Diamond synthesis by DC thermal plasma CVD at 1 atm

Diamond crystals and films have been success full y synthesized by DC thermal plasma jet CVD at a pressure of I atrn. A novel triple torch plasma reactor has been used to generate a convergent plasma volume to entrain the participating gases. Three coalescing plasma jets produces! by this reactor direct the dissociated and ionized gaseous species onto ( 100) silicon wafer substrates where the diamond grows. In a typical 10-min run, depending on the method of .substrate preparation, either microcrystals with sizes up to 8 m or continuous films with thicknesses of 1–2 m have been obtained. X-ray diffraction, scanning electron microscopy, and Raman spectroscopy have been used for the characterization of the crystals and of the films.     

Voltammetry Under Microfluidic Control,a Flow Cell Aproach

A generic approach to the design, construction and experimental characterization of novel microelectrochemical reactors (MECR) is presented. Structurally well‐defined rectangular microchannels incorporating electrochemical sensors were fabricated using a propriety photosensitive glass and photolithographic techniques. Microelectrode sensors were produced via evaporation to yield, gold, silver or platinum bands of approximate lengths 10–50 μm. The approach outlined permits cells of dimensions in the range: height 50–100 μm, width 100–500 μm and length 1–3 cm to be accurately constructed, in single or array configurations and were characterized via a voltammetric study utilizing electrolyte solutions containing N,N,N′N′‐Tetramethyl‐1,4‐phenylenediamine. In all cases, the test cells were constructed so that the three dimensional hydrodynamic boundary layer within the cells would significantly influence the reagent transport and therefore the observed current density at the microelectrodes. The current/flow rate relationship observed was analogous to the response of the observed within the macroscopic channel flow cells, where typically the cell design is restricted to configurations where a two dimensional transport analysis can be performed.     

Influence of biomass on hydrodynamics of an internal loop airlift reactor

The effect of the biomass presence on the overall circulation velocity, the linear velocities both in the riser and the downcomer and the overall gas hold-up was studied in a three-phase internal loop airlift reactor (ILALR). The measured data were compared with those obtained using a two-phase system (air—water). All experiments were carried out in a 40 dm³ ILALR at six different biomass concentrations (ranging from 0 g dm⁻³ to 7.5 g dm⁻³), at a temperature of 30°C, under atmospheric pressure. Air and water were used as the gas and liquid model media, respectively. Pellets of Aspergillus niger produced during the fermentation of glucose to gluconic acid in the ILALR were considered solid phase. In addition, liquid velocities were measured during the fermentation of glucose to gluconic acid using Aspergillus niger. All measurements were performed in a bubble circulation regime. At given experimental conditions the effect of the biomass on the circulation velocities in the ILALR was negligible. However, increasing of the biomass concentration led to lower values of the total gas hold-up. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Effect of the shear rate on pullulan production from beet molasses by Aureobasidium pullulans in an airlift reactor

The effect of the shear rate on pullulan production from beet molasses by Aureobasidium pullulans P56 in an airlift reactor was investigated. A maximum polysaccharide concentration (18.5 g/L), biomass dry weight (14.0 g/L), polysaccharide yield (38.5%), and sugar utilization (96%) was achieved at a shear rate of 42 s⁻¹. A. pullulans grown on beet molasses produced a mixture of pullulan and other polysaccharides. The highest value of pullulan proportion (30% of total polysaccharide) was obtained at a low shear rate (42 s⁻¹). The apparent viscosity of the fermentation broth increased as the shear rate increased up to 42 s⁻¹ and then decreased. On the other hand, the dissolved oxygen concentration and the volumetric mass transfer coefficient increased with the increase of the shear rate from 21 to 84 s⁻¹. The external addition of L-glutamic acid, olive oil, and Tween-80 improved significantly the production of crude polysaccharide (27.0 g/L), but the pullulan content of the polysaccharide was low (20%).     

甲烷直接氧化制甲醇Ⅲ．反应气吹扫催化膜反应器（RSCMR）

用溶胶－凝胶法制备了“ＳｉＯ＿２／陶瓷”非对称无机膜，并用该膜制备了反应气吹扫催化膜反应器（ＲＳＣＭＲ）装置。在ＲＳＣＭＲ上考察了甲烷一步催化氧化制甲醇反应。结果表明，在研究的范围内，增加氧气或甲烷的浓度和吹扫气的流速（即总的反应气流量）有利于提高甲醇的收率；甲醇在反应条件下的热不稳定性是影响目标反应选择性的重要原因。ＲＳＣＭＲ较膜反应器（ＣＭＲ）系统能更有效地抑制甲醇的热分解，因而可得到较ＣＭＲ更高的甲醇收率。当反应温度为７００℃时，甲醇的收率在ＣＭＲ中为０．５ｇ／ｍ￣２ｈ，在ＲＳＣＭＲ中可达０．９ｇ／ｍ￣２ｈ。     

Zr（Ⅳ）／PVA功能膜的膜催化酯化反应研究

在催化与渗透汽化分离技术相偶合的渗透汽化型膜反应器中，研究了羧酸酯的液相合成反应．实验中制备了两类具有强酸催化活性的ｚｒ（Ⅳ）／ＰＶＡ（聚乙烯醇）功能膜，采用管式膜方式，以乙酸正丁酯的合成反应为探针，对这类新型的催化反应技术在催化活性、分离性能以及分离对反应转化的影响等方面进行了探索性研究。从得到的结果看，膜催化酯化反应过程的反应条件和缓，转化率可达到９８％，反应的选择性为１００％．     

