Effects of hydrochloride acid dealumination of mordenite(MOR) catalysts for the synthesis of 1-phenyl-1-xylyl ethane(PXE) were investigated. The structure and acidity of catalysts were characterized by XRD, BET, XRF, FT-IR, 27Al NMR and NH3-TPD techniques. The catalytic performance of the acid-treated MOR zeolites was studied through using the alkylation of o-xylene with styrene. The test results showed that the strength of remaining Br?nsted acid sites increased despite the reduction of total number of acid sites after dealumination, and the micropores of HMOR were slightly enlarged coupled with the formation of secondary mesopores. Additionally, the modified HMOR zeolites showed longer catalyst life with the styrene conversion rate retained. Among the catalysts employed in this study, the modified mordenite that was dealuminated by HCl(2 mol/L) could be used repeatedly without significant loss of activity and selectivity during six catalytic runs, which have been ascribed to its specific acidity and structural properties.
Kong JieSheng XiaoliZhou YumingZhou ShijianZhang Zewu
The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2- physisorption, and NH3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical prop- erties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger extemal surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.
Huang LiZhou ShijianZhou YumingZhang YiweiXu JunWang Li
The influence of mischmetal addition on physicochcmical properties of PtSnNa/ZSM-5 catalyst was studied by means of XRF, H2 chemisorption, XRD, TPR, NH3-TPD and TPO techniques. The results showed that the presence of mischmetal had an obvious impact on the catalytic performance of the PtSnNa/ZSM-5 catalyst. A suitable content of mischmetal not only could enhance the interactions between Pt species and the support, but also inhibit the formation of coke during the reaction, thus improving the catalytic activity and stability. In our experiments, when the content of mischmetal was 3m%, the catalyst exhibited best catalytic performance. However, the continuous addition of mischmetal could promote the reduction of Sn species to metallic tin, which was disadvantageous to the reaction.
Solid-state grinding is a simple and effective method to introduce guest species into the channels of microporous materials through filling.The structure and the surface acidity of the materials were obtained from BET isotherms and NH3-TPD,respectively.XRD,UV-vis,UV diffuse-reflectance,and TEM were used to characterize the phases,and the morphology,respectively.The clustered layers of MgO-Al2O3phases were formed in the internal pore surface and were highly dispersed inside the channels of the ZSM-5 host.So the volume of MgO-Al2O3/ZSM-5 composite was larger than the ZSM-5 zeolite itself and some mesoporous channels appeared when Mg/Al species entered the channels.Meanwhile,new acid sites emerged in MgO-Al2O3/ZSM-5 composite and the acid amount of the sample changed.The improved Pt dispersion and the increased acid content would cause the increase of propane conversion and the modification of selectivity during the reaction.
Zhou ShijianZhouYumingSheng XiaoliZhangYiweiZhang ZewuShi JunjunKong Jie
The effects of the sequence for impregnation of metal precursors on the performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation to propene were studied in this paper.Some methods such as XRD,TPDA,BET,H2-TPR,XPS,ICP,TEM and hydrogen chemisorption were used to characterize the catalysts.The structure of ZSM-5 zeolite was not destroyed by the introduction of metal components.Meanwhile the different impregnation sequence of metal precursors could affect the behavior of Sn4+species entering the ZSM-5 channel,and the interaction between platinum and tin species,as well as the degree for reduction of Pt and Sn components.As a result,the prepared catalysts exhibited different reaction activity and selectivity.Compared with the co-impregnation treated catalyst,the catalysts prepared by the sequential impregnation method showed better catalytic activity in propane dehydrogenation,especially the one prepared through impregnation with tin precursor at first.Finally,a model for the effect of impregnation sequence on the distribution of Pt and Sn species in PtSnNa/ZSM-5 catalyst was proposed.
Liu HuiZhou YumingZhang YiweiSheng XiaoliZhang ZewuZhou Shijiang
The alumina-modified SBA-15 （A12OJSBA-15） zeolite was prepared in a non-aqueous system by using toluene as the solvent, and was used to support the PtSn-based catalyst for propane dehydrogenation. The BET surface area mea- surements, hydrogen chemisorption, FT-IR spectroscopy, NH3-TPD, XPS and TPO techniques were used to characterize the catalysts. Test results showed that the addition of alumina not only could modify the acid function of the support but also the structure of the metallic phase, thus affecting their catalytic properties. Among these catalysts studied, the PtSn/AI203 （5%）/ SBA-15 catalyst exhibited a best catalytic performance in terms of propane conversion and selectivity to propene. The high catalytic performance might be attributed to the relatively good Pt metal dispersion and/or the strong interaction between Pt and Sn species.
Abstract： The present article compares the propane dehydrogenation performance of alumina binder-added PtSnNa/ A1SBA-15 catalysts prepared via three different procedures in comparison with the performance of a binder-free PtSnNa/ AISBA-15 catalyst. All these catalysts have been investigated by reaction tests and some physico-chemical characterizations such as BET, H2 chemisorption, catalytic grain crushing strength, NHa-TPD and TPO analyses. Test results showed that the addition of alumina binder could enhance the mechanical strength of catalyst evidently. Moreover, the different preparation procedures not only modified the characteristics of both acid and metal functions but also affected the coke deposition on the catalysts. Among these catalysts studied, the catalyst prepared by impregnation followed by the agglomeration of alumi- na binder had exhibited the highest catalytic activity and stability compared with other catalyst samples undergoing different preparation procedures. The possible reason may be attributed to the highest metallic dispersion and the strong interactions among Pt, Sn and the support.
The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 （AlSBA-15） and alumina-modified SBA-15 （Al2O3/SBA-15）, for propane dehydrogenation were investigated. Al2O3/SBA-15 was prepared either by an impregnation method using aluminum nitrate aqueous solution, or by the treatment of SBA-15 with a Al（OC3H7）3 solution in anhydrous toluene. N2-physisorption, FT-IR spectroscopy, solid-state 27Al MAS NMR spectroscopy, hydrogen chemisorption, XRF, NH3 temperature-programmed desorption, X-ray photoelectron spectroscopy and TPO were used to characterize these samples. Among these catalysts, the PtSn-based catalyst supported on Al2O3/SBA-15, which was grafted with Al（OC3H7）3, exhibited the best catalytic performance in terms of activity and stability The possible reason was due to the high Pt metal dispersion and/or the strong interactions among Pt, Sn, and the support.
The effect of cerium addition on the catalytic performance of propane dehydrogenation over PtSnNaIZSM-5 catalyst has been investigated by reaction tests and some physicochemical characterization such as XRD, BET, TEM, XPS, NH3-TPD, H2 chemisorption, TPR and TPO techniques. It has been found that with suitable amount of cerium addition, the platinum dispersion increased, while the carbon deposition tended to be eliminated easily. In these cases, the presence of cerium could not only realize the better distribution of metallic particles on the support, but also strengthen the interactions between Sn species and the support. Additionally, XPS spectra confirmed that more amounts of tin could exist in oxidized form, which was advantageous to the reaction. In our experiments, PtSnNaCe （1.1 wt%）/ZSM-5 catalyst exhibited the best catalytic performance. After running the reaction for 750 h, propane conversion was maintained higher than 30% with the corresponding selectivity to propylene of about 97%.
