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1.
赵乐乐  王守信  王远洋 《工业催化》2015,23(11):874-881
以活性成分负载量、负载顺序和焙烧温度等关键制备参数因素进行正交实验设计制备了V_2O_5-WO_3/TiO_2催化剂,对其进行XRD和TPR表征,并在自行设计搭建的SCR烟气脱硝实验平台上评价其(300~390)℃的SCR脱硝性能。结果表明,活性成分钒和钨绝大多数以非晶态形式存在于载体表面,且具有良好的分散性;主要活性成分V_2O_5负载量越高,脱硝率越高;400℃焙烧温度可以形成催化反应所需的晶相,且维持催化剂较高的比表面积;催化剂低温活性和高温活性是由表面富集和各种成分之间相互作用共同产生的结果,活性组分与载体之间的相互作用对315℃低温脱硝活性影响明显,以先钒后钨负载顺序为宜,表面富集对390℃高温脱硝活性起主要作用,以钒钨同时负载或先钒后钨负载顺序较好;随着m(WO_3)∶m(V_2O_5)的增加,在7.5∶1处催化剂的脱硝率升至最高,随后迅速下降,WO_3负载质量分数以6%为宜。在优化条件V_2O_5负载质量分数0.8%、WO_3负载质量分数6%、先钒后钨负载和400℃焙烧温度下制备了催化剂并进行脱硝性能验证,315℃低温脱硝活性达到69.56%。  相似文献   

2.
An investigation has been carried out of the effect of vanadia loading on the activity and selectivity ofV2O5TiO2 aerogel catalysts, prepared by a two-step procedure, for the reduction of NO by propane. The structure of catalysts have been characterized by laser Raman spectroscopy and XRD measurements. At vanadia loading levels below ca. 4.4 wt%, the vanadia is present in the form of coordinated polymeric species, whereas crystallites of V2O5 are formed at higher vanadia contents. At this critical level of 4.4 wt% V2O5, the kinetic measurements showed also a maximum in the activity per mass of catalyst which very likely indicated that the coordinated polymeric surface species are more active than crystalline V2O5. The selectivity towards the formation of dinitrogen decreased as the loading increased, presumably because of the formation of larger polymeric species and V2O5 crystallites, below and above the critical loading level, respectively. For the reduction of NO by propane, titania supported vanadia aerogel catalysts are significantly more active, per mass of catalyst, and more selective towards N2 formation than conventionalV2O5TiO2 and V2O5Al2O3 aerogel catalysts, at vanadia loading levels below ca. 11 wt%.  相似文献   

3.
Pure and K-doped vanadia/titania prepared by different methods have been studied in order to elucidate the role of vanadia species (monomeric, polymeric, bulk) in catalytic toluene partial oxidation. The ratio of different vanadia species was controlled by treating the catalysts in diluted HNO3, which removes bulk vanadia and polymeric vanadia species, but not the monomeric ones, as was shown by FT-Raman spectroscopy and TPR in H2. Monolayer vanadia species (monomeric and polymeric) are responsible for the catalytic activity and selectivity to benzaldehyde and benzoic acid independently on the catalyst preparation method. Bulk V2O5 and TiO2 are considerably less active. Therefore, an increase of the vanadium concentration in the samples above the monolayer coverage results in a decrease of the specific rate in toluene oxidation due to the partial blockage of active monolayer species by bulk crystalline V2O5. Potassium diminishes the catalyst acidity resulting in a decrease of the total rate of toluene oxidation and suppression of deactivation. Deactivation due to coking is probably related to the Brønsted acid sites associated with the bridging oxygen in the polymeric species and bulk V2O5. Doping by K diminishes the amount of active monolayer vanadia leading to the formation of non-active K-doped monomeric vanadia species and KVO3.  相似文献   

