不同的制备方法对PtSnNa/AlSBA-15 催化剂在丙烷脱氢性能的影响

The present article compares the propane dehydrogenation performance of alumina binder-added PtSnNa/ AlSBA-15 catalysts prepared via three different procedures in comparison with the performance of a binder-free PtSnNa/AlSBA-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, NH3-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 alumina 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.     

Propane Dehydrogenation on PtSnNa/AlSBA-15 Catalyst:Influence of Tin as a Promoter

PtSnNa/AlSBA-15 catalysts with different amounts of Sn were prepared for propane dehydrogenation.The catalysts were characterized by XRF,BET,H2 chemisorption,NH3-TPD,H2-TPR,and TPO techniques.Test results indicated that the presence of tin not only modified the acid function and the interfacial character between metal and support,but also reduced the coke deposition effectively.Among these catalysts investigated thereby,the PtSn(0.7%)Na/AlSBA-15 catalyst had the best catalytic performance in terms of propane conversion and stability.With the continuous addition of Sn,more amounts of Sn0 species appeared,which was unfavorable to the reaction.The PtSn(0.7%)Na/AlSBA-15 catalyst was parametrically characterized in order to obtain necessary information to integrate the process operating conditions.A weight hourly space velocity of 3 h-1,a reaction temperature of 610 ℃ and a H2/C3H8 molar ratio of 0.25 were found to be optimum conditions for achieving a higher dehydrogenation activity of the catalyst.     

Influence of Alumina Content on Catalytic Performance of PtSn/Al2O3/SBA-15 Catalysts for Propane Dehydrogenation

The alumina-modified SBA-15 (Al2O3/SBA-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 measurements, 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/Al2O3 (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.     

Effect of Strontium Addition to Platinum Catalyst for Propane Dehydrogenation

PtSnSr/HZSM-5 catalysts with different amounts of strontium were prepared by sequential impregnation method,and characterized by BET analysis,TEM,NH3-TPD,H2-TPR,TPO and TG techniques.The results showed that the addition of strontium could modify the characteristics and properties of both acid function and metal function of Pt-Sn-based catalysts.In this case,PtSnSr/HZSM-5 catalyst with an appropriate amount of Sr(1.2%) showed higher catalytic activity and lower amount of coke deposits than PtSn/HZSM-5 catalyst.However,excessive loading of Sr could facilitate the reduction of Sn,which was unfavorable to the reaction.Afterwards,1.0 m% of Na was added into the PtSnSr(1.2%)/HZSM-5 catalyst to improve the catalytic performance in propane dehydrogenation,and this catalyst displayed the best catalytic performance during our experiments.After having been subjected to reaction for 5h,the PtSnNa(1.0%)Sr(1.2%)/HZSM-5 catalyst had achieved a higher than 95% selectivity towards propene along with a corresponding propane conversion rate of 32.2%.     

Design of the Metal Precursors Molecular Structures in Impregnating Solutions for Preparation of Efficient Ni Mo/Al_2O_3 Hydrodesulfurization Catalysts

The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]~(4-)-like, [P2Mo18O62]~(6-)-like and [P2Mo5O23]~(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]~(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]~(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]~(4-)-like, [P2Mo18O62]~(6-)-like and [P2Mo5O23]~(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.     

混合稀土的添加对PtSnNa/ZSM-5催化剂丙烷脱氢性能的影响

The influence of mischmetal addition on physicochemical properties of PtSnNa/ZSM-5 catalyst was studied by means of XRF,H 2 chemisorption,XRD,TPR,NH 3-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.     

