生产99Mo、131I和89Sr医用同位素的水溶液堆

99Mo1、31I和89Sr等医用同位素对人类健康和医学的发展具有非常重要的作用。与靶辐照反应堆相比,用水溶液堆生产99Mo1、31I和89Sr具有安全性好,结构简单,经济价值高,无靶件制备、溶解工艺,产生废物少等优点,用水溶液堆生产医用同位素具有很好的发展前景。由于多堆芯水溶液堆、高功率水溶液堆均能显著提高产率,低富集度235U水溶液堆符合核不扩散条约中对235U浓缩度的要求,因此这三种堆是水溶液堆未来的发展方向。     

Asymmetric catalysis in a micro reactor—Ce, Yb and Lu catalysed enantioselective addition of trimethylsilyl cyanide to benzaldehyde

A T-shaped micro reactor was used for the optimisation of reaction conditions for the enantioselective silylcyanation of benzaldehyde catalysed by lanthanide-pybox complexes. Compared to a conventional batch procedure, higher conversion was observed within shorter reaction time. The micro reactor process involving Lu(III) afforded essentially the same enantioselectivity as the batch process (73 vs 76% ee), whereas the enantioselectivity was lower in the micro reactor for catalysts containing Yb(III) (53 compared to 72%). Ce(III) provided very low selectivity in both types of processes (1 and 11% ee, respectively). A study of the effect of additives showed that the enantioselectivity in the Yb catalysed reaction performed in the micro reactor could be increased to 66%, whereas only a minor improvement, to 78% ee, was observed in the reaction with Lu.     

Synthesis of Biodiesel from Palm Oil in Capillary Millichannel Reactor: Effect of Temperature,Methanol to Oil Molar Ratio,and KOH Concentration on FAME Yield

Application of microtube reactor for the continuous synthesis of biodiesel has been widely studied due to excellent performance in liquid-liquid phase reaction. In order to commercialize biodiesel production, integration of microtube reactor is highly recommended. Therefore, in this study, synthesis of biodiesel was carried out in capillary millichannel reactor with inner diameter of 1.59 mm using methanol and potassium hydroxide (KOH) as base catalyst with palm oil as a feedstock. The influences of reaction temperature, methanol to oil molar ratio, and KOH concentration on the production of fatty acid methyl ester (FAME) were examined. The highest FAME yield was achieved at 60 ˚C with 23:1 methanol to oil molar ratio and 5 wt% of KOH concentration.     

Periodic, Mixed-Mode, and Chaotic Regimes in the Belousov–Zhabotinskii Reaction Catalyzed by Ferroin

The periodic, mixed-mode, and chaotic regimes in the ferroin-catalyzed Belousov–Zhabotinskii (BZ) reaction observed in a continuous stirred tank reactor (CSTR) reactor at various flow rates were experimentally studied. It was found that an increase in the flow rate resulted in the appearance of various complex oscillations. The possibility of the numerical simulation of experimentally observed asymptotic mixed-mode oscillations and chaotic regimes with the use of a kinetic scheme that includes experimental rate constants of each step of the ferroin-catalyzed BZ reaction was first demonstrated. The reaction scheme adequately describes the bifurcation sequence of experimentally observed oscillating regimes.     

Morphology,Nanostructure, and Processability of Reactor Powders of Ultrahigh-Molecular-Weight Polyethylene Produced on Self-Immobilizing Catalytic Systems

The possibility of heterogenization of a polymer system by using new post-metallocene catalytic systems comprising phenoxy-imine titanium halide complexes with different ligand environments modified by oxyallyl groups was studied with the aim of decreasing sticking of the reactor powders of ultra-high-molecular-weight polyethylene (UHMWPE RPs) suitable for solid-phase processing. The effective use of selfimmobilizing systems for the manufacture of UHMWPE RPs with reduced sticking to the reactor walls and the stirrer, but with somewhat reduced strength of the UHMWPE RP-based articles is shown.     

