Variable temperature13C MAS NMR of KFe2Mn(CO)12 in the solid state and as aCatalyst precursor on a carbon support

Variable temperature¹³C MAS NMR spectra are reported for¹³CO-enriched KFe₂Mn(CO)₁₂ as a solid and also as dispersed clusters on a carbon support. The spectrum of KFe₂Mn(CO)₁₂ at 300 K agrees with the proposed structure for this cluster and shows that the cluster is static. Two bridging carbonyl resonances are clearly resolved and, by comparison with¹³C MAS NMR spectra of Mn₂(CO)₁₀ and Fe₂(CO)₉, all terminal resonances for the cluster can be assigned. When the cluster is supported on carbon, two broad resonances are observed at room temperature which are assignable to KFe₂Mn(CO)₁₂ and a decomposition product, Mn₂(CO)₁₀. The carbonyl ligands in both supported clusters are completely averaged, and KFe₂Mn(CO)₁₂ on the carbon surface demonstrates fluxional behavior similar to that observed for the cluster in solution. For this fluxional process, activation energies of 0.6 kcal/mol and 0.5 kcal/mol are estimated for carbon-supported KFe₂Mn(CO)₁₂ and Mn₂(CO)₁₀, respectively.     

球形和圆柱形变换催化剂宏观活性评价新方法

运用“ 催化反应单元” 概念提出了球形私圆柱形变换催化剂的宏观活性评价新方法, 即催化剂分层整齐排列各粒、各层间填充细小惰性颗粒的排列方式和消除了内外扩散影响的反应器结构以这种方法所做的活性评价试验结果置信度高, 其二级反应速率常数k_T有解析解, 可以此作为变换催化剂宏观活性评价标准与催化剂的填充层数无关.     

CO hydrogenation over potassium-promoted Fe/carbon catalysts

The effects of potassium on the catalytic behavior in CO hydrogenation over K-promoted Fe/carbon catalysts having low K/Fe ratios were investigated. Even though the doses of potassium were low the promotional effects were pronounced, especially on the olefin-to-paraffin ratio, and theC ₃ toC ₄ olefin selectivities of the K-promoted catalysts were as high as 51 to 66 mol%. Over the catalysts having no or low potassium content the olefin-to-paraffin ratio and the ratio of the CO₂ formation rate to the rate of CO conversion to hydrocarbons remained roughly the same regardless of temperature, while over the K-promoted catalysts having higher potassium content they increased with temperature. Formation of significant amounts of filamentous carbon was observed in the K-promoted catalysts; however, the carbon deposition did not appear to affect the inherent activity and selectivity of the K-promoted catalysts.     

超临界CO_2萃取技术在中草药开发中的应用进展

分析了我国中药发展的形势及其应用新技术的必要性 ,论述了超临界CO2 萃取技术在我国中草药开发中应用的现状及优越性 ,提出了如何应用超临界CO2 萃取技术进行中药开发的对策与展望。     

REACTOR-MEMBRANE PERMEATOR CASCADE FOR ENHANCED PRODUCTION AND RECOVERY OF H2 AND CO2 FROM THE CATALYTIC METHANE-STEAM REFORMING REACTION