ELUCIDATION OF HYDRODESULFURIZATION AND HYDROGENATION MECHANISMS USING RADIOISOTOPE TRACER METHODS

To meet the specification of sulfur and aromatic contents in diesel fuel, it is necessary for refiners to develop a new catalyst with high activity of hydrodesulfurization and hydrogenation. In the present study, the properties of noble metal catalysts for hydrodesulfurization and hydrogenation in the presence of sulfur compounds have been investigated. The hydrogenation activity of phenanthrene (PHE) on single noble metal and double noble metal catalysts-Pt/Al2O3, Pd/Al2O3 and Pd-Pt/Al2O3 in the presence of dibenzothiophene (DBT) was performed in a fixed bed flow reactor. The Pt based catalysts revealed the similar HDS activities and higher HYD activity compared with convertional Mo based catalysts. The maximum activity was obtained around 320℃ for both catalyst types. The Pt based catalysts produced perhydrophenanthrene as a major product at the maximum activity in the hydrogenation of PHE while the Mo based catalysts produced octahydrophenanthrene. A ^35S radioisotope pulse tracer method (^35S RPTM) was used to estimate the behavior of sulfur on the working catalysts and to clarity the differences between Pt and Mo based catalysts. Very little amount of labile sulfur was accumulated on the Pt and Pd catalysts in the HDS of [^35S]DBT (PtS0.25 or PdS0.25). This indicates that the mechanism of DBT HDS on noble metal catalysts is significantly different from that on conventional Mo based catalysts where Mo is present as MoS2 less than 60% of which can be labile in the case of Co-Mo/Al2O3. Another Ru-Cs/Al2O3 catalysts were also prepared and the behavior of sulfur on the working catalyst was compared with those of Mo based catalysts and Pt and Pd catalysts. The values of labile sulfur in the kIDS reaction for Ru-Cs catalysts approximately correspond to RS0.5-0.74. These amounts of labile sulfur are much higher than those for Pt and Pd catalysts. The result suggests that the oxidation state of Ru species is present between the oxidation states of Pt or Pd and Mo, and can change in the wide range during the HDS reaction, different from PtS0.25 (PdS0.25) and MoS2 which is unchangeable under the usual HDS conditions. From the approach of using [^35S]H2S it was found that the labile sulfur was hardly formed during the presulfiding procedure but was formed only during the actual HDS. This is also a unique character of Ru catalysts.     

镓对PtSnNa/ZSM-5催化剂丙烷脱氢反应性能的影响

PtSnNaGa/ZSM-5 catalysts with different contents of Ga were prepared and characterized by X-ray diffraction (XRD), nitrogen adsorption, hydrogen chemisorption, ammonia temperature-programmed desorption (NH3-TPD), hydrogen temperature-programmed reduction (H2-TPR), and temperature-programmed oxidation (TPO) techniques. The performances of these catalysts for propane dehydrogenation were investigated. The test results indicated that the addition of Ga not only could improve the catalytic stability and propene selectivity, but also could effectively prevent the catalysts from coking. It was found that the PtSnNaGa(0.5 m%)/ZSM-5 catalyst exhibited the best performance in terms of propene selectivity and propane conversion. The high catalytic performance was most probably attributed to the presence of Ga that could strength- en the interaction between metals and the support to stabilize the catalytic active sites.     

Hydroisomerization performance of platinum supported on ZSM-22/ZSM-23 intergrowth zeolite catalyst

Hydroisomerization catalysts Pt/ZSM-22,Pt/ZSM-23,and Pt/ZSM-22/ZSM-23 were prepared by supporting Pt on ZSM-22,ZSM-23,and intergrowth zeolite ZSM-22/ZSM-23,respectively.The typical physicochemical properties of these catalysts were characterized by X-Ray Diffraction(XRD),N2 absorption-desorption,Pyridine-Fourier Transform Infrared(Py-FTIR),Transmission Electron Microscopy(TEM),X-Ray Fluorescence(XRF),Scanning Electron Microscopy(SEM) and NH3-Temperature Programmed Desorption(NH3-TPD),and the performance of these catalysts in n-dodecane hydroisomerization was evaluated in a continuous down-flow fixed bed with a stainless steel tubular reactor.The characterization results indicated that the intergrowth zeolite ZSM-22/ZSM-23 possessed the dual structure of ZSM-22 and ZSM-23,and the catalyst Pt/ZSM-22/ZSM-23 had similar pores and weak acidity to Pt/ZSM-22 and Pt/ZSM-23 catalysts.Moreover,Pt/ZSM-22/ZSM-23 catalyst showed a high selectivity in hydroisomerization of long chain n-alkanes to mono-branched isomers.The evaluation results for n-dodecane hydroisomerization indicated that the activity of Pt/ZSM-22/ZSM-23 was the lowest,while the hydroisomerization selectivity was the highest among the three catalysts.The maximum yield of i-dodecane product was 68.3% over Pt/ZSM-22/ZSM-23 at 320 oC.     