Design,construction and study of a continuously fed ohmically heated reactor for powdered solid sample digestion

The design, construction and testing of an ohmically heated graphite reactor for digestion of continuously fed powdered (<100-μm diameter) solid samples are discussed. The system operates in a continuous sample feed mode with a 100% power 3-kW duty cycle. The configuration provides a means of protecting the graphite reactor from contact with air and an efficient method of cooling the electrodes. Furthermore, the design includes a simple interface between the reactor and the powder feeder as well as between the reactor and the plasma. Experiments conducted on SO-4 Soil Certified Reference Material (CRM) as well as on 1646 Estuarine Sediment CRM demonstrated that a linear relationship existed between the integrated time-dependent signal and the net sample mass fed when the reactor's output was fed directly into an inductively coupled plasma atomic emission spectrometer (ICP-AES). The comparison between the experimental and theoretical composition ratios for both CRMs led to good agreement, between 0.27% and 11%, for elements certified in both CRMs. Absolute limits of detection of the order of 6–7 ng for Al, Ca and Fe were achieved. Under normal operating conditions, the power dissipated in the reactor was found to be of the order of 2–3 kW with corresponding temperatures of ∼2400 to ∼2700 K.     

Modeling and analysis of high‐impact poly(propylene) production processes, 1. Effect of chemical poisoning on particle size distribution and gel formation

This work presents a simple model for a two‐stage process of high impact poly(propylene) (HIPP) production. The model predicts the bivariate distribution of particle size and polymer composition. It takes into account the effect of chemical poisoning on gel particle formation. The result shows that poisoning the solid catalyst is not an effective method for gel reduction. A better approach is to saturate the polymer particles with a co‐catalyst in reactor 1 and poison the co‐catalyst in reactor 2. It is also shown that the residence time distribution (RTD) of reactor 1 has a strong effect on the gel particle formation. A continuous reactor with narrow RTD is advantageous for gel reduction. The model provides some guidance for the analysis and design of the HIPP production process.     

Thermal decomposition mechanisms of the methoxyphenols: formation of phenol, cyclopentadienone, vinylacetylene, and acetylene

The pyrolyses of the guaiacols or methoxyphenols (o-, m-, and p-HOC(6)H(4)OCH(3)) have been studied using a heated SiC microtubular (μ-tubular) reactor. The decomposition products are detected by both photoionization time-of-flight mass spectroscopy (PIMS) and matrix isolation infrared spectroscopy (IR). Gas exiting the heated SiC μ-tubular reactor is subject to a free expansion after a residence time of approximately 50-100 μs. The PIMS reveals that, for all three guaiacols, the initial decomposition step is loss of methyl radical: HOC(6)H(4)OCH(3) → HOC(6)H(4)O + CH(3). Decarbonylation of the HOC(6)H(4)O radical produces the hydroxycyclopentadienyl radical, C(5)H(4)OH. As the temperature of the μ-tubular reactor is raised to 1275 K, the C(5)H(4)OH radical loses a H atom to produce cyclopentadienone, C(5)H(4)═O. Loss of CO from cyclopentadienone leads to the final products, acetylene and vinylacetylene: C(5)H(4)═O → [CO + 2 HC≡CH] or [CO + HC≡C-CH═CH(2)]. The formation of C(5)H(4)═O, HCCH, and CH(2)CHCCH is confirmed with IR spectroscopy. In separate studies of the (1 + 1) resonance-enhanced multiphoton ionization (REMPI) spectra, we observe the presence of C(6)H(5)OH in the molecular beam: C(6)H(5)OH + λ(275.1?nm) → [C(6)H(5)OH ?] + λ(275.1nm) → C(6)H(5)OH(+). From the REMPI and PIMS signals and previous work on methoxybenzene, we suggest that phenol results from a radical/radical reaction: CH(3) + C(5)H(4)OH → [CH(3)-C(5)H(4)OH]* → C(6)H(5)OH + 2H.     

