures such as the adjustable sex change of component and valence state and crystal network structure make its research in fields such as light, electricity, magnetic, catalysis become focus.Mesopore oxide has large specific area and flourishing pore structure, this catalytic activity high for catalyst has provides material base, result of study by the CO catalytic oxidation confirms that mesopore oxide material has high catalytic activity, but the research that mesopore oxide material is eliminated for the catalysis of benzene homologues yet there are no report.Therefore; carry out the especially research of the synthetic and benzene homologues catalysis elimination performance of mesoporous composite oxides of mesopore oxide; not only to the synthetic of mesoporous composite oxides with use and have important using value and scientific meaning, catalysis elimination and the atmospheric environment protection of benzene homologues also had great importance.
Summary of the invention
In view of this, the invention provides a kind of Catalysts and its preparation method of eliminating for the air toluene catalytically, this catalyst is with low cost and have a good low temperature toluene catalytically combustion activity.
The invention discloses a kind of catalyst for the elimination of air toluene catalytically, the active component of this catalyst is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure.
Further, in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1.5:1 ~ 1:1.5.
The invention also discloses the preparation method of the above-mentioned catalyst of eliminating for the air toluene catalytically, may further comprise the steps:
1) single-steeping: template be impregnated in the solution of molysite and manganese salt, solvent evaporated and dry the processing make siccative again;
2) bakes to burn the article: calcination steps 1 in Muffle furnace) siccative that makes;
3) double-steeping: the product behind the bakes to burn the article be impregnated in again in the solution of molysite and manganese salt, solvent evaporated and dry the processing make siccative again;
4) after baking: the siccative that calcination steps 3 again in Muffle furnace) makes;
5) template is removed: spend the product after template washs after baking, remove the template in the product;
6) washing oven dry: the product that washing is removed behind the template is extremely neutral, and then oven dry makes described catalyst.
Further, in described step 1) and the step 3), template is mesoporous KIT-6 template, and molysite is ferric nitrate, and manganese salt is manganese nitrate, and the solvent of molysite and manganese salt is absolute ethyl alcohol.
Further, in the described step 1), the consumption of template is 1:1 with the ratio of the gross weight of ferric nitrate and manganese nitrate.
Further, described step 2) and in the step 4), the design parameter of roasting is: siccative heating rate with 5 K/min in the room temperature Muffle furnace is warming up to 573 ~ 773 K, then constant temperature calcining 2 ~ 4 h under 573 ~ 773 K.
Further, in the described step 5), removing template is the NaOH solution of concentration 2mol/L.
Beneficial effect of the present invention is:
1) composite oxides with meso-hole structure that form take base metal manganese and iron are as active component, decrease the catalyst cost;
2) catalyst of the present invention is at high reaction velocity (66,000 mLh
-1G
-1), show good toluene catalytically combustion activity under the low reaction temperature (＜523 K), have good low temperature toluene catalytically combustion activity;
3) the present invention makes mesoporous Fe-Mn composite oxide catalysts with molysite and manganese salt by hard template method, and the method technique is simple, and mild condition is easily controlled, good reproducibility.
Description of drawings
In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing, wherein:
Fig. 1 is the XRD spectra of the catalyst of embodiment 1 ~ 5;
Fig. 2 is the TEM figure of the catalyst of embodiment 1 ~ 5.
The specific embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
The active component of the catalyst of the present embodiment is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure, and in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1:1.
The preparation method of the catalyst of the present embodiment may further comprise the steps:
1) single-steeping: template be impregnated in the ethanol solution of ferric nitrate and manganese nitrate (consumption of template is 1:1 with the ratio of the gross weight of ferric nitrate and manganese nitrate), constantly under the stirring condition in 313 K evaporate to dryness anhydrous ethanol solvents, get raw material, the gained raw material is freeze-day with constant temperature 24 h under 373 K, make siccative; Described template is mesoporous KIT-6 template, and its synthetic method is with reference to such as Publication about Document: F. Kleitz, S.H. Choi, R. Ryoo. Cubic
Ia3
dLarge mesoporous silica:synthesis and replication to platinum nanowires, carbon nanorods and carbon nanotubes [J]. Chem. Commun., 17 (2003) 2136 – 2137.;
2) bakes to burn the article: the siccative that step 1) makes heating rate with 5 K/min in the room temperature Muffle furnace is warming up to 673 K, then constant temperature calcining 2 h under 673 K;
3) double-steeping: the product behind the bakes to burn the article be impregnated in again in the ethanol solution of ferric nitrate and manganese nitrate (consumption and the single-steeping of nitrate are identical), constantly under the stirring condition in 313 K evaporate to dryness anhydrous ethanol solvents, get raw material, the gained raw material is freeze-day with constant temperature 24 h under 373 K, make siccative;
4) after baking: the siccative that step 3) makes heating rate with 5 K/min in the room temperature Muffle furnace is warming up to 773 K, then constant temperature calcining 2 h under 773 K;
5) template is removed: spend the product behind the template washing after baking, during washing under 323K stir process, centrifugation after the washing, and then add and remove template so repeats 4 times, the template in the product is removed substantially; The described template that goes is the NaOH solution of concentration 2mol/L;
6) washing oven dry: the product that washing is removed behind the template is extremely neutral, and then oven dry makes described catalyst.