4.
A series of titania (anatase)-supported vanadia catalysts ranging in V2O5 content from 0.4 to 9.9 mol% was prepared by wet impregnation technique, characterized by BET surface area measurement and X-ray diffraction, and evaluated for ammoxidation of 3-picoline. The average oxidation number of vanadium in the fresh and used catalysts was determined by titrimetric methods. The ammoxidation activity and the average oxidation number were observed to increase with vanadia loading up to 3.4 mol% in the catalyst which corresponds to a monolayer coverage. The phase transformation of anatase to rutile after the reaction was observed at a V2O5 loading of 5.9 mol%. The slow decrease of ammoxidation activity beyond 3.4 mol% V2O5 was attributed to the coverage of active monomeric VOx species on the support by bulk vanadia and by other oxides, and also to compound formation with ammonia.  相似文献   

5.
A novel multiwalled carbon nanotube (CNTs) supported vanadium catalyst was prepared. The structure of catalyst prepared was characterized by TEM, BET, FTIR, XRD and temperature-programmed desorption (TPD) methods. The results indicated that vanadium particles were highly dispersed on the wall of carbon nanotubes. The V2O5/CNT catalysts showed good activities in the SCR of NO with a temperature range of 373–523 K. The Lewis acid sites on the surface of V2O5/CNT are the active sites for the selective catalytic reduction (SCR) of NO with NH3 at low temperatures. It was suggested that the reaction path might involve the adsorbed NH3 species reacted with NO from gaseous phase and as well as the adsorbed NO2 species. The diameter of CNTs showed positive effect on the activities of the catalysts. Under the reaction conditions of 463 K, 0.1 Mpa, NH3/NO = 1, GHSV = 35,000 h−1, and V2O5 loading of 2.35 wt%, the outer diameter of CNTs of 60–100 nm, the NO conversion was 92%.  相似文献   

6.
The molecular structures and reactivity of the group V metal oxides (V2O5, Nb2O5 and Ta2O5) were compared. Their solid state structural chemistry, physical and electronic properties, number of active surface sites and their chemical reactivity properties were examined. For the bulk oxides, the solid state structural chemistry and the physical and electronic properties are well established. The number of active surface sites and the distribution of surface redox/acid sites were determined with methanol chemisorption and methanol oxidation, respectively. These studies revealed that the active surface sites present in pure V2O5 are primarily redox sites and the active surface sites in pure Nb2O5 are essentially acidic in nature. Furthermore, the surface redox sites present in pure V2O5 are orders of magnitude more active than the surface acid sites in pure Nb2O5. Consequently, the catalytic properties of bulk V2O5–Nb2O5 mixed oxides are dominated by the vanadia component. For the supported metal oxides, where the group V metal oxides are present as two-dimensional metal oxide overlayers, the structural and electronic properties are not well established in the literature. From a combination of molecular spectroscopic characterization methods (e.g., XANES, Raman, IR and UV–Vis DRS), it was possible to obtain this fundamental information. Methanol chemisorption studies demonstrated that a similar number of active surface sites are present in the supported vanadia and niobia catalyst systems. Similar to their bulk oxides, the surface vanadia species possess redox characteristics and the surface niobia species primarily possess acidic characteristics (Lewis acidity). The surface niobia species was a very sluggish redox site during oxidation reactions (e.g., methanol oxidation to formaldehyde and SO2 oxidation to SO3), but significantly promoted the surface vanadia redox sites for oxidation reactions that required dual surface redox and acid sites (e.g., butane oxidation to maleic anhydride and selective catalytic reduction of NOx by NH3 to produce N2). These new fundamental insights are allowing for the molecular engineering of group V metal oxide catalysts (especially vanadia and niobia). In contrast, the molecular structure and reactivity properties of Ta2O5 catalysts are not yet established and will require significant research efforts.  相似文献   

7.
A series of V2O5–TiO2 aerogel catalysts were prepared by sol–gel method with subsequent supercritical drying with CO2. The aerogel catalysts showed much higher surface areas and total pore volumes than V2O5–TiO2 xerogel and impregnated V2O5–TiO2 catalysts. Two species of surface vanadium in the aerogel catalysts were identified by Raman measurements: monomeric vanadyl and polymeric vanadates. The selective oxidation of hydrogen sulfide in the presence of excess water and ammonia was studied over these catalysts. Aerogel catalysts showed very high conversion of H2S without harmful emission of SO2. Temperature programmed reduction (TPR), XRD and Raman analyses revealed that the high catalytic performance of the aerogel catalysts originated from their highly dispersed VOx species and high reducibility.  相似文献   