Whey Treatment by AnSBBR with Circulation: Effects of Organic Loading,Shock Loads,and Alkalinity Supplementation

The main objective of this work was to investigate the effect of volumetric loading rate (VLR), shock load, and alkalinity supplementation on the efficiency and stability of an Anaerobic Sequencing Batch Biofilm Reactor (AnSBBR) containing polyurethane foam cubes. Mixing in the reactor, which was kept at 30 ± 1°C, occurred by recirculating the liquid phase. The reactor treated 2.5 l cheese whey in 8-h cycles, at concentrations of 1, 2, and 4 g COD l⁻¹, which corresponded to VLRs of 3, 6, and 12 g COD l⁻¹ day⁻¹, respectively. Application of single-cycle shock loads of 6, 12, and 24 g COD l⁻¹ day⁻¹ did not impair reactor performance. In addition, for VLRs of 3, 6, and 12 g COD l⁻¹ day⁻¹, alkalinity supplementation to the influent, at the end of each assay, could be reduced to 75, 50, and 50%, respectively, in relation to supplementation at the beginning of the assay. During reactor operation a viscous polymer-like material was formed between the polyurethane foam cubes, which increased at higher VLR. Finally, addition of salts to the influent improved reactor efficiency.     

A novel flow reactor for studying reactions on liquid surfaces coated by organic monolayers: methods, validation, and initial results

A new flow reactor has been developed that allows the study of heterogeneous kinetics on an aqueous surface coated by an organic monolayer. Computational fluid dynamics simulations have been used to determine the flow characteristics for various experimental conditions. In addition a mathematical framework has been developed to derive the true first-order wall loss rate coefficient, k(1st)(w), from the experimentally observed wall loss rate, k(obs). Validation of the new flow reactor is performed by measuring the uptake of O(3) by canola oil as a function of pressure and flow velocity and the reactive uptake coefficients of N(2)O(5) by aqueous 60 wt % and 80 wt % H(2)SO(4). Using this new flow reactor, we also determined the reactive uptake coefficient of N(2)O(5) on aqueous 80 wt % H(2)SO(4) solution coated with an 1-octadecanol (C(18)H(37)OH) monolayer. The uptake coefficient was determined as (8.1 +/- 3.2) x 10-4, which is about 2 orders of magnitude lower compared to the reactive uptake coefficient on a pure aqueous 80 wt % H(2)SO(4) solution. Our measured reactive uptake coefficient can be considered as a lower limit for the reactive uptake coefficient of aqueous aerosols coated with organic monolayers in the atmosphere, because in the atmosphere organic monolayers will likely also consist of surfactants with shorter lengths and branched structures which will have a smaller overall effect.     

Solvent-free asymmetric olefin hydroformylation catalyzed by highly cross-linked polystyrene-supported (R,S)-BINAPHOS-Rh(I) complex

Using an (R,S)-BINAPHOS-Rh(I) catalyst that is covalently anchored to a highly cross-linked polystyrene support, asymmetric hydroformylation of olefins was performed in the absence of organic solvents. The reaction of cis-2-butene, a gaseous substrate, provided (S)-2-methylbutanal with 100% regioselectivity and 82% ee upon treatment with H(2) (12 atm) and CO (12 atm) in a batchwise reactor equipped with a fixed bed. The polymer-supported catalyst was applicable to a continuous vapor-flow column reactor, and thus, 3,3,3-trifluoropropene was converted into (S)-2-trifluoromethylpropanal with an iso/normal ratio of 95/5 and 90% ee. Less volatile olefins, such as styrene, vinyl acetate, 1-alkenes, and fluorinated alkenes, were successfully converted into the corresponding isoaldehydes with high ee values, when they were injected through a supercritical CO(2)-flow column reactor. Successive injection of a series of olefins realized the conversion of an olefin library into an optically active aldehyde library.     

Evaluation of a sensitive,reasonable, and fast detection method for 55Fe in steel

Journal of Radioanalytical and Nuclear Chemistry - A pilot study to quantify 55Fe in steel from a reactor vessel of a nuclear power plant by accelerator mass spectrometry (AMS) without any chemical...     