The active component of the catalyst of the present embodiment is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure, and in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1:1.5.
The preparation method of the catalyst of the present embodiment is identical with embodiment 1.
Embodiment 3
The active component of the catalyst of the present embodiment is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure, and in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1:1.2.
The preparation method of the catalyst of the present embodiment is identical with embodiment 1.
Embodiment 4
The active component of the catalyst of the present embodiment is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure, and in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1.2:1.
The preparation method of the catalyst of the present embodiment is identical with embodiment 1.
Embodiment 5
The active component of the catalyst of the present embodiment is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure, and in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1.5:1.
The preparation method of the catalyst of the present embodiment is identical with embodiment 1.
The catalyst of embodiment 1 ~ 5 is used for the catalysis elimination of air toluene, carries out the activity rating of catalyst; The activity rating of catalyst carries out in internal diameter is the miniature tubular fixed-bed reactor of 8 mm under normal pressure, and thermocouple is built in the reactor, and reaction temperature is by the control of ü GU-708P type temperature programming controller, and microreactor places tube furnace; Toluene waste gas by volume percentage comprises: toluene 1.0 % and air 99.0 %; Concrete operation step is as follows:
Measure 50 mg catalyst and pack in the reaction tube of miniature tubular fixed-bed reactor, be warmed up to reaction temperature, pass into the toluene waste gas of described composition, at this reaction temperature and 66,000 mLh
-1G
-1Constant temperature is eliminated toluene (air mass flow is controlled by flowmeter) under the reaction gas air speed condition, detect online residual toluene content in the tail gas by the GC-7900II type gas-chromatography with hydrogen flame detector, testing conditions is: detector temperature 493 K, injector temperature 433 K, post case temperature perseverance is 433 K.
The toluene conversion result that above-mentioned catalyst activity evaluation experimental obtains is as follows:
Can find out from above-mentioned toluene conversion result, catalyst of the present invention is at high reaction velocity (66,000 mLh
-1G
-1), show good toluene catalytically combustion activity under the low reaction temperature (＜523 K), can reach 100% toluene removal rate when the 493K such as: the catalyst of Fe:Mn=1:1 (embodiment 1), the catalyst of Fe:Mn=1:1.2 (embodiment 3) can reach the toluene removal rate greater than 99% when 503K, can be effectively the concentration of toluene in the air be dropped to below 100 ppm, reach the purpose that purifies air.And existing non-precious metal catalyst for the benzene homologues catalytic combustion generally needs reaction temperature more than 533 K just can reach toluene removal rate about 95% (such as document, Deng J G, Zhang L, Dai H X, Chak-Tong A. Hydrothermally fabricated single-crystal line strontium-substituted lanthanum manganite microcubes for the catalytic combustion of toluene [J]. J. Mol. Catal. A:Chem., 2009,299 (1-2): the above reaction temperature of record 533 K just can reach the toluene removal rate about 95% in the 60-67. document).As seen, catalyst of the present invention has good low temperature toluene catalytically combustion activity.
The catalyst of embodiment 1 ~ 5 is carried out X-ray diffraction analysis; X-ray diffraction analysis adopts on the Rigaku Rigaku D/Max-2500/PC of Co., Ltd. type X-ray diffractometer and carries out; Cu K
αBe radiographic source, λ=1
.5418, Ni filtering, it is 40 kV that pipe is pressed, Guan Liuwei 200 mA, sweep speed is 5
°/ min, sweep interval are 20-80
°, scanning step is 0.02
°
The XRD spectra of the catalyst of the embodiment 1 ~ 5 that X-ray diffraction analysis obtains as shown in Figure 1, has mainly detected MnFe in the prepared Mn-Fe oxide catalyst as shown in Figure 1
2O
4And Fe
2O
3Phase, but all XRD diffraction peak intensities that detect phase are weak and the peak is wider, show in the prepared Mn-Fe oxide catalyst, the degree of crystallinity of existing phase is relatively poor, mainly exist with highly dispersed state or amorphous form, the high catalytic activity of catalyst that exists for of this highly dispersed state species has been established material base.
The catalyst of embodiment 1 ~ 5 is carried out the TEM experiment; The Tecnai G that the TEM experiment is produced in FEI Co.
2Carry out on the Spirit transmission electron microscope, accelerating potential 120 kV are with specimen mortar porphyrize, in absolute ethyl alcohol after the ultrasonic dispersion, get supernatant and be added drop-wise on the copper mesh that supports carbon film, can be in observing samples microscopic appearance and structure under the transmission electron microscope after the placement certain hour drying.
