Search Results

You are looking at 51 - 60 of 90 items for :

  • Refine by Access: All Content x
Clear All
Reaction Kinetics, Mechanisms and Catalysis
Authors: Lixia Wang, Wanchun Zhu, Dafang Zheng, Xue Yu, Jing Cui, Mingjun Jia, Wenxiang Zhang, and Zhenlu Wang

Abstract  

The reaction of direct transformation of ethanol to ethyl acetate was investigated on reduced Cu/ZrO2 catalysts prepared by a co-precipitation procedure. The catalytic performances of these Cu–Zr mixed oxides were considerably influenced by changing the molar ratio of Cu to Zr. The highest selectivity to ethyl acetate was found over Cu/ZrO2(1) catalyst (molar ratio of Cu to Zr was 1). A variety of characterization techniques, such as N2 adsorption, XRD, XPS, TPR and NH3-TPD were carried out on the catalysts. The results revealed that the presence of a certain amount of Cu+ species may play very important role in improving the selectivity to ethyl acetate of the Cu/ZrO2 catalysts.

Restricted access

Abstract  

A series of phosphorus modified Si-MCM-41 catalysts prepared via the impregnation method were used for the vapor-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam. The catalysts were characterized by XRD, N2 adsorption, FT-IR, and NH3-TPD. The results indicated that weak acid sites increased with P content, leading to enhanced catalytic activity. The catalyst with Si/P mol ratio of 25 showed best performance at 633 K. The conversion of cyclohexanone oxime and the selectivity for caprolactam were 92.7 and 64.2%, respectively. The P–OH groups are main active sites for the Beckmann rearrangement. Grafting acid hydroxyl groups to cover the Si–OH groups may be a good way to improve the selectivity for this reaction.

Restricted access

Abstract  

The reaction of urea with ZnO was investigated by FTIR and TPD. It was found that urea was thermally decomposed into isocyanic acid on ZnO, and the adsorbed isocyanic acid reacted with ZnO to form zinc isocyanate. Catalytic evaluation showed that ZnO had high activity towards urea methanolysis in a batch reactor, and zinc element and isocyanate were all detected in the product solution. Furthermore, the soluble zinc content was proportional to the DMC yield. Sample analyses suggested that the soluble zinc existed in the form of Zn(NCO)2(NH3)2, which originated from the reaction of ZnO with urea. It was the complex (not ZnO) that catalyzed the urea methanolysis. Based on these observations, a possible mechanism was suggested.

Restricted access

Abstract  

Temperature-programmed desorption (TPD) of water was applied to characterize short-time dealuminated HZSM-5 zeolites. Using a regularization method, distribution functions of the effective desorption energy of water were calculated. The results clearly show that during dealumination a new adsorption site is formed which can be attributed to non-framework or transient aluminium species. The highest concentration of these sites was observed for a dealumination time of 25-30 min. NO adsorption studies support this result. Furthermore, it could be concluded that the heterogeneity and the average acid strength of the remaining Si-OH-Al groups of the dealuminated samples do not change compared to the Si-OH-Al groups of the parent HZSM-5 zeolite.

Restricted access

Abstract  

The activity of solid niobic acid treated with sulfuric acid and with phosphoric acid was tested in the catalytic esterification of oleic acid and in transesterification of soybean oil with methanol. X-ray diffraction studies revealed niobic acid treated with sulfuric acid to be an amorphous solid, while niobic acid treated with phosphoric acid presented a crystalline phase, probably due to the formation of hydrogen niobium phosphate. Among the characterization methods employed here, XPS was particularly instrumental in showing that niobium dihydrogen phosphate and niobium hydrogen sulfate moieties are the acidic active sites responsible for the catalytic effect. The latter is more active according to ammonia TPD studies. Yields as high as 78% in the esterification of oleic acid with methanol and 40% in the transesterification of soybean oil catalyzed by NbSO4 were recorded.

Restricted access

Abstract  

Alkaline earth metal (Mg, Ca, Sr and Ba) ions were exchanged into Hβ zeolite, which were used as the supports to load the noble metal Pt to prepare bifunctional catalysts for hydroisomerization of n-heptane. The catalysts were characterized by ICP, XRD, BET, NH3-TPD, H2-TPR and H2-chemisorption techniques, and evaluated in an atmospheric fixed bed reactor. The catalysts promoted by the alkaline earth metals are revealed to present much higher selectivity to isomerization than the counterpart Pt/Hβ. Moreover, the Ba-bearing catalyst loaded with 0.4 wt% Pt and 5:1 molar ratio of Ba to Pt gives a very high selectivity to iso-heptanes 95.4% with a considerable high conversion of n-heptane 61.7%. The promotion effect of alkaline earth metals is briefly discussed in relation to characterization data.

