Zeolite based films, membranes and membrane reactors: Progress and prospects

The integration of reaction and separation in catalytic membrane reactors has received increasing attention during the past 30 years. The combination promises to deliver more compact and less capital-intensive processes with substantial savings in energy consumption. With the advent of new inorganic materials and processing techniques, there has been renewed interest in exploiting the benefits of membranes in many industrial applications. Zeolite membranes, however, have only recently been considered for catalytic membrane reactor applications. Despite the significant recent interest in these types of membranes there are relatively few reports of the application of such membranes in high-temperature catalytic membrane reactor applications. This can be attributed to a number of limitations that still need to be addressed such as the relatively high price of membrane units, the difficulty of controlling the membrane thickness, permeance, high-temperature sealing, reproducibility and the dilemma of upscaling. A number of research efforts, with some degree of success have been directed to finding solutions to the remaining challenges. This review makes a critical assessment of what has been achieved in the past few years in terms of hurdles that still stand in the way of the successful implementation of zeolite membrane reactors in industry.     

Conversion of used vegetable oils to liquid fuels and chemicals over HZSM-5, sulfated zirconia and hybrid catalysts

Thailand’s food manufacturing uses about 47 Million liters per year of vegetable oil. Used vegetable oil is classified as waste, but has potential for conversion into liquid fuel. This research studied the catalytic conversion of used vegetable oil to liquid fuel, where investigation was performed in a batch microreactor over a temperature range of 380–430 °C, initial pressure of hydrogen gas over 10–20 bars, and reaction time of 45–90 minutes. Catalysts such as HZSM-5, Sulfated Zirconia and hybrid of HZSM-5 with Sulfated Zirconia were used to determine the conversion and yield of gasoline fraction. The major products obtained were liquid products, hydrocarbon gases and small amounts of solids. Liquid products were analyzed by simulated distillation gas chromatograph and the product distribution was obtained. Hybrid catalyst HZSM-5 with Sulfated Zirconia showed the highest yield of gasoline with a 26.57 wt% at a temperature of 430 °C, initial hydrogen pressure at 10 bars, and reaction time of 90 minutes in the ratio of hybrid HZSM-5 with Sulfated Zirconia at 0.3: 0.7.     

取代水杨醛Schiff碱金属配合物催化氧化脱硫性能

以水杨醛类Schiff碱为配体,与Co(NO_3)_2、Cu(NO_3)_2反应合成6种Salen(M)型配合物Ⅰ～Ⅵ。以1-己硫醇、二丁基硫醚和2-甲基噻吩为模型化合物配制模拟油体系,考察了配合物Ⅰ～Ⅵ的催化氧化脱硫性能,并分析了配合物结构与氧化脱硫性能的关系。结果表明,6种配合物在75 min时的总脱硫效果为Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ,Ⅵ的总脱硫率为31.9%。对1-己硫醇及二丁基硫醚脱除效果最佳的是Ⅴ,脱除率分别为74.2%和65.1%;对2-甲基噻吩脱除效果最好的是Ⅰ,脱除率为26.8%。构效关系研究表明,中心金属离子与O_2的配位能力越强,配体的共轭体系越大、电子云密度越高,配合物的脱硫性能越好;通过IR和离子色谱对单一硫化物模拟油体系氧化前后的产物进行分析发现,硫化物氧化后皆生成相应的砜类或亚砜类,且1-己硫醇和二丁基硫醚被进一步氧化生成SO_3~(2–)或SO_4~(2–)。     

A STUDY ON THE PERFORMANCE OF THE CATALYTIC POROUS-WALL THREE-PHASE REACTOR

A theoretical investigation of a catalytic porous-wall reactor in which gaseous and liquid reactants approach each other from opposite sides of the catalyst is undertaken. Equations for the annular liquid-channel are coupled with those for the catalytic wall and solved numerically and analytically using a simplified model. For the model reaction under study, the main design and operation parameters which affect reactor performance are the Thiele modulus, Peclet number, width of the liquid channel and the inlet concentration of the reactant in the liquid phase.

The effect of reactor configuration is peculiar to the cylindrical geometry because the thickness and relative location of the catalytic wall as well as the selection of the liquid and gas channels can influence the reactor performance. Thin-walled catalyst tubes have larger effectiveness factors and as the tube radius approaches that of the reactor, conversion in the reactor increases especially when the liquid is saturated with the gaseous reactant. Concentration of the liquid reactant in the feed has a significant effect if the reactant is depleted at some point inside the catalyst wall. Since the reaction zone width can be adjusted by changing the feed composition, this might have important implications with respect to selectivity.     