8.
TiO2-SiO2 with various compositions prepared by the coprecipitation method and vanadia loaded on TiO2-SiO2 were investigated with respect to their physico-chemical characteristics and catalytic behavior in SCR of NO by NH3 and in the undesired oxidation of SO2 to SO3, using BET, XRD, XPS, NH3-TPD, acidity measurement by the titration method and activity test. TiO2-SiO2, compared with pure TiO2, exhibits a remarkably stronger acidity, a higher BET surface area, a lower crystallinity of anatase titania and results in allowing a good thermal stability and a higher vanadia dispersion on the support up to high loadings of 15 wt% V2O5. The SCR activity and N2 selectivity are found to be more excellent over vanadia loaded on TiO2-SiO2 with 10–20 mol% of SiO2 than over that on pure TiO2, and this is considered to be associated with highly dispersed vanadia on the supports and large amounts of NH3 adsorbed on the catalysts. With increasing SiO2 content, the remarkable activity decrease in the oxidation of SO2 to SO3, favorable for industrial SCR catalysts, was also observed, strongly depending on the existence of vanadium species of the oxidation state close to V4+ on TiO2-SiO2, while V5+ exists on TiO2, according to XPS. It is concluded that vanadia loaded on Ti-rich TiO2-SiO2 with low SiO2 content is suitable as SCR catalysts for sulfur-containing exhaust gases due to showing not only the excellent de-NOx activity but also the low SO2 oxidation performance.  相似文献   

9.
The catalytic oxidation of sulfur dioxide to sulfur trioxide over several binary (MxOy/TiO2) and ternary (V2O5/MXOY/TiO2) supported metal oxide catalysts was systematically investigated. The supported metal oxide components were essentially 100% dispersed as surface metal oxide species, as confirmed by Raman spectroscopy characterization. The sulfur dioxide oxidation turnover frequencies of the binary catalysts were all within an order of magnitude (V2O5/TiO2>Fe2O3/TiO2>Re2O7/TiO2  CrO3/TiO2  Nb2O5/TiO2>MoO3/TiO2  WO3/TiO2). An exception was the K2O/TiO2 catalysts, which is essentially inactive for sulfur dioxide oxidation. With the exception of K2O, all of the surface metal oxide species present in the ternary catalysts (i.e., oxides of V, Fe, Re, Cr, Nb, Mo and W) can undergo redox cycles and oxidize SO2 to SO3. The turnover frequency for sulfur dioxide oxidation over all of these catalysts is approximately the same at both low and high surface coverages. This indicates that the mechanism of sulfur dioxide oxidation is not sensitive to the coordination of the surface metal oxide species. A comparison of the activities of the ternary catalysts with the corresponding binary catalysts suggests that the surface vanadium oxide and the additive surface metal oxide redox sites act independently without synergistic interactions. The V2O5/K2O/TiO2 catalyst showed a dramatic reduction in the catalytic activity in comparison to the unpromoted V2O5/TiO2 catalyst. The ability of K2O to significantly retard the redox potential of the surface vanadia species is primarily responsible for the lower catalytic activity of the ternary catalytic system. The fundamental insights generated from this research can potentially assist in the molecular design of the air pollution control catalysts: (1) the development of catalysts for low temperature oxidation of SO2 to SO3 during sulfuric acid manufacture (2) the design of efficient SCR DeNOx catalysts with minimal SO2 oxidation activity and (3) improvements in additives for the simultaneous oxidation/sorption of sulfur oxides in petroleum refinery operations.  相似文献   