Hydroisomerization of n-heptane on Pt promoted phosphomolybdate catalysts

Phospbomolybdate （PMo） with varying Mo loadings ranging from 5-30 wt% on alumina were prepared by incipient wetness impregnation method. 0.5 wt% of Pt was further loaded in order to prepare the bifunctional （metal-acid） Pt-PMo/Al2O3 catalysts. Thus prepared catalysts showed very high catalytic activities for n-heptane hydroisomerization compared with Pt impregnated MoO3 catalysts supported either on Al2O3 or on AIPO4. The conversion of n-heptane increased with Mo loading up to 20 wt% and slightly decreased with further Mo loading. However, the selectivity towards isomers showed an increasing trend up to 30 wt% of Mo in the catalyst. A relationship between catalytic activity and acidic strength was established in the present study.     

固相研磨法合成MgO-Al2O3/ZSM-5及其丙烷脱氢催化反应性能的研究

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.     

Synthesis of Novel Series of Benzothieno [2,3-d] Pyrimidine Derivatives, Promising Anticancer Agents

An extension of the authors＇ previous discovery of in vitro antitumor activity of substituted thino [2,3-d] prymidine derivatives is reported. The synthesis of some new spirothino [2,3-d] prymidine （4a-f）, imidazolidin, substituted prymidinyl and substituted thiazolidine thino [2,3-d] prymidine derivatives have been described. Thirteen of the obtained compounds were selected by the NCI and evaluated for their in vitro anticancer activity. Seven of the investigated compounds, 4a, 8a, 9a, （12a, b）, 14a and 15a, displayed high anticancer activity in the primary assay. These compounds have been selected for a full anticancer screening against a 60-cell panel assay where they showed non-selective broad spectrum and promising activity against all cancer cell lines. Compounds 12a and 12b proved to be the active members in this study compared to 5-fluorouracil and cyclophosphamide as reference drugs, respectively. Compounds 12a and 12b were identified as promising lead compounds, evaluated for their in-vitro antitumor activity.     

负载型V_2O_5/AlPO_4催化剂在丙烷氧化脱氢中的催化作用

采用浸渍法在自制的无定型磷酸铝ＡｌＰＯ４载体上负载０．６％～６．０％的Ｖ２Ｏ５，所制的催化剂在丙烷氧化脱氢反应中具有较好的催化性能，如３．０％Ｖ２Ｏ５／ＡｌＰＯ４催化剂在丙烷转化率为１４．２％时，丙烯选择性可达４９．１％，丙烯收率达７．０％。考察了不同反应条件下催化剂的性能，ＸＲＤ、ＩＲ和Ｒａｍａｎ光谱表明，Ｖ２Ｏ５在ＡｌＰＯ４上主要是以高度分散的钒氧物种存在；ＥＳＲ结果证明催化剂中存在Ｖ４＋物种，暗示Ｖ５＋／Ｖ４＋氧化还原偶参与了氧化还原反应。     

低碳烃在Zn/PLC上的芳构化反应性能

评价了丙烷和C4烃在Zn/PLC催化剂上的芳构化反应活性 ,并与Zn/HZSM 5催化剂进行了比较。结果表明 ,丙烷和C4烃在Zn/PLC催化剂上具有一定的反应活性 ,但其芳烃选择性低于Zn/HZSM 5催化剂 ,这主要是由于PLC和HZSM 5作为载体的酸性特征及孔结构不同所造成的。在Zn/PLC催化剂上 ,丙烷芳构化主要转化为苯 ,C4烃芳构化主要转化为二甲苯。而在Zn/HZSM 5催化剂上 ,丙烷和C4烃芳构化主要转化为甲苯。Ga3 + 或Pt4+ 的引入明显改善了Zn/PLC催化剂的丙烷和C4烃芳构化性能。     