Study on methanol reforming–inorganic membrane reactors combined with water–gas shift reaction and relationship between membrane performance and methanol conversion

When a methanol reforming–membrane reactor is employed as a hydrogen generator for proton exchange membrane fuel cell (PEMFC), three important aims should be simultaneously achieved in one process, which are methanol conversion improvement, high hydrogen recovery, and high CO removal efficiency. To achieve the aims, we investigated five different configurations of a membrane reactor (a methanol reforming–microporous membrane (MMi) reactor, methanol reforming–mesoporous membrane (MMe) reactor, methanol reforming–mesoporous membrane–water–gas shift (MMeW) reactor, methanol reforming–macroporous membrane (MMa) reactor and methanol reforming–macroporous membrane–water–gas shift (MMaW) reactor). As a result, the MMi reactor was not suitable for a hydrogen carrier of PEMFC due to low hydrogen recovery. The MMe and MMa reactor showed low CO removal efficiency due to low permselectivity of the mesoporous and macroporous membrane. In contrast, the MMeW and MMaW reactor gave simultaneously methanol conversion improvement, high hydrogen recovery, and high CO removal efficiency in one process. The low CO removal efficiency due to low permselectivity of the mesoporous and macroporous membrane was significantly enhanced by the water–gas shift reaction in the permeate side of the MMeW and MMaW reactor. In addition, based on the reaction results in the MMi, MMe and MMa reactor, it was confirmed that methanol conversion in a membrane reactor system is higher as a membrane used in a membrane reactor has higher total permeance difference (∑permeance of products − ∑permeance of reactants).     

Digestion efficiency study of an intraplasmic reactor for in-situ,halogen assisted direct solid sample digestion by Inductively Coupled Plasma Atomic Emission Spectroscopy

A new type of intraplasmic reactor designed for in-situ, batch digestion of refractory solid samples, the Modified Direct Sample Introduction (MDSI) reactor, is presented and qualitatively evaluated with CH₃Cl, Cl₂ and Freon-12 as gaseous halogenating reagents. A comparison of the digestion capabilities of MDSI and CH₃Cl or Freon-12 assisted electrothermal vaporization is also presented. The refractory model compounds used were Al₂O₃ and SiO₂, which were deposited inside the reactor as 10 μl of a 1% m/m slurry. A soil sample SO-3 CRM was also used to evaluate the detection limits, which were found to be in the ppb range for sensitive lines (Cu and Pb) and in the ppm range for less sensitive lines (Al, Fe, Si and Zn). The results obtained indicate that the MDSI reactor design rapidly achieved a sufficiently high temperature for quantitative vaporization of the samples. The study of the various halogenating reagents show that (1) the presence of carbon in the halogenating reagent acts as a reducing agent for the oxides and also forms a protective pyrolitic graphite coating on the reactor's inner walls, thereby reducing analyte permeation into those walls and (2) the ideal gaseous halogenating reagent must exhibit a good thermal stability to intermediate temperatures (∼200°C) to avoid premature decomposition. The reactive intermediates must also be thermally stable to avoid formation of soot that may plug the reactor and reduce the vaporization. Of all reagents tested. Freon12 remains the reagent of choice for in-situ digestion of refractory solids.     

Ignition of coal powders in the presence of natural gas,oxygen, and reactive admixtures

At elevated temperatures (650–750°C), coating the inner surface of the reactor with coal dust exerts a significant effect on the ignition of hybrid coal-gas mixtures because coal evolves an effective inhibitor of methane combustion upon heating. The hybrid mixtures consisting of a coal powder and a stoichiometric natural gas-oxygen mixture do not ignite in the reactor lined with coal dust.     

Influence of feedstock source on biocatalyst stability and behavior,and on reactor performance,in continuous intensified ethanol fermentation

An ethanol process based on a gas-lift tower fermenter arrangement was used as a model system to show the strong dependence of reactor behavior on the developing chemical environment within the reactor. The reactor performance limits for realistic substrates—starch and molasses—are characterized and compared with those attainable on an ideal substrate, glucose.