10.
碱金属化合物对V2O5/AC催化剂低温脱硝的影响   总被引:1,自引:1,他引:0       下载免费PDF全文
韩斌  雷志刚  刘茜  陈标华 《化工学报》2013,64(8):2867-2874
研究了碱金属化合物(K2SO4)对活性炭(AC)担载五氧化二钒(V2O5)组成的V2O5/AC催化剂的低温脱硝活性的影响。发现在V2O5/AC催化剂表面负载碱金属化合物(K2SO4)后其脱硝活性大大降低。用等体积浸渍法制备了V2O5/AC催化剂和Kx-V2/AC(x=0.5,1,2)催化剂。采用5种模型对动力学实验数据进行关联。结果显示,无论V2O5/AC催化剂是否负载K2SO4,Eley-Rideal模型均比其他模型可更好地描述SCR脱硝反应,碱金属化合物(K2SO4)的存在提高了反应活化能,但并不改变反应机理。  相似文献   

11.
Reactivity of V2O5&z.sbnd;WO3TiO2 de-NOx catalysts by transient methods   总被引:1,自引:0,他引:1  
The reactivity of ternary V2O5&z.sbnd;WO3TiO2 de-NOxing catalysts with compositions similar to those of commercial catalysts (WO3 ca. 9% w/w, V2O5 < 2% w/w) is investigated by transient techniques (temperature programmed desorption, TPD; temperature programmed surface reaction, TPSR; and temperature programmed reaction, TPR). The results indicate that the reactivity of the ternary catalysts in the SCR reaction increases on increasing the vanadia loading, and that the ternary catalysts are more active than the corresponding binary vanadia-titania samples with the same V2O5 loading. Indeed the SCR reaction is monitored at lower temperatures and high NO conversions are also preserved at high temperatures. TPSR and TPR data show that at low temperatures the SCR reaction occurs via a redox mechanism that involves at first the participation of the catalyst lattice oxygen and then the reoxidation of the reduced sites by gas-phase oxygen. Based on TPSR and TPR data, the higher reactivity of the ternary catalysts has been related to their superior redox properties, in line with previous chemico-physical characterisation studies. The catalyst redox properties thus appear as a key-factor in controlling the reactivity of V2O5&z.sbnd;WO3TiO2 de-NOxing catalysts at low temperatures. The results also show that at high temperatures the surface acidity plays an important role in the adsorption and activation of ammonia.  相似文献   

12.
Alumina–silica mixed oxide, synthesized by the sol–gel technique, was used as a support for dispersing and stabilizing the active vanadia phase. The catalysts were characterized employing 51V and 1H solid-state MAS NMR, diffuse reflectance FT-IR, BET surface area measurements. The partial oxidation activities of the catalysts were tested using methanol oxidation as a model reaction. 51V solid-state NMR studies on the calcined catalysts showed the peaks corresponding to the presence of both tetrahedral and distorted octahedral vanadia species at low vanadia loadings and with an increase in V2O5 content, the 51V chemical shifts corresponding to amorphous V2O5 like phases were observed. DRIFTS studies of the catalysts indicated the vibrations corresponding tetrahedral vanadia species at low and medium loadings and at high V2O5 contents the vibrations corresponding V=O bonds of V2O5 agglomerates were observed. The V/Al–Si catalysts exhibited high selectivity for the dehydration product dimethyl ether in the methanol partial oxidation studies showing the predominance of the acidic nature of the alumina–silica support over the redox properties of the active vanadia phase.  相似文献   

