CN102909031B - 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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- CN102909031B CN102909031B CN201210459694.6A CN201210459694A CN102909031B CN 102909031 B CN102909031 B CN 102909031B CN 201210459694 A CN201210459694 A CN 201210459694A CN 102909031 B CN102909031 B CN 102909031B
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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 eliminated for toluene catalytically in air.
Background technology
In today that environment for human survival goes from bad to worse, environmental pollution receives the great attention of common people, 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 matter (Volatile Organic Fempounds-VOCs) is the important component part of atmosphere pollution, and VOCs is of a great variety, 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 strong carcinogenicity and poisons the effect of central nervous system, have caused the great attention of countries in the world.World many countries has formulated the atomosphere quality standard of benzene homologues, is 5 μ g/m as European Union performed the average annual concentration limit of benzene in air from 1 day December in 2000
3, rising on January 1st, 2006 is 1 μ g/m
3.In the World Health Organization (WHO) regulation air, the per day exposure concentration limit value of toluene is 8.21 μ g/m
3.Benzene homologues also has close ties with Atmospheric Photochemical Smog, aerocolloidal formation, generates the photochemical fog that toxicity is larger.Processing method for benzene homologues can be divided into two large classes usually: a class is non-destructive technique and 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 process the benzene homologues gas of low concentration under far below direct ignition temperature condition, has the advantages that purification efficiency is high, non-secondary pollution, energy consumption are low, is one of the most effective processing method of process benzene homologues application.
Domestic and international researcher has carried out a large amount of correlative study to catalyst for catalytic combustion, 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, benzene homologues catalyst for catalytic combustion used mainly contains noble metal catalyst, comprises containing Pt, Pd, Ru and Au etc., due to high, selective good, the long service life of activity, and there is the advantages such as good antitoxin performance, cause the great interest of researcher.Although noble metal catalyst has lot of advantages, due to its expensive and limit noble metal catalyst benzene homologues eliminate in application.Therefore, cheap in recent years catalyst of transition metal oxide causes the broad interest of people.Research for catalyst of transition metal oxide finds, composite oxide catalysts shows superior catalytic activity and stability, even can reach the catalytic effect of noble metal catalyst, and price exist very large advantage, and easily obtain, therefore have broad application prospects.
In addition, there is the defects such as specific area is little, hole is undeveloped, pore-size distribution is irregular in conventional metal oxide, which greatly limits the performance of its catalytic performance.In the last few years, the research of mesoporous material obtains huge development, develop into non-silicon-based material by silica-base material, wherein mesoporous metallic oxide material is due to some special natures such as adjustable sex change and crystal network structure of component and valence state, makes it become focus in the research in the field such as optical, electrical, magnetic, catalysis.Mesopore oxide has large specific area and flourishing pore structure, this catalytic activity high for catalyst has provides material base, confirm that mesopore oxide material has high catalytic activity by the result of study of CO catalytic oxidation, but research mesopore oxide material being used for the catalytic removal of benzene homologues have not been reported.Therefore; carry out the mesopore oxide especially synthesis of mesoporous composite oxides and the research of benzene homologues catalytic removal performance; not only to the synthesis of mesoporous composite oxides and application, there is important using value and scientific meaning, the catalytic removal of benzene homologues and atmospheric environment protection are also had great importance.
Summary of the invention
In view of this, the invention provides a kind of Catalysts and its preparation method eliminated for toluene catalytically in air, this catalyst is with low cost and to have good low temperature toluene catalytic combustion active.
The invention discloses a kind of catalyst eliminated for toluene catalytically in air, 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 above-mentioned preparation method for the catalyst of toluene catalytically elimination in air, comprise the following steps:
1) single-steeping: template be impregnated in the solution of molysite and manganese salt, then solvent evaporated also dry process, obtained siccative;
2) bakes to burn the article: calcination steps 1 in Muffle furnace) obtained siccative;
3) double-steeping: the product after bakes to burn the article be impregnated in again in the solution of molysite and manganese salt, then solvent evaporated also dry process, obtained siccative;
4) after baking: calcination steps 3 again in Muffle furnace) obtained siccative;
5) template is removed: spend the product after template washing after baking, remove the template in product;
6) washing is dried: washing removes the product after template to neutral, then dries, obtained described catalyst.
Further, in described step 1) and 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 described step 1), the ratio of the gross weight of the consumption of template and ferric nitrate and manganese nitrate is 1:1.
Further, described step 2) and step 4) in, the design parameter of roasting is: siccative is warming up to 573 ~ 773 K with the heating rate of 5 K/min in room temperature Muffle furnace, then constant temperature calcining 2 ~ 4 h under 573 ~ 773 K.
Further, in described step 5), template is gone to be the NaOH solution of concentration 2mol/L.
