Pt supported on Zn modified silicalite-1 zeolite as a catalyst for n-hexane aromatization

Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.

Synthesis and characterization of zeolite X obtained from kaolin for adsorption of Zn(Ⅱ)

This study deals with the synthesis and characterization of low-silica zeolite X, from calcined Kalabsha kaolin, for adsorption of Zn(Ⅱ) ions from aqueous solution. The synthesis processes is performed under hydrother-mal treatment in alkaline solutions. The obtained zeolite samples are characterized using X-ray diffraction, grain size distribution, surface area, and SEM. The critical molar ratios of both SiO2/Al2O3 and K2O/Na2O are about 2.9 and 0.16, respectively. Those ratios are needed to give individual low silica zeolite X in a minimum reaction time. The adsorption capacity of the synthesized products is determined by adsorption of Zn(Ⅱ) ions from solution. The results suggest that the zeolite obtained could be converted to a beneficial product, which will be used in future as an ion exchanger in removing heavy metals from wastewaters.

Alkylation of toluene with tert-butyl alcohol over HPW-modified Hβ zeolite

An Hβ-supported heteropoly acid （H3PW12O40 （HPW）/Hβ） catalyst was successfully prepared by wetness impregnation, and investigated in the alkylation of toluene with tert-butyl alcohol for the synthesis of 4-tert-butyltoluene （PTBT）. X-ray diffraction, scanning electron microscopy, transmis- sion electron microscopy, fourier-transform infrared spectroscopy, inductively coupled plas- ma-optical emission spectrometry, the brunauer emmett teller （BET） method, tempera- ture-programmed NH3 desorption, and pyridine adsorption infrared spectroscopy were used to characterize the catalyst. The results showed that loading HPW on Hβ effectively increased the B acidity and decreased the pore size of Hβ. The B acidity of HPW/Hβ was 142.97 μmol/g, which is 69.74% higher than that of Hβ （84.23 μmol/g）. The catalytic activity of the HPW/Hβ catalyst was much better than that of the parent Hβ zeolite because of its high B acidity. The toluene conversion over HPW/Hβ reached 73.1%, which is much higher than that achieved with Hβ （54.0%）. When HPW was loaded on Hβ, the BET surface area of Hβ decreased from 492.5 to 379.6 m2/g, accompa- nied by a significant decrease in the pore size from 3.90 to 3.17 nm. Shape selectivity can therefore play an important role and increase the product selectivity of the HPW/Hβ catalyst compared with that of the parent Hβ. PTBT （kinetic diameter 0.58 nm） can easily diffuse through the narrowed pores of HPW/Hβ, but 3-tert-butyltoluene （kinetic diameter 0.65 nm） diffusion is restricted because of steric hindrance in these narrow pores. This results in high PTBT selectivity over HPW/Hβ （around 81%）. The HPW/Hβ catalyst gave a stable catalytic performance in reusability tests.

Catalytic roles of the acid sites in different pore channels of H‐ZSM‐5 zeolite for methanol‐to‐olefins conversion

H‐ZSM‐5 zeolite is a typical catalyst for methanol‐to‐olefins(MTO)conversion.Although the performance of zeolite catalysts for MTO conversion is related to the actual location of acid sites in the zeolite framework,the catalytic roles of the acid sites in different pore channels of the H‐ZSM‐5 zeolite are not well understood.In this study,the MTO reaction network,involving the aromatic cycle,alkene cycle,and aromatization process,and also the diffusion behavior of methanol feedstock and olefin and aromatic products at different acid sites in the straight channel,sinusoidal channel,and intersection cavity of H‐ZSM‐5 zeolite was comparatively investigated using density functional theory calculations and molecular dynamic simulations.The results indicated that the aromatic cycle and aromatization process occurred preferentially at the acid sites in the intersection cavities with a much lower energy barrier than that at the acid sites in the straight and sinusoidal channels.In contrast,the formation of polymethylbenzenes was significantly suppressed at the acid sites in the sinusoidal and straight channels,whereas the alkene cycle can occur at all three types of acid sites with similar energy barriers and probabilities.Consequently,the catalytic performance of H‐ZSM‐5 zeolite for MTO conversion,including activity and product selectivity,can be regulated properly through the purposive alteration of the acid site distribution,viz.,the location of Al in the zeolite framework.This study helps to elucidate the relation between the catalytic performance of different acid sites in the H‐ZSM‐5 zeolite framework for MTO conversion,which should greatly benefit the design of efficient catalyst for methanol conversion.

H-Y-zeolites induced heterocyclization:Highly efficient synthesis of substituted-quinazolin-4(3H) ones under microwave irradiation

A highly efficient synthesis of 2-amino-N-substituted-benzamides was performed by the condensation ofisatoic anhydride with several amines in solvent-free conditions under microwave irradiation. H-Y-zeolites induced heterocyclization of these products with ortho-esters under similar conditions afforded the relevant substituted-quinazolin-4（3H）ones in high yields.

Effect of combining the metals of group VI supported on H-ZSM-5 zeolite as catalysts for non-oxidative conversion of natural gas to petrochemicals

The most prestigious catalyst applied in natural gas （methane） non-oxidative conversion to petrochemicals is 6%Mo/H-ZSM-5. Chromium, molybdenum and tungsten are the group VI metals. Hence, in this work, 6%Mo/H-ZSM-5 was correlated with 3%Cr＋3%Mo/H-ZSM-5 and 3%W＋3%Mo/H-ZSM-5 as catalysts to examine their promoting or inhibiting effects on the various reactions taking place during methane conversion. The catalytic activities of these catalysts were tested in a continuous flow fixed bed reactor at 700℃ and a GHSV of 1500 ml·g^-1·h^-1 Characterization of the catalysts using XRD, TGA and TPD were investigated. XRD and NH3-TPD showed greater interaction between the W-phase and the Bronsted acid sites in the channels of the zeolite than between Cr-phase and the acid sites in the zeolite.

Catalytic Synthesis of Hexyl-naphthalene over H-type Zeolites

H-type zeolites（ HY, Hβ, and HM） were synthesized and characterized by XRD, NH3-TPD, and Py-IR. Selectively catalytic alkylation of naphthalene with n-hexanol to hexyl-naphthalene over the zeolites was carried out. The experimental results show that the catalytic activities of the zeolites are mainly determined by their acid properties and pore structures. The larger the pore diameter is, the higher the catalytic activity is. NH3-TPD profiles show that Hβ and HM have lower acid strengths than HY. HY has both the highest activity and highest selectivity for the hexylnaphthalene. Higher reaction temperatures and longer reaction time are beneficial to the production of β-hexyl-naphthalene over the HY zeolite.

ADSORPTION EQUILIBRIUM OF ETHYLENE-CARBON DIOXIDE MIXTURE ON ZEOLITE ZSM5 AND ITS CORRELATION

Binary gas mixture adsorption equilibrium data for the ethylene-carbon dioxide system were obtained for cation exchanged forms of ZSM5 (Li^+, Na^+, K^+, Rb^+, Mg^(+2), Ca^(+2), Sr^(+2), and Ba^(+2)) for the gas phase CO_2 mole fracion of 0.766 at 308K and 101. 3kPa. The experimental adsorption phase diagrams were obtained for CO_2-C_2H_4 on NaZSM5 and MgZSM5. Single component adsorption isotherms for CO_2 and C_2H_4 were also obtained for these two zeolites. The single component data were used to obtain parameters derived in the vacancy solution model (VSM) and the statistical thermodynamic model(STM). These parameters were, in turn, used to predict binary mixture isotherms for these two zeolites. The agreement between experimental data and predicted value is generally good.

A Study of Acidic Sites in H[M]-ZSM-5 Zeolites by XPS, IR and TPD

The present paper covers an X-ray photoelectron spectroscopic (XPS) method proposed for identifying Bronsted and Lewis acidic sites in zeolites and estimating acidic strength of these sites. It was found that the adsorption of pyridine on different acidic sites of H[M]-ZSM-5 zeolites exhibited three peaks: A (402.20-401.30 eV), B (400.95-400.40 eV) and C (399. 40-399. 10 eV). The peaks A and B are assigned to the N(?) level of pyridine adsorbed on Bronsted and Lewis acidic sites, and peak C is assigned to the N(?) level of pyridine adsorbed on a weak Lewis site and/or strongly physisorbed pyridine, respectively. The comparison of the ratio of the Bronsted and Lewis acidic sites determined from the relative intensities of the N(?), peaks with IR spectroscopic data shows that there is an inhomoge-neous distribution of Bronsted and Lewis acidic sites in H[M]-ZSM-5 zeolites. The N(?), binding energies of pyridine adsorbed on these zeolites directly reflect acidic strength, and these results are in good agreement with those observed in NH3-TPD experiments.

SHIP－IN－BOTTLE SYNTHESIS AND CHARACTERIZATION OF Ru_4H_4（CO）_（12）ENTRAPPED WITHIN NaY ZEOLITE

The ruthenium hydrido-carbonyl cluster in NaY zeolite,synthesized by the reaction of Ru3(CO)(12)/NaY with hydrogen,was characterized by FTIR,UV-VIS and EXAFS spectroscopies.

Alkylation of Benzene with Propene over Hβ Zeolite──The Effect of Reaction Conditions on the Distribution of Products

he effects of reaction temperature , flow rate of carrier gas , space velocity andbenzene to propene ratio on the alkylation of benzene with propene over Hβ zeolitewere investigated. At lower flow rate of carrier gas and space velocity, higher ben-zene to propene ratio the formation of cumene is favoured due to the difference be-tween rates of reactions of the alkylation of benzene (or cumene) with propene andthe alkyltranslation of diisopropylbenzene with benzene. The propylbenzene is pro-duced directly by the alkylation of benzene with propene.

AMINATION OF ETHANOL WITH AMM0NIA OVER H βZEOLITE

Ethylamine is sc feetively produced in the aminationof ethanol with ammonia over H β zeolite.

Zn/H-ZS M-5轻烃芳构化催化剂中Zn与分子筛协同作用的研究

分析了Al2 O3 的加入引起Zn/H ZSM 5催化剂芳构化活性和选择性下降以及稳定性有所改善的原因在于高温焙烧或水热处理 ,使掺有粘结剂氧化铝的Zn/H ZSM 5催化剂表面锌组元的再分布 ,即Al2 O3 上的锌含量增加 ,而处于H ZSM 5沸石上的锌浓度降低。较为系统地探讨了Al2 O3 和ZnO/Al2 O3 的芳构化催化作用以及锌组元和ZnO/Al2 O3的引入对HZSM 5性能的影响。论证了在Zn/H ZSM 5催化剂中只有处于分子筛表面的Zn组元才能同分子筛B酸中心产生协同作用 ,从而改善H ZSM 5分子筛的芳构化活性与选择性 ,而在经过焙烧和水热处理的混有Al2 O3 的Zn/H ZSM 5催化剂中 ,分布在Al2 O3 上的锌组元几乎不与分子筛发生协同作用 。

C_4H_8N_2H_4·Zn(HPO_3)_2的水热合成和结构表征

A new zinc hydrogen phosphite C4H8N2H4·Zn（HPO3）2 was prepared by hydrothermal method in the presence of piperazine as a structure-directing agent and the crystal structure was determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, IR, ICP, elemental analysis and TG analysis. This compound has one-dimensional anionic chains containing four-membered rings built from corner-sharing linked alternating ZnO4 tetrahedra and HPO3 pseudo pyramids. The zinc hydrogen phosphite chains are interacted with the templates of diprotonated piperazine by N—H…O hydrogen bond. Crystal data for C4H8N2H4·Zn（HPO3）2∶monoclinic, space group C2/c. a=1.774 8（2） nm, b=0.724 28（9） nm, c=0.880 87（11） nm, β= 105.345（3）°, V=1.091 9（2） nm 3, Z=4, Dc=1^907 Mg/m 3, R1=0.022 9, wR2=0.058 8.

Zn/H-ZSM-5催化剂上的二甲醚芳构化反应

考察了H-ZSM-5和Zn/H-ZSM-5催化剂的二甲醚芳构化性能.结果表明,H-ZSM-5分子筛催化剂酸性的增强和酸中心的增多有利于二甲醚芳构化.当在H-ZSM-5催化剂中加入2%Zn时,在360oC下反应时总芳烃收率从50.0%增加至66.2%,C8芳烃收率从28.6%增加到39.0%.反应温度升高到480oC时,总芳烃收率增加至78.0%.

五味子多糖对H_(22)荷瘤小鼠血清Zn、Se水平变化的干预作用研究

目的:研究H22荷瘤小鼠血清免疫相关微量元素Zn和Se水平的改变及五味子多糖的干预作用。方法:采用H22荷瘤小鼠,五味子多糖给药1w后采血,分离血清,原子分光光度法检测各组小鼠血清Zn和Se的水平。结果:Zn的含量在三个实验组间无显著性差异;而模型组小鼠的血清Se含量极显著低于正常组小鼠(P<0.01),给药组小鼠的Se含量则显著高于模型组小鼠(P<0.05)。结论:血清Se水平很可能是五味子多糖作用的靶点之一,五味子多糖可以通过上调H22荷瘤小鼠的血清Se水平来增强其抗肝癌的能力。

Zn(H_2PO_4)_2-N[CH_2CH_2OPO(OH)_2]_3对碳钢的协同效应与缓蚀机理研究

采用失重法、表面观察法、极化曲线法、氩离子刻蚀法和 XPS分析法研究 Zn(H2 PO4 ) 2 - N[CH2 CH2 OPO(OH) 2 ]3在海水中对碳钢的协同效应与缓蚀机理。结果发现 :50 % Zn(H2 PO4 ) 2 +50 % N[(CH2 CH2 OPO(OH) 2 ]3(XM- 30 3)在海水中对碳钢具有明显的协同缓蚀效应。 50 % Zn(H2 PO4 ) 2 +50 % N[CH2 CH2 OPO(OH) 2 ]3(XM- 30 3)主要为阴极抑制型缓蚀剂。缓蚀膜主要为沉积膜 ,膜层的主要组分有 Zn3(PO4 ) 2 、Fe PO4 、Fe2 O3和 N[CH2 CH2 OPO(OH) 2 ]3等。

Al_2O_3对Zn/HZSM-5芳构化催化剂的影响

研究了 Al2 O3的加入对 Zn改性 HZSM-5催化剂性能的影响。应用分析电镜 (TEM-EDS)对催化剂进行了微区元素组成分析 ,比较了 Al2 O3、Zn/ Al2 O3、HZSM-5以及 Zn/ Al2 O3+ HZSM-5机混催化剂的芳构化性能和 Zn分布 ,并初步探讨了影响 Zn组元分布的因素。结果表明 ,加入 Al2 O3的 Zn改性 HZSM-5催化剂在经过高温焙烧或水热处理后 ,原来处于分子筛上的 Zn组元部分迁移至 Al2 O3上 ,其芳构化活性和选择性降低 ,但稳定性有所改善 ;只有分布在分子筛表面的 Zn组元 ,才能有效地改善 HZSM-5分子筛的芳构化性能。

正己烷在Zn/HZSM-5上芳构化反应机理的探讨

比较了正己烷在HZSM 5、Al2 O3和ZnO/Al2 O3催化剂上的反应性能 ,探讨了锌含量和水热处理对Zn/HZSM 5芳构化性能的影响。发现B酸是芳构化反应不可缺少的活性中心 ,Zn L因其氢解作用促进烃类的活化和脱氢 ,Al L酸只是对正己烷有较弱的活化作用。提出了正己烷在Zn/HZSM 5上的芳构化反应机理。

Zn(Leu)SO_4·0.5H_2O在丙酮-水混合溶剂中的结晶动力学

确定了Zn(Leu)SO4 ·0 5H2 O在水 -丙酮中结晶生长的最佳体积比为 1∶5,用微量热法测定了该结晶生长过程在 2 98 15K时的放热量及产热速率,计算了动力学常数,认为结晶过程符合Burton Cabrera Grank位错理论.同时测定了Zn(Leu)SO4 ·0 5H2 O 2 98 15K时在纯水中的溶解焓为(3 17± 0 0 9)kJ·mol-1,计算了Zn(Leu)2 +(aq)的标准生成焓为( - 10 88 2 6± 4 2 8)kJ·mol-1.