13.
Molecular structure and reactivity of the Group V metal oxides   总被引:2,自引:0,他引:2  
The physical, electronic and reactivity properties of bulk and supported Group V metal oxides (V, Nb, Ta and Db) were compared at the molecular level. Dubnium is a very short-lived element, 60 s, whose properties have not been extensively studied, but can be predicted from knowledge of the other members of the Group V metal oxides. Bulk V2O5 possesses platelet morphology with the active surface sites only located at the edges: primarily surface redox sites and some surface acidic sites. Bulk Nb2O5 and Ta2O5, as well as to be expected for bulk Db2O5, possess isotropic morphologies and the active surface sites relatively homogeneously dispersed over their surfaces: only surface acidic sites. However, the bifunctional bulk V2O5 was found to exhibit a much higher specific acidic catalytic activity than the acidic bulk Nb2O5 and Ta2O5, the latter being almost identical in their specific acidic catalytic activity. The bulk properties of the Group V metal oxides were essentially transferred to the analogous supported Group V metal oxides, where the active Group V metal oxides were present as a two-dimensional monolayer on various oxide supports (e.g., Al2O3, TiO2, ZrO2 as well as Nb2O5 and Ta2O5). For supported vanadia catalysts, the active surface sites were essentially redox sites, with the exception of supported V2O5/Al2O3 that also contained strong acidic sites. For supported niobia and tantala catalysts, as well as to be expected for supported dubnia catalysts, the active surface sites were exclusively acidic sites. However, the TOFredox for the supported vanadia catalysts and the TOFacidic for the supported niobia and tantala catalysts varied over several orders of magnitude as a function of the specific oxide support with the electronegativity of the oxide support cation. However, the TOFredox varied inversely to that of the TOFacidic variation because of the opposite requirements of these active surface sites. Surface redox sites are enhanced by reduction and surface acidic sites are enhanced by stabilization (lack of reduction). The current fundamental understanding of the Group V metal oxides allows for the molecular engineering of their metal oxide applied catalytic materials.  相似文献   

14.
Alumina-, silica-, and titania-supported vanadium oxide systems with V2O5 loadings ranging from 3 to 12 wt.%, corresponding to 0.02–0.09 V/(Al,Si,Ti) atomic ratios, were prepared by atomic layer deposition (ALD) and compared with the corresponding impregnated catalysts. The surface acidic properties of the supports and catalysts were investigated using ammonia adsorption microcalorimetry to determine the number and strength of the surface acid sites. Deposition of V2O5 on alumina and titania supports gave rise to catalysts with lower amounts of acid sites than the respective supports, while for the samples prepared on silica, an increase of the number of acid sites was observed after V2O5 deposition. As a common trend, the surface acid strength was greater for the ALD catalysts than for the impregnated ones, suggesting a stronger interaction of the VO species with the support centers, which act as electron attractor centers creating Lewis-like vanadium species. Redox cycles were performed, involving temperature programmed reduction (TPR) analyses separated by an oxidation treatment (TPO). The results evidenced the good reversibility of the redox behavior of the vanadium centers in every case, while significant differences were observed when comparing the temperatures of reduction (Tmax). Lower Tmax values were observed for the better dispersed vanadia catalysts. After reduction, the V centers had a final formal average oxidation state corresponding to +3 or less (+2.5 to +2). The reactivity of the vanadia systems was examined by measuring their performance for the oxidation of o-xylene to phthalic anhydride. Activity tests indicated the superior selectivity of the V2O5 systems based on the more acidic supports (Al2O3 and TiO2). The nature of the support governed the activity, and the more concentrated catalysts gave rise to improved selectivity to phthalic anhydride.  相似文献   

15.
A series of B-doped V2O5/TiO2 catalysts has been prepared the by sol-gel and impregnation methods to investigate the influence of B-doping on the selective catalytic reduction (SCR) of NOx with NH3. X-ray diffraction, Brunauer-Emmett-Teller specific surface area, scanning electron microscope, X-ray photoelectron spectroscopy, temperature-programmed reduction of H2 and temperature-programmed desorption of NH3 technology were used to study the effect of the B-doping on the structure and NH3-SCR activity of V2O5/TiO2 catalysts. The experimental results demonstrated that the introduction of B not only improved the low-temperature SCR activity of the catalysts, but also broadened the activity temperature window. The best SCR activity in the entire test temperature range is obtained for VTiB2.0 with 2.0% doping amount of B and the NOx conversion rate is up to 94.3% at 210 ℃. The crystal phase, specific surface area, valence state reducibility and surface acidity of the active components for the as-prepared catalysts are significantly affected by the B-doping, resulting in an improved NH3-SCR performance. These results suggest that the V2O5/TiO2 catalysts with an appropriate B content afford good candidates for SCR in the low temperature window.  相似文献   