New Environmental Friendly Yellow Ceramic Pigments of the Type （Fe^ⅢM^Ⅴ）-TiO2

The family of Cr（Ⅲ） and Fe（Ⅲ）-doped rutile pigments of nominal composition （M^ⅢM^V）xTi1-2xO2, with M^Ⅲ = Cr（Ⅲ） or Fe（Ⅲ） and M＇（V） = Sb, Nb, Ta, with x = 0.03, 0.15 and 0.25 were investigated as ceramic pigments covering the yellow-ochre-brown palette. The formulations containing Fe（Ⅲ） are novel compositions not included in the commercial rutile pigments. The materials were characterized by XRD （X-ray diffraction） analysis and FTIR （Fourier transformed infrared spectroscopy）. The transition temperature from anatase-to-rutile was estimated by the evolution of the spectral patterns. This crystal phase transition is responsible of the color formation. A higher distortion of TiO6 octahedra is observed in the case of （FeSb） containing cells which contribute to the enhancement of the light absorption. The coloring performance of all the formulations were evaluated by enameling the mixtures containing 5% pigments and commercial frits representative of single and double firing industrial processes. The chromatic values obtained are in the yellow to brown domain of the chromatic plot, depending on the composition of the pigment-frit batch. In the case of the Fe-glazes, and particularly the combination （FeNb）, the chromatic values are close to the best yellow tinting. This new FeNb-rutile pigment could be a more benign substitute of Cr-yellow pigments. The homogeneity of the enamels was confirmed by SEM （scanning electron microscopy）-EDAX （energy dispersive X-ray analysis） microscopy.     

Synthesis of N-Substituted （Z）-3-（ （2-Benzyl）-4-Ox opent-2-yl） Pyrrole-2,5-Diones （Maleimides）

A series of N-substituted （Z）-3-（（2-benzyl）-4-oxopent-2-yl）pyrrole-2,5-diones were synthesized and characterized. The compounds were synthesized from dimethyl-2-（（Z）-2-（benzylamino）-4-oxopent-2-en-3-yl） fumarate （9） and dimethyl acetylenedi-carboxylate followed by reaction with some amines in refluxing ethanol. The identification of the compounds were based on spectroscopic analysis such as 1R （infrared）, UV （ultraviolet）, ^1H-NMR （nuclear magnetic resonance） and the microanalysis of the elements （CHN （microanalysis）） data.     

An Eco-friendly Method for Novel Scaffolds： Novel N2-Substituted Fused Pyrazolo （4＇,3＇：5,6） Pyrano （2,3-d） Pyrimidine Terminated by Hydroxy Group

Four components have been reacted in water and in the presence of N-morpholine yielded pyrnopyrazole as a simple substrate for novel N2-acyclonucleoside derivatives of fused pyranopyrazole. The sodium salt of fused pyranopyrazole reacted with halo alcohols led to the formation of new scaffolds from fused pyranopyrazole derivatives. All newly prepared compounds are characterized spectroscopically.     

Features of Polymethacrylic Acid and Poly-2-Methyl-5-Vinylpyridine Hydrogels Remote Interaction in an Aqueous Medium

The remote interaction of polymethacrylic acid hydrogel with a poly-2-methyl-5-vinylpyridine hydrogel was studied. The aim of work was to study the dependence of the swelling coefficient, the conductivity and the pH of the water solutions of intergel system at different mass ratios from time were studied. The goal was achieved by using following methods： pH-metry, conductometry and gravimetry.     

L3-Edge Jump and Shift on White-Line of Pd Interlayer for Trilaminar Neutron Production Target under H2^＋ Irradiation

Interlayer Pd for the Li/Pd/Cu neutron target for BNCT （boron neutron capture therapy） was characterized after 0.1-5 keV H2^＋ irradiation by XAFS （X-ray absorption fine structure） technique, and following conclusions were derived： （1） from the XAFS observation of white line of Pd, remarkable Pd L3 edge jump was found in 1.1-3 times higher than before irradiation in low irradiation fluence; （2） this fact indicates increase of hole density in Pd 4d-band, whereas, no change was observed for XASF spectra of Ag sample under the same irradiation conditions; （3） remarkable Pd L3 edge shift of 0.12-0.66 eV was also found with increase of H2＋ irradiation energy in low fluence, and drastically decreased after peak in high irradiation energy and fluence; （4） implanted protons deposited in Pd as negative under the balance of electron population enhanced by proton irradiation and charge transfer.     

A New Method of Producing Radionuclide-Labeled Microspheres for Radionuclide Therapy

This work is devoted to obtaining radionuclide-labeled microspheres for radionuclide therapy as a therapeutic drug with a selective method of delivery. The nature of magnetic microspheres and quantitative elemental composition radiopreparats was considered. We have developed a new method of producing radionuclide-labeled microspheres （radiopharmaceutical ^140Nd-microspheres） for radionuclide therapy.