Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst

The kinetics of the selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂ has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<T_R<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O₂, and essentially 0 with respect to NH₃. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH₃ was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) Cu^I is oxidized by O₂ to “Cu^II-oxo”, (ii) “Cu^II-oxo” reacts with NO to yield “Cu^II-N_xO_y”, and (iii) finally “Cu^II-N_xO_y” is reduced by NH₃ to give N₂, H₂O, and the regeneration of Cu^I (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that Cu^I or “Cu^II-oxo” species constitute the rate-determining active center.     

Study on Adsorption and Diffusion in Zeolite

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Dehydration of water/1-1-dimethylhydrazine mixtures by zeolite membranes

In this research, dehydration of water/1-1-dimethylhydrazine (UDMH) mixtures by zeolite NaA and hydroxy sodalite membranes has been investigated. Support of these membranes has been tubular mullites that have been made by extruding a mixture of about 67–75% kaolin clay and 33–25% distilled water using an extruder. Zeolite NaA and hydroxy sodalite membranes have been coated on the external surface of the porous supports by the hydrothermal synthesis.

UDMH/water mixtures have been separated at ambient temperature and pressure by pervaporation (PV) using these zeolite membranes. These membranes showed very high selectivity of water for all UDMH mixtures. For the UDMH/water mixtures, separation factor as high as 10 000 has been obtained for UDMH feed concentration of 2%. Total mass fluxes of 1.05–0.2 kg/(m² h) have been also obtained.     

Dealuminated Y Zeolite for Water-Driven Adsorption Heat Pumps: Hydrothermal Stability

Silica gel or zeolites AlPO-5 and SAPO-34 are recommended as adsorbents in water-driven heat pumps because of their selective water uptake. Secondary energy, like solar energy, can be used for regeneration of loaded adsorbers. In case of the availability of only low energy levels, the use of dealuminated Y zeolite (DAY) is the better choice because of the infinitely variation of its hydrophilic properties by tailoring of the framework Si/Al ratio. Actual data on the hydrothermal stability of DAY are lacking. Thus, we report on the long-term behavior of DAY zeolites with different Si/Al ratios.     

不同填料曝气生物滤池启动挂膜试验研究

不同填料曝气生物滤池在相同条件下进行挂膜试验。进水流向为上流式,挂膜方式为复合接种挂膜,即先用活性污泥闷曝接种,然后逐步提高进水流速,直到滤料表面形成稳定的生物膜。结果表明:33 d后挂膜成功,在温度为16～24℃,水力停留时间(HRT)为1 h,DO为6 mg/L的情况下,陶粒BAF对CODMn和NH3—N的去除率分别为23%和80%;沸石BAF的去除率分别为27%和84%;组合填料BAF去除效果最好,去除率分别为32%和92%。     

Zeolite based trace humidity sensor for high temperature applications in hydrogen atmosphere

We present a humidity sensor based on H-ZSM-5 type zeolite that is suitable to detect traces of humidity (10–110 ppm_V) under harsh conditions, e.g. reducing atmosphere (H₂) and high temperature (up to 600 °C). By means of complex impedance spectroscopy (IS) we show that the zeolite sensor responds linearly towards minimal changes in humidity. Therefore this result indicates that the zeolite sensor is capable to detect traces of humidity in processes where high temperatures in a hydrogen environment are required.     

沸石矿为模板制备多孔炭的研究

以几种沸石矿为模板、蔗糖为碳源，通过模板法制备了多孔炭，并用77K氮气吸附和X射线衍射仪(XRD)进行了表征。结果表明：此方法可以制备出具有一定比表面积和较大中孔容积的多孔炭．其中孔率随着模板中孔容积的增大而增加，但在所制多孔炭中存有少量的杂质。     

分子筛催化合成MTBE反应失活动力学

在改性β分子筛液相催化异丁烯与甲醇合成MTBE反应动力学的基础上,考察了内扩散阻力和催化剂失活对醚化反应的影响。假设符合平行失活机理,建立了带内扩散阻力的失活动力学方程,通过实验数据拟合确定了失活动力学参数。计算结果表明,醚化失活机理符合平行失活机理,异丁烯与甲醇合成MTBE的同时,发生副反应生成积碳是失活的原因。该失活动力学方程能很好地拟合试验数据,统计检验表明在置信度为99%以下是适合的。用所建失活模型预测了反应温度、催化剂颗粒度及进料时间对催化剂相对活性、有效因子和异丁烯转化率的影响。     

Radiation and thermal effects on porous and layer structured materials as getters of radionuclides

The long term radiation and thermal effects on porous and layer structured materials that may function as getters for radionuclides have been evaluated using accelerated laboratory experiments including energetic electron, ion or neutron irradiation, as well as high-temperature thermal annealing. The materials studied include: zeolites, layered silicates (mica and smectite clays), open framework structured apatite and crystalline silicotitanate (CST) which is an important synthetic ion-exchange material for the chemical separation of high-level liquid radioactive wastes.In situ transmission electron microscopy during irradiation by energetic electrons and ions has shown that all the studied materials are susceptible to irradiation-induced amorphization. Amorphization can be induced by ionization and/or direct displacement processes. Amorphization may be preceded or accompanied with dehydration, layer spacing reduction and gas bubble formation. In the case of zeolites, CST and some layer silicates, radiation effects are significantly enhanced at higher temperatures. In fact, thermal annealing at high temperatures alone can cause complete amorphization of zeolites. Our experiments have shown that amorphization or even partial amorphization will cause a dramatic reduction (up to 95%) in ion-exchange and sorption/desorption capacities of zeolite for radionuclides, such as Cs and Sr. Because the near-field or chemical processing materials (e.g., zeolites or CST) will receive a substantial radiation dose after they have incorporated radionuclides, our results suggest that radiation effects may, in some cases, retard the release rate of sorbed or ion-exchanged radionuclides.     

Influence of Solution pH and Ionic Strength on Chromate Uptake by Surfactant-Modified Zeolite

In this study, the influence of solution pH and ionic strength on sorption of chromate by surfactant-modified zeolite was tested. The sorption of chromate followed a Langmuir isotherm under different pH and ionic strength conditions. However, as the solution pH and ionic strength increased, the Langmuir sorption coefficient of chromate decreased systematically, reflecting an increased competition of background electrolyte anions against chromate for sorption sites. The chromate sorption maximum also decreased slightly as the solution pH and ionic strength increased. The stoichiometric relationship between chromate sorption and counterion desorption further indicated that chromate sorption on surfactant-modified zeolite surfaces was mainly due to surface anion exchange. In addition, increases in background electrolyte reduced counterion desorption and resulted in a better surfactant bilayer formation.