     

Controlling Polyolefin Properties by In‐Reactor Blending, 1–Polymerization Process,Precise Kinetics,and Molecular Properties of UHMW‐PE Polymers

A multipurpose reactor setup for catalytic slurry ethylene polymerization is presented. With the developed multi‐stage polymerization (MSP) method the production of polyolefin in‐reactor blends is accessible. Precisely controlled polymerizations are executed at isothermal, isobaric, and isoperibolic steady state conditions in a dynamic power compensated reactor. The described system realizes fast (<10 s) and constant temperature control (±0.1 K), applying electrical heat compensation in combination with mass flow technique. Single‐ and MSP with a highly active ZN‐catalyst are applied to produce uni‐ and bimodal polyethylenes with controlled fractions of molecular weight (UHMW and medium‐MW PE). Polymerization kinetics and molecular weights (IV, GPC) are presented.

     

A microfluidic reactor for rapid,low‐pressure proteolysis with on‐chip electrospray ionization

A microfluidic reactor that enables rapid digestion of proteins prior to on‐line analysis by electrospray ionization mass spectrometry (ESI‐MS) is introduced. The device incorporates a wide (1.5 cm), shallow (10 µm) reactor ‘well’ that is functionalized with pepsin‐agarose, a design that facilitates low‐pressure operation and high clogging resistance. Electrospray ionization is carried out directly from a short metal capillary integrated into the chip outlet. Fabrication, involving laser ablation of polymethyl methacrylate (PMMA), is exceedingly straightforward and inexpensive. High sequence coverage spectra of myoglobin (Mb), ubiquitin (Ub) and bovine serum albumin (BSA) digests were obtained after <4 s of residence time in the reactor. Stress testing showed little loss of performance over ～2 h continuous use at high flow rates (30 µL/min). The device provides a convenient platform for a range of applications in proteomics and structural biology, i.e. to enable high‐throughput workflows or to limit back‐exchange in spatially resolved hydrogen/deuterium exchange (HDX) experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of an open tube in series with a packed capillary column on liquid chromatographic performance: The influence of particle diameter,temperature, and system pressure

A postcolumn reactor or a simple open tube connecting a capillary column to, for example, a mass spectrometer affects the performance of a capillary liquid chromatography system in two ways: stealing pressure from the column and adding band-spreading. This effect is especially intolerable in fast separations. Our calculations show that in the presence of a 25 μm radius postcolumn reactor, column (50 μm radius) efficiency (number of theoretical plates) is severely reduced by more than 75% with a t₀ of 10 s and a particle diameter from 1 to 5 μm for unretained solutes at room temperature. Therefore, it is necessary to minimize the reactor's effect and to improve the column efficiency by optimizing postcolumn conditions. We derived an equation that defines the observed number of theoretical plates (N_obs) taking into account the two effects stated above, which is a function of the maximum pressure P_m, the particle diameter d_p, the reactor radius a_r, the column radius a_c, the desired dead time t₀, the column temperature T and zone capacity factor k″. Poppe plots were obtained by calculations using this equation. The results show that for a t₀ shorter than 18 s, a P_m of 4000 psi, and a d_p of 1.7 μm, a 5 μm radius reactor has to be used. Such a small reactor is difficult to fabricate. Fortunately, high temperature helps to minimize the reactor effect so that reactors with manageable radius (larger than 12.5 μm) can be used in many practical conditions. Furthermore, solute retention diminishes the influence of a postcolumn reactor. Thus, a 12.5 μm reactor supersedes a 5 μm reactor for retained solutes even at a t₀ of 5 s (k″ > 3.8, or k′ > 2.0).     

Enantioseparation of (R,S)-ketoprofen using Candida antarctica lipase B in an enzymatic membrane reactor

An enzymatic membrane reactor (EMR) for enantioseparation of (R,S)-ketoprofen via Candida antarctica lipase B (CALB) as biocatalyst was investigated. A comparative study of free and immobilized CALB was further conducted. The catalytic behaviour of CALB in an EMR was affected by the process parameters of enzyme load, substrate concentration, substrate molar ratio, lipase solution pH, reaction temperature, and substrate flow rate. Immobilization of CALB in the EMR was able to reduce the amount of enzyme required for the enantioseparation of (R,S)-ketoprofen. Immobilized CALB in the EMR assured higher reaction capacity, better thermal stability, and reusability. It was also found to be more cost effective and practical than free CALB in a batch reactor.