Beneficial effect of the present invention is:
1) composite oxides with meso-hole structure formed with base metal manganese and iron, for active component, considerably reduce catalyst cost;
2) catalyst of the present invention is at high reaction velocity (66,000 mLh
-1g
-1), to show good toluene catalytic combustion under low reaction temperature (< 523 K) active, has good low temperature toluene catalytic combustion active;
3) molysite and manganese salt are obtained mesoporous Fe-Mn composite oxide catalysts by hard template method by the present invention, and the method technique is simple, and mild condition is easily controlled, reproducible.
Accompanying drawing explanation
In order to make the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail, 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.
Detailed description of the invention
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
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, comprises the following steps:
1) single-steeping: template to be impregnated in the ethanol solution of ferric nitrate and manganese nitrate (ratio of the gross weight of the consumption of template and ferric nitrate and manganese nitrate is 1:1), in 313 K evaporate to dryness anhydrous ethanol solvents under continuous stirring condition, obtain raw material, gained raw material is freeze-day with constant temperature 24 h under 373 K, obtained siccative; Described template is mesoporous KIT-6 template, and its synthetic method reference is 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) obtains is warming up to 673 K with the heating rate of 5 K/min in room temperature Muffle furnace, then constant temperature calcining 2 h under 673 K;
3) double-steeping: the product after bakes to burn the article be impregnated in again ferric nitrate and (consumption and the single-steeping of nitrate are identical) in the ethanol solution of manganese nitrate, in 313 K evaporate to dryness anhydrous ethanol solvents under continuous stirring condition, obtain raw material, gained raw material is freeze-day with constant temperature 24 h under 373 K, obtained siccative;
4) after baking: the siccative that step 3) obtains is warming up to 773 K with the heating rate of 5 K/min in room temperature Muffle furnace, then constant temperature calcining 2 h under 773 K;
5) template is removed: spend the product after template washing after baking, during washing under 323K stir process, centrifugation after washing, and then adds template, and so repeat 4 times, the template in product is removed substantially; The described template that goes is the NaOH solution of concentration 2mol/L;
6) washing is dried: washing removes the product after template to neutral, then dries, obtained described catalyst.
embodiment 2
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 catalytic removal of toluene in air, carries out the activity rating of catalyst; The activity rating of catalyst is carry out in the miniature tubular fixed-bed reactor of 8 mm at ambient pressure in internal diameter, and thermocouple is built in reactor, and reaction temperature is controlled by ü GU-708P type temperature programming controller, and microreactor is placed in 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 to load 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, in this reaction temperature and 66,000 mLh
-1g
-1under reaction gas space velocities, constant temperature eliminates toluene (air mass flow is controlled by flowmeter), by residual toluene content in the GC-7900II type gas-chromatography on-line checkingi tail gas of band 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:
As can be seen from above-mentioned toluene conversion result, catalyst of the present invention is at high reaction velocity (66,000 mLh
-1g
-1), to show good toluene catalytic combustion under low reaction temperature (< 523 K) active, such as: the catalyst (embodiment 1) of Fe:Mn=1:1 can reach the toluene removal rate of 100% when 493K, the catalyst (embodiment 3) of Fe:Mn=1:1.2 can reach the toluene removal rate being greater than 99% when 503K, effectively the concentration of toluene in air can be dropped to 100 below ppm, reach the object purified air.And the existing non-precious metal catalyst for benzene homologues catalytic combustion generally just need can reach the toluene removal rate of about 95% (as document in the reaction temperature of 533 more than K, 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 reaction temperature recording 533 more than K in 60-67. document just can reach the toluene removal rate of about 95%).Visible, it is active that catalyst of the present invention has good low temperature toluene catalytic combustion.
The catalyst of embodiment 1 ~ 5 is carried out X-ray diffraction analysis; X-ray diffraction analysis adopts on Rigaku Co., Ltd. Rigaku D/Max-2500/PC type X-ray diffractometer and carries out; Cu K
αfor radiographic source, λ=1
.5418, Ni filtering, pipe pressure is 40 kV, Guan Liuwei 200 mA, and sweep speed is 5
°/ min, sweep interval is 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, as shown in Figure 1, mainly detected MnFe in obtained Mn-Fe oxide catalyst
2o
4and Fe
2o
3thing phase, but the XRD diffraction peak intensity of all recognizate phases is more weak and peak is wider, show in obtained Mn-Fe oxide catalyst, the degree of crystallinity of existing thing phase is 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 established material base.
The catalyst of embodiment 1 ~ 5 is carried out TEM experiment; The Tecnai G that TEM experiment is produced in FEI Co.