脉冲电晕环境中13X分子筛对NO分解作用的研究

在常温、常压下，利用脉冲电晕放电产生冷等离子体，使一氧化氮发生分解，直接生成氮气和氧气，用四极杆质谱仪在线测量反应过程中反应物和生成物的变化。在自行研制的实验台上，考察了13X分子筛在不同的脉冲电晕放电条件下，表现出来的不同特性及其对反应转化率的影响。在30 ℃～430 ℃、流量375 mL/min～1 333 mL/min，分析了该反应过程中13X分子筛对转化率的促进作用。在同一脉冲放电条件下，控制13X分子筛的温度为200 ℃，转化率从30 ℃时的1.2%上升到19.7%；转化率最高可以达到35.9%。并对反应过程中13X分子筛的吸附特性做了初步探讨。     

Simulation of a Combined Isomerization Reactor & Pressure Swing Adsorption Unit

The Total Isomerization Process developed by Union Carbide in 1970 (Gary, 1987) for the conversion of normal paraffin's to their isomers consists of a reactor followed by a PSA unit each operating at similar pressures and temperatures. The combination of these two operations in one unit in a Pressure Swing Adsorption Reactor (PSAR) process may provide an increased throughput and a significant cost saving in ancillary equipment.The simulation of a mathematical model linking the catalyst packed-bed and the adsorbent packed-bed is reported. The catalyst is a Pd/Y-zeolite and the adsorbent is 5A zeolite. The simulated feed consists of 17% each of n- and isopentane with the remainder being hydrogen. The mathematical model assumes dispersed plug-flow in both sections, constant velocity in the reactor section but varying in the adsorber, with mass transfer in the adsorber section due to external fluid film resistance and macropore diffusion in series. The fraction of the total column length occupied by the catalyst (denoted by ) is accounted for in the model by solving numerically using orthogonal collocation on finite elements. Parameters varied are the ratio of catalyst/column length (), temperature range (506–533 K), high pressure (15–20 bars), with the low pressure held constant at 2 bars. The catalyst/column ratio has a strong effect at low temperatures. The optimum catalyst/column length ratio appears to be controlled by the low pressure step and occurs at = 0.7 for the assumptions used in this work.     

Enhancing the enzymatic hydrolysis of cellulosic materials using simultaneous ball milling

One of the limiting factors restricting the effective and efficient bioconversion of softwood-derived lignocellulosic residues is the recalcitrance of the substrate following pretreatment. Consequently, the ensuing enzymatic process requires relatively high enzyme loadings to produce monomeric carbohydrates that are readily fermentable by ethanologenic microorganisms. In an attempt to circumvent the need for larger enzyme loadings, a simultaneous physical and enzymatic hydrolysis treatment was evaluated. A ball-mill reactor was used as the digestion vessel, and the extent and rate of hydrolysis were monitored. Concurrently, enzyme adsorption profiles and the rate of conversion during the course of hydrolysis were monitored. α-Cellulose, employed as a model substrate, and SO₂-impregnated steam-exploded Douglas-fir wood chips were assessed as the cellulosic substrates. The softwood-derived substrate was further posttreated with water and hot alkaline hydrogen peroxide to remove >90% of the original lignin. Experiments at different reaction conditions were evaluated, including substrate concentration, enzyme loading, reaction volumes, and number of ball beads employed during mechanical milling. It was apparent that the best conditions for the enzymatic hydrolysis of α-cellulose were attained using a higher number of beads, while the presence of air-liquid interface did not seem to affect the rate of saccharification. Similarly, when employing the lignocellulosic substrate, up to 100% hydrolysis could be achieved with a minimum enzyme loading (10 filter paper units/g of cellulose), at lower substrate concentrations and with a greater number of reaction beads during milling. It was apparent that the combined strategy of simultaneous ball milling and enzymatic hydrolysis could improve the rate of saccharification and/or reduce the enzyme loading required to attain total hydrolysis of the carbohydrate moieties.     

Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

The effects of temperature and pressure on the steam reforming of methane 3H2+CO) were investigated in a membrane reactor (MR) with a hydrogen permeable membrane. The studies used a novel silica-based membrane prepared by using the chemical vapor deposition (CVD) technique with a permeance for H2 of 6.0×l0-8 mol·m-2·s-1·Pa-1 at 923 K. The results in a packed-bed reactor (PBR) were compared to those of the membrane reactor at various temperatures (773-923 K) and pressures (1-20 atm, 101.3-2026.5 kPa) using a commercial Ni/MgAl2O4 catalyst. The conversion of methane was improved significantly in the MR by the countercurrent removal of hydrogen at all temperatures and allowed product yields higher than the equilibrium to be obtained. Pressure had a positive effect on the hydrogen yield because of the increase in driving force for the permeance of hydrogen. The yield of hydrogen increased with pressure and reached a value of 73×10-6 mol·g-1·s-1 at 2026.5 kPa and 923 K which was higher by 108% than the value of 35×10-6 mol·g-1·s-1 obtained for the equilibrium yield. The results obtained with the silica-based membrane were similar to those obtained with various other membranes as reported in the literature.