The catalytic reforming of methane by steam is an important industrial process that produces H₂, CO and CO₂, thus chemically transforming natural gas, coal gas and light hydrocarbon feedstocks to synthesis gas or hydrogen fuel. Methane-steam reforming may consist of a number of reactions depending on the reforming catalyst, operating conditions and feedstock composition, The typical industrially desirable reactions are the reverse of methanation (CH₄ + H₂O = CO + 3H₂) and the water-gas shift (CO + H₂O = CO₂ + H₂). Both reactions are equilibrium limited and the composition of the mixture that exits the reformer is in accordance with the one calculated thermodynarmically. Removal of reaction products at the reactor exit by means of selective membrane permeation can offer improved CH₄ conversions and CO₂ and H₂ yields, assuming the subsequent utilization of the reject streams by a second methane-steam reformer. We numerically investigated the feasibility of a system of two tubular methane-steam reformers, in series with an intermediate permselective polyimide membrane permeator, as means of improving the overall CH₄ conversion and the H₂, CO₂ yields over conventional methane-steam reforming equilibrium reaction-separation schemes that are currently in industrial practice. The unique feature of the permselective polyimide separator is the simultaneous removal of H₂ and CO₂ versus CH₄ and CO from the reformed streams. The utilized 6FDA-3,3', 5,5'-TMB aromatic polyimide was reportedly characterized [10] and found to exhibit superior permselective properties compared with other polyimides of the same or different dianhydride sequence. Conversion and yield of the designed reactor-membrane permeator reforming system can be maximized by optimizing the permselective properties of the membrane material and the design variables of the reactors and the permeator. Product recovery and purity in the permeate stream need to be compromised to overall enhance methane conversion and product yield. The operating variables that were varied to investigate their effect on the magnitude of conversion and yield included the inlet pressure of the first reformer, the temperature of both reformers, and the permeator dimensionless Pe' number (variation of the first two variables results to a drastic change in the composition of the reformed stream that enters into the permeator). The numerical results show that the new reformer-membrane permeator cascade process can be more effective (it can offer increased CH₄ conversions and H₂, CO₂ yields) than conventional equilibrium methane-steam reforming reaction-separation processes currently in practice.     

掺铜TiO^2光催化剂光催化氧化还原性能的研究

利用浸渍法制备了掺铜二氧化钛光催化剂，分别以乙酸降解和二氧化碳还原反应为探针，研究了催化剂的光催化氧化光催化还原性能．结果表明，铜掺杂能显著提高催化剂的光催化性能；结合光电子能谱、X光衍射分析等物理表征结果，对铜掺杂改性机制进行了讨论．     

The kinetics of CO2 hydrogenation on a Rh foil promoted by titania overlayers

Submonolayer deposits of titania on a Rh foil have been found to increase the rate of CO₂ hydrogenation. The primary product, methane, exhibits a maximum rate at a TiO _x coverage of 0.5 ML which is a factor of 15 higher than that over the clean Rh surface. The rate of ethane formation displays a maximum which is 70 times that over the unpromoted Rh foil; however, the selectivity for methane remains in excess of 99%. The apparent activation energy for methane formation and the dependence of the rate on H₂ and CO₂ partial pressure have been determined both for the bare Rh surface and the titania-promoted surface. These rate parameters show very small variations as titania is added to the Rh catalyst. The methanation of CO₂ is proposed to start with the dissociation of CO₂ into CO_(a) and O_(a), and then proceed through steps which are identical to those for the hydrogenation of CO. The increase in the rate of CO₂ hydrogenation in the presence of titania is attributed to an interaction between the adsorbed CO, released by CO₂ dissociation, and Ti³⁺ ions located at the edge of TiO _x islands covering the surface. Differences in the effects of titania promotion on the methanation of CO₂ and CO are discussed in terms of the mechanisms that have been proposed for these two reactions.     

Selective CO oxidation in the presence of hydrogen over supported Pt catalysts promoted with transition metals

Selective CO oxidation in the presence of excess hydrogen was studied over supported Pt catalysts promoted with various transition metal compounds such as Cr, Mn, Fe, Co, Ni, Cu, Zn, and Zr. CO chemisorption, XRD, TPR, and TPO were conducted to characterize active catalysts. Among them, Pt-Ni/γ-Al₂O₃ showed high CO conversions over wide reaction temperatures. For supported Pt-Ni catalysts, Alumina was superior to TiO₂ and ZrO₂ as a support. The catalytic activity at low temperatures increased with increasing the molar ratio of Ni/Pt. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Ni and Pt was determined to be 5. This Pt-Ni/γ A1₂O₃ showed no decrease in CO conversion and CO₂ selectivity for the selective CO oxidation in the presence of 2 vol% H₂O and 20 vol% CO₂. The bimetallic phase of Pt-Ni seems to give rