Kinetic modelling of the catalytic conversion of synthesis gas

A kinetic study for the one-step conversion of synthesis gas to gasoline on a ZnO–Cr₂O₃–ZSM-5 catalyst is described. On this catalyst, three reactions are involved in the overall transformation of synthesis gas: the methanol synthesis, the conversion of methanol to hydrocarbons and the water–gas shift reaction. Under the operating conditions selected for the study, it was found that the water–gas shift was at equilibrium and the methanol was completely converted to hydrocarbons. Consequently, it was postulated that the kinetics of the limiting reaction step, the methanol synthesis on the ZnO–Cr₂O₃ component, was the one that controls the overall reaction rate. Three kinetic model equations describing the rate of synthesis gas conversion on the bifunctional catalyst, were considered to fit the data of the experimental runs performed in a Berty well-mixed reactor. Those equations were derived under very special conditions where the methanol decomposition term could be neglected. It was also observed that in the kinetic equations a term involving the fugacity of CO₂ was required to predict the rate properly. The catalyst deactivation was also taken into account in the analysis.     

水杨醛型腙类试剂测定铝的研究

合成了以水杨醛为母体的４种腙类新荧光试剂，并对其与铝的荧光反应性能进行了比较研究，结果表明，５－溴－水杨醛水杨酰腙是一种优良试剂。它与铝在ｐＨ５．４醋酸－醋酸铵缓冲溶液中形成１３型荧光配合物，其λｅｘ＝３７０ｎｍ，λｅｍ＝４６０ｎｍ。建立的分析方法检测下限为１．１ｎｇ／ｍＬ，相对标准偏差为１．４５％。考察了３０余种共存离子的干扰情况。直接应用于葡萄糖注射液及常见饮料中微量铝的测定，结果满意。     

Evidence for non-site-isolation in ZSM-5 from ion-exchange and catalytic studies

Ion exchange of HZSM-5 samples with alkali metal cations, using metal chloride solutions, results in partially exchanged zeolites, MHZSM-5, M = Li, Na, K or Cs. The degree of exchange is found to increase with increasing ionic radius of the cations. The catalytic properties of the alkalized zeolites were evaluated using the reaction conditions under which the catalytic activity of the HZSM-5 samples in terms of n-hexane cracking is proportional to the aluminium content. From the residual catalytic activity exhibited by the Na-, K- and CsHZSM-5 samples it is concluded that each of the larger Na⁺, K⁺ and Cs⁺ ions is influencing more than one AlO ₄ ^– tetrahedron, implying that the aluminium sites in ZSM-5 are not isolated. The ion-exchange results are then interpreted in terms of non-isolated aluminium sites. The ion-exchange and catalytic properties of the zeolites as a function of aluminium content are also discussed.     

Sex pheromone specificity as a reproductive isolating mechanism among the sibling speciesArchips argyrospilus andA. mortuanus and other sympatric tortricine moths (Lepidoptera: Tortricidae)

MaleArchips argyrospilus (Walker) were maximally attracted to a 60404200 admixture of (Z)-11-tetradecenyl, (E)-11-tetradecenyl, (Z)-9-tetradecenyl and dodecyl acetates. The identification of (Z)-9-tetradecenyl acetate, in addition to the other 3 components reported previously, is the first report of a 4-component pheromone system in moths.Archips mortuanus Kearfoot, a sibling species, was maximally attracted to a blend of the same components, but in a 90101 mix of the tetradecenyl acetates. Among a number of tortricine moths that co-occur on apples and other hosts in New York, British Columbia, and elsewhere, differences in diel rhythms of attraction and seasonal distribution are insufficient to maintain reproductive isolation. Although the attractant systems of these species often possess components in common, males are maximally attracted to a speciesspecific blend. In tortricine moths attraction specificity appears to be a paramount mechanism for species partitioning.     

Combustion of methane over palladium ZSM-5 and mordenite catalysts

The effect of Pd-loading on Pd-NaZSM-5 and Pd-NaMordenite catalysts prepared by ion exchange was studied for methane combustion with excess oxygen (1% CH₄, 18% O₂, balance N₂) in the temperature range 40–500°C. Fresh and calcined samples (3 h, 450°C) showed methane conversions proportional to Pd-loading on Pd-NaZSM-5 catalysts, while conversions decreased with Pd-loading on calcined Pd-NaMordenite catalysts. TOF (number of methane molecules converted per second per Pd²⁺ ion) for over exchanged Pd-NaZSM5-116 was low as compared to under exchanged Pd-NaZSM5-80 and Pd-NaZSM5-58 samples. Close TOF's were found for the last two samples at 330°C. TOF differences in Pd-NaMordenite catalysts demonstrate the heterogeneity of Pd⁺² sites due to structurally nonidentical locations of cations. TOF's appear to be related to Na/Pd ratios in both catalyst types. Apparent activation energies for Pd-NaZSM-5 materials are higher than those for Pd-NaMordenite catalysts.     

改性5A分子筛对水中As(Ⅴ)的吸附作用研究

改性5A分子筛是一种高效吸附材料。实验用5A分子筛作为载体,制备了该吸附剂,并表征了其基本性质。结果表明,改性5A分子筛对As(Ⅴ)具有很高的吸附率和选择性;室温下,pH=7时,改性5A分子筛吸附As(Ⅴ)的吸附等温线符合Langmuir型和Freundlich型。     

Effect of the metal oxide loading on the activity of silica supported MoO3 and V2O5 catalysts in the selective partial oxidation of methane

Precipitated silica catalysts loaded with either MoO₃ (0.2–4.0 wt%) or V₂O₅ (0.2–5.3 wt%) have been studied in the selective partial oxidation of methane to formaldehyde with molecular oxygen at 520 °C. The functionality of the SiO₂ surface towards the formation of HCHO is significantly promoted by V₂O₅, while it is depressed by the MoO₃.     

酯对钼系Ziegler-Natta催化剂引发丁二烯聚合的影响

以MoCl_4(Mo)为主催化剂,甲苯氧基二异丁基铝(Al)为助催化剂,在加氢汽油溶剂中,研究了8种酯对丁二烯(Bd)聚合的影响。结果表明,凡是能够溶解在酯中的Mo与Al所组成的二元催化体系,大多能很好地引发Bd聚合,并有较高的催化活性。酯的主要作用是增加Mo在加氢汽油中的溶解性,对聚合物的分子量影响不大,对微观结构几乎无影响。