对叔丁基苯甲酸甲酯加氢合成对叔丁基苯甲醛

以对叔丁基苯甲酸甲酯为原料,二氧化锰负载氧化物为催化剂,在常压固定床反应器上考察了加氢还原催化剂对制备对叔丁基苯甲醛的影响因素,并获得了最佳反应条件为:反应温度为 380~400℃,酯的液时空速为 5mL/h,氢气的气时空速约为1050h-1及合适的催化剂:15%~20%MnO2 /γ Al2O3。     

NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

Study of the copper leaching in the wet oxidation of phenol with CuO-based catalysts: Causes and effects

Catalytic wet oxidation of phenol as a model pollutant has been performed in a three phase fixed-bed reactor (FBR) by using a commercial catalyst based on copper oxide in order to analyze the variables affecting significantly the copper leaching. It has been found that temperature has an almost negligible influence in the range studied (70–160 °C). On the contrary, an important effect of the pH value was noticed. The copper leaching reduces when the pH of the solution fed to the reactor increases, being almost negligible at pH ≥ 5. Moreover, the composition of the reaction media also influences the leaching. Higher copper concentrations than those expected by the effect of the acid aqueous media have been measured in the reactor effluent when phenol, catechol, hydroquinone, p-benzoquinone and maleic acid are present in the reaction media. On the contrary, oxalic acid has a negative influence on the leaching, since it captures the copper in solution to form copper oxalate which precipitates on the catalyst surface. For a previously acidified medium, the acetic and formic acids do not have any other effect on the copper leaching. It has been also demonstrated that as copper in solution decreases, so does phenol conversion, because the homogeneous catalysis contributes significantly to the oxidation reactions even in fixed-bed reactors.     

微孔无机膜反应器研究

主要介绍了无机膜在化学反应中的应用－－膜反应器研究，对膜反应器的特点、类型、应用、影响因素以及与其它反应器的比较进行了评述，并对其应用前景进行了展望。     

SELECTIVITY STUDIES IN THE PHOTOCHLORINATION OF METHANE II: EFFECT OF THE RADIATION SOURCE OUTPUT POWER AND OUTPUT SPECTRAL DISTRIBUTION

The effect of the output power and output spectral distribution of the radiation energy fed to a photoreactor upon the reaction yield and selectivities is studied both theoretically and experimentally. The study aims at the analysis of these influences in a series reaction such as the photochlorination of methane where methylene chloride and eventually chloroform are the most valuable products. The computational model employed has been verified for a group of selected conditions by means of bench-sale experiments.

It is found that the chlorine conversion shows the expected square root dependence with respect to the Local Volumetric Rate of Energy Absorption (LVREA). This dependence, in a first approximation, can also be assigned to the effect of the radiation source output power upon yield. It is also found that by manipulating the amount of radiation power fed to the reactor it is possible to ascertain the operating conditions favoring the production of predetermined intermediate products (e.g., methylene chloride or chloroform).

It is concluded that the use of customized lamps especially designed for each particular product on the basis of feasible changes in the characteristics of the existing radiation sources will favor a selective and more economical production of some of the stable intermediates, i.e., lamp design is an important feature in any optimal process design.     

Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals

An approach for biomass flash pyrolysis in a circulating fluid bed (CFB) reactor with continuous solids regeneration is described in this study. The unit is capable of performing conventional and catalytic biomass pyrolysis with the proper solid selection. The production of improved quality liquid products in a direct step through catalytic pyrolysis is investigated in this work. Both conventional and catalytic biomass pyrolysis can be effectively performed in this CFB unit. Flash pyrolysis conditions were achieved and liquid product yields of ∼70 wt% (on biomass feed) were obtained. The effect of specific operating variables including the type of inorganic solid material and the solid/biomass ratio was established on the final liquid product quality and yield. Solid materials considered included silica sand, a commercial fluid catalytic cracking catalyst and a ZSM-5 additive. Catalytic biomass pyrolysis generally leads to the production of additional water, coke and gases compared to conventional pyrolysis. However, the obtained liquid product quality and composition is improved.