Restricted access

The contribution of thermal methods of analysis to the study of the structure and reactivity of vanadium-phosphorus oxides is examined. In particular, data are reported on the solid-state reaction VOHPO4·1/2H2O→(VO)2P2O7+2 H2O for VOHPO4·1/2H2O prepared in different ways, on the redox properties of oxidation and reduction of vanadium for catalysts prepared with different P∶V atomic ratios in the range 0.9–1.3, and on the surface properties determined by TPD of catalysts with different P∶V ratios. The relationship between these properties and the catalytic properties in the selective oxidation ofn-butane and but-1-ene is discussed.

Restricted access
Journal of Thermal Analysis and Calorimetry
Authors: S. Aukkaravittayapun, C. Thanachayanont, T. Theapsiri, W. Veerasai, Y. Sawada, T. Kondo, S. Tokiwa, and T. Nishide

Abstract  

Fluorine-doped tin dioxide (FTO) films were deposited on silicon wafers by inverted pyrosol technique using solutions with different doping concentration (F/Sn=0.00, 0.12, 0.75 and 2.50). The physical and electrical properties of the deposited films were analyzed by SEM, XRF, resistivity measurement by four-point-probe method and Hall coefficient measurement by van der Pauw method. The electrical properties showed that the FTO film deposited using the solution with F/Sn=0.75 gave a lowest resistivity of 3.210–4 ohm cm. The FTO films were analyzed by temperature programmed desorption (TPD). Evolved gases from the heated specimens were detected using a quadruple mass analyzer for mass fragments m/z, 1(H+), 2(H2 +), 12(C+), 14(N+), 15(CH3 +), 16(O+), 17(OH+ or NH3 +), 18(H2O+ or NH4 +), 19(F+), 20(HF+), 28(CO+ or N2 +), 32(O2 +), 37(NH4F+), 44(CO2 +), 120(Sn+), 136(SnO+) and 152(SnO2 +). The majority of evolved gases from all FTO films were water vapor, carbon monoxide and carbon dioxide. Fluorine (m/z 19) was detected only in doped films and its intensity was very strong for highly-doped films at temperature above 400C.

Restricted access

Abstract  

Interaction between 1-methylnaphthalene and alkali-metal X and Y zeolites has been investigated using TPD. All spectra show only a single peak, the temperature of which changes with the nature and amount of the alkali-metal cation and the Si/Al ratio of the faujasite. A correlation between peak temperature and average charge of structural oxygen atoms of the zeolite is shown. On the basis of the atomic charge distribution in the 1-methylnaphthalene molecule, it is, suggested that adsorption is initiated by interaction between the alkali-metal cation and the carbon atom of the methyl group. Simultaneously, an interaction involving hydrogens atoms of the aromatic rings and structural oxygen atoms of the zeolite occurs, except for X samples containing high amounts of large alkali-metal cations.

Restricted access

Abstract  

β-MCM41 composite molecular sieves were hydrothermally synthesized using NaOH treated β zeolite as precursors, and Pt/β-MCM41 bifunctional catalysts were prepared by impregnation. Hβ, desilicated Hβ by NaOH treatment (Dβ), and the physical mixture of Hβ and MCM41 (β+MCM41) were also used as control supports for bifunctional catalysts. All the catalysts were characterized by ICP, XRD, BET, nitrogen adsorption–desorption isotherm and NH3-TPD, and evaluated in the hydroisomerization of n-heptane using an atmospheric fixed bed flow reactor. Dβ, β+MCM41, or β-MCM41 supported Pt catalysts showed higher selectivity to isoheptanes than the counterpart Pt/Hβ did due to the presence of mesopores in addition to the zeolite micropores. Moreover, Pt/β-MCM41 was demonstrated to be a much more selective catalyst among them because the connection between mesopores and micropores accelerated the diffusion of larger molecules of isoheptanes. Under optimal conditions, Pt/β-MCM41 provided a very high selectivity to isomerization of 96.5%, coupled with a considerable high conversion of n-heptane of 56.0%.

Restricted access