2spirit transmission electron microscope carries out, accelerating potential 120 kV, will test sample mortar porphyrize, in absolute ethyl alcohol after ultrasonic disperse, get supernatant to be added drop-wise to and to support on the copper mesh of carbon film, can in observing samples microscopic appearance and structure under transmission electron microscope after placing certain hour drying.
TEM tests the TEM figure of the catalyst of the embodiment 1 ~ 5 obtained as shown in Figure 2, shows that the preparation process of embodiment 1 ~ 5 can copy the meso-hole structure of KIT-6 template well, and the obtained Mn-Fe composite oxide catalysts with flourishing meso-hole structure.Schemed from TEM, the aperture of obtained Mn-Fe composite oxide catalysts is about 7.0 nm, the situation of change on obtained Mn-Fe composite oxide catalysts of Mn/Fe mol ratio has impact, 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 obtained Mn-Fe composite oxide catalysts prosperity, for the absorption of reactant molecule and activation provide superior condition, also for the diffusion in catalyst of reactant and product molecule and migration provide superior condition, this catalytic activity that can be catalyst high lays the foundation.
In the present invention, the kind of template, molysite, manganese salt, the concrete technology parameter etc. of drying, roasting, all suitably can adjust according to the requirement of hard template method, all can realize object of the present invention.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by referring to the preferred embodiments of the present invention, invention has been described, but those of ordinary skill in the art is to be understood that, various change can be made to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (2)
1. for the catalyst that toluene catalytically in air is eliminated, it is characterized in that: the active component of this catalyst is be the composite oxides with meso-hole structure that 1:1 forms by Fe and Mn by atomic ratio, comprises the following steps:
1) single-steeping: mesoporous KIT-6 template be impregnated in the ethanol solution of ferric nitrate and manganese nitrate, the ratio of the gross weight of the consumption of template and ferric nitrate and manganese nitrate is 1:1, then solvent evaporated dry process, obtained siccative;
2) bakes to burn the article: the siccative that step 1) is obtained is placed in Muffle furnace, is warming up to 573 ~ 773 K, then constant temperature calcining 2 ~ 4 h under 573 ~ 773 K with the heating rate of 5 K/min;
3) double-steeping: the product after bakes to burn the article be impregnated in again in the ethanol solution of ferric nitrate and manganese nitrate, then solvent evaporated also dry process, obtained siccative;
4) after baking: calcination steps 3 again in Muffle furnace) obtained siccative, method of operating is with step 2);
5) template is removed: with the product after the NaOH solution washing after baking of concentration 2mol/L, remove the template in product;
6) washing is dried: washing removes the product after template to neutral, then dries, obtained catalyst.
2. the preparation method for the catalyst of toluene catalytically elimination in air according to claim 1, is characterized in that: comprise the following steps:
1) single-steeping: mesoporous KIT-6 template be impregnated in the ethanol solution of ferric nitrate and manganese nitrate, the ratio of the gross weight of the consumption of template and ferric nitrate and manganese nitrate is 1:1, then solvent evaporated dry process, obtained siccative;
2) bakes to burn the article: the siccative that step 1) is obtained is placed in Muffle furnace, is warming up to 573 ~ 773 K, then constant temperature calcining 2 ~ 4 h under 573 ~ 773 K with the heating rate of 5 K/min;
3) double-steeping: the product after bakes to burn the article be impregnated in again in the ethanol solution of ferric nitrate and manganese nitrate, then solvent evaporated also dry process, obtained siccative;
4) after baking: calcination steps 3 again in Muffle furnace) obtained siccative, method of operating is with step 2);
5) template is removed: with the product after the NaOH solution washing after baking of concentration 2mol/L, remove the template in product;
6) washing is dried: washing removes the product after template to neutral, then dries, obtained catalyst.
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| CN103212406B (en) * | 2013-04-19 | 2015-04-22 | 重庆工商大学 | MnOx catalyst for catalytically eliminating benzene series in air and preparation method of MnOx catalyst |
| CN105032356B (en) * | 2015-06-05 | 2017-08-11 | 中国科学院生态环境研究中心 | A kind of hollow ferrimanganic composite materials prepared based on etching template and its 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 |
| CN109012656B (en) * | 2018-08-07 | 2021-03-30 | 广东工业大学 | Ordered mesoporous gamma-MnO2Catalyst, preparation method and application thereof |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260248A (en) * | 1992-08-28 | 1993-11-09 | Carus Corporation | Stable high temperature manganese based oxidation catalyst |
| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260248A (en) * | 1992-08-28 | 1993-11-09 | Carus Corporation | Stable high temperature manganese based oxidation catalyst |
| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
Non-Patent Citations (1)
| Title |
|---|
| Mesoporous ferrihydrite with incorporated manganese for rapid removal of organic contaminants in air;Thomas Mathew et al;《Chemical Communications》;20120924;第48卷(第89期);第10987页第2段及图1 * |
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