The TEM figure of the catalyst of the embodiment 1 ~ 5 that the TEM experiment obtains shows that the preparation process of embodiment 1 ~ 5 can copy the meso-hole structure of KIT-6 template well, and makes the Mn-Fe composite oxide catalysts with flourishing meso-hole structure as shown in Figure 2.By TEM figure as can be known, the aperture of prepared Mn-Fe composite oxide catalysts is about 7.0 nm, the variation of Mn/Fe mol ratio has impact to the situation of prepared Mn-Fe composite oxide catalysts, and the catalyst of Fe/Mn=1.0 and Fe/Mn=1.2 has larger aperture and pore structure more clearly.The meso-hole structure of prepared Mn-Fe composite oxide catalysts prosperity, for absorption and the activation of reactant molecule provides superior condition, also diffusion and the migration in catalyst provides superior condition for reactant and product molecule, and this can be the high catalytic activity of catalyst and lays the foundation.
Among the present invention, the kind of template, molysite, manganese salt, the concrete technology parameters of drying, roasting etc. all can suitably be adjusted according to the requirement of hard template method, all can realize purpose of the present invention.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (7)
1. one kind is used for the catalyst that the air toluene catalytically is eliminated, and it is characterized in that: the active component of this catalyst is the composite oxides of Fe and Mn, and the composite oxides of described Fe and Mn have meso-hole structure.
2. the catalyst of eliminating for the air toluene catalytically according to claim 1, it is characterized in that: in the composite oxides of described Fe and Mn, the atomic ratio of Fe and Mn is 1.5:1 ~ 1:1.5.
3. the preparation method of claim 1 or the 2 described catalyst of eliminating for the air toluene catalytically is characterized in that: may further comprise the steps:
1) single-steeping: template be impregnated in the solution of molysite and manganese salt, solvent evaporated and dry the processing make siccative again;
2) bakes to burn the article: calcination steps 1 in Muffle furnace) siccative that makes;
3) double-steeping: the product behind the bakes to burn the article be impregnated in again in the solution of molysite and manganese salt, solvent evaporated and dry the processing make siccative again;
4) after baking: the siccative that calcination steps 3 again in Muffle furnace) makes;
5) template is removed: spend the product after template washs after baking, remove the template in the product;
6) washing oven dry: the product that washing is removed behind the template is extremely neutral, and then oven dry makes described catalyst.
4. the preparation method of the catalyst of eliminating for the air toluene catalytically according to claim 3, it is characterized in that: in described step 1) and the step 3), template is mesoporous KIT-6 template, and molysite is ferric nitrate, manganese salt is manganese nitrate, and the solvent of molysite and manganese salt is absolute ethyl alcohol.
5. the preparation method of the catalyst of eliminating for the air toluene catalytically according to claim 4, it is characterized in that: in the described step 1), the consumption of template is 1:1 with the ratio of the gross weight of ferric nitrate and manganese nitrate.
6. the preparation method of the catalyst of eliminating for the air toluene catalytically according to claim 3, it is characterized in that: described step 2) and in the step 4), the design parameter of roasting is: siccative heating rate with 5 K/min in the room temperature Muffle furnace is warming up to 573 ~ 773 K, then constant temperature calcining 2 ~ 4 h under 573 ~ 773 K.
7. the preparation method of the catalyst of eliminating for the air toluene catalytically according to claim 3, it is characterized in that: in the described step 5), removing template is the NaOH solution of concentration 2mol/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212406A (en) * | 2013-04-19 | 2013-07-24 | 重庆工商大学 | MnOx catalyst for catalytically eliminating benzene series in air and preparation method of MnOx catalyst |
| CN106732539A (en) * | 2016-11-29 | 2017-05-31 | 西安元创化工科技股份有限公司 | Compound non-noble metal oxide catalyst for catalysis burning toluene and its preparation method and application |
| US20180056268A1 (en) * | 2015-06-05 | 2018-03-01 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Hollow iron-manganese composite material prepared by etching template process and application thereof |
| CN109012656A (en) * | 2018-08-07 | 2018-12-18 | 广东工业大学 | A kind of order mesoporous γ-MnO2Catalyst and its preparation method and application |
| CN111036232A (en) * | 2019-12-20 | 2020-04-21 | 南京工业大学 | Composite metal oxide catalyst for catalytic combustion and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212406A (en) * | 2013-04-19 | 2013-07-24 | 重庆工商大学 | MnOx catalyst for catalytically eliminating benzene series in air and preparation method of MnOx catalyst |
| US20180056268A1 (en) * | 2015-06-05 | 2018-03-01 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Hollow iron-manganese composite material prepared by etching template process and application thereof |
| US10493425B2 (en) * | 2015-06-05 | 2019-12-03 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Hollow iron-manganese composite material prepared by etching template process and application thereof |
| CN106732539A (en) * | 2016-11-29 | 2017-05-31 | 西安元创化工科技股份有限公司 | Compound non-noble metal oxide catalyst for catalysis burning toluene and its preparation method and application |
| CN106732539B (en) * | 2016-11-29 | 2019-05-17 | 西安元创化工科技股份有限公司 | For being catalyzed the compound non-noble metal oxide catalyst and its preparation method and application of burning toluene |
| CN109012656A (en) * | 2018-08-07 | 2018-12-18 | 广东工业大学 | A kind of order mesoporous γ-MnO2Catalyst and its preparation method and application |
| CN111036232A (en) * | 2019-12-20 | 2020-04-21 | 南京工业大学 | Composite metal oxide catalyst for catalytic combustion and preparation method thereof |
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