16.
Characterization by temperature programmed reduction   总被引:1,自引:0,他引:1  
Fresh and used EUROCAT Oxide-2 catalyst made up of V2O5, WO3 and TiO2 with SiO2, Al2O3 and CaO as main additives have been studied by means of temperature programmed reduction (TPR). As in the EUROCAT Oxide-1 project (V2O5/TiO2 catalysts) for similar conditions similar profiles were obtained in the different laboratories. In contrast to the V2O5/TiO2 catalysts (EUROCAT Oxide-1 project), where the vanadia content could be determined by TPR with reasonable reliability, the exact determination of the vanadia and tungsta loading for the ternary catalysts is not possible because of the occurrence of several superimposed phenomena (reduction of vanadia, tungsta and titania and formation/reduction of CaWO4, reactions are not completed at maximal temperature reached), which are not discernible by TPR.  相似文献   

17.
利用溶胶-凝胶技术原位合成V2O5-WO3/TiO2介孔结构脱硝催化剂。通过XRD、BET、SEM和XPS等手段对催化剂结构与组成进行表征,发现结构导向剂CTAB促进催化剂的比表面积和孔容的增加,促进催化剂活性组分的分散与裸露的V活性组分数量增加;且随CTAB含量的增加,V4+/V5+的比值降低,即降低了催化剂表面钒物种的氧化能力,有利于提高催化剂的低温脱硝活性与高温选择性。催化活性评价结果表明,CTAB对催化剂的脱硝活性有显著促进作用,当CTAB的添加量为0.01(质量)时,催化剂的脱硝活性大于90%的温度窗口最宽为212~393℃,200℃时脱硝效率达85.6%。  相似文献   

18.
The application of different techniques (diffuse reflectance-UV–vis, 51V NMR, FT-IR of adsorbed pyridine and TPR-H2) in the characterization of vanadia supported on mesoporous Al2O3 catalysts shows that the nature of the vanadium species depends on the V-loading. At V-content lower than 15 wt.% of V-atoms (30% of the theoretical monolayer), vanadium is mainly in a tetrahedral environment. Higher V-contents in the catalyst leads to the formation of octahedral V5+ species and V2O5-like species. Both XRD and textural results indicate that the mesoporous structure of the support is mostly maintained after the vanadium incorporation, and therefore high surface areas were obtained on the final catalysts. Al2O3-suppported vanadia catalysts are active and selective in the oxidative dehydrogenation of ethane, although the catalytic behavior depends on the V-loading. High rates of formation of ethylene per unit mass of catalyst per unit time have also been observed as a consequence of the high dispersion of V-atoms on the surface of the support.  相似文献   

19.
In situ Raman spectroscopy was used for studying the ternary 2% CrO3–6% V2O5/TiO2 catalyst, for which a synergistic effect between vanadia and chromia leads to enhanced catalytic performance for the selective catalytic reduction (SCR) of NO with NH3. The structural properties of this catalyst were studied under NH3/NO/O2/N2/SO2/H2O atmospheres at temperatures up to 400 °C and major structural interactions between the surface chromia and vanadia species are observed. The effects of oxygen, ammonia, water vapor and sulfur dioxide presence on the in situ Raman spectra are presented and discussed.  相似文献   

20.
黄燕  孟庆华  金迁  王康  陈雪红  杨刚 《工业催化》2015,23(4):301-306
采用共沉淀法、溶胶-凝胶法和浸渍法制备了V2O5质量分数4%和WO3质量分数6%的V2O5-WO3/TiO2选择性催化还原催化剂,对比了3种方法制备的催化剂选择性催化还原NO性能。采用X射线衍射、热重、N2吸附-脱附和程序升温还原等对制备的V2O5-WO3/Ti O2催化剂的结构和性质进行表征,结果表明,共沉淀法制备的V2O5-WO3/TiO2催化剂具有更好的选择性催化还原NO活性和更大的比表面积,影响共沉淀法选择性催化还原NO活性的主要因素是催化剂的热稳定性、表面羟基数量、比表面积、粒径分布以及V、W与Ti之间的内在作用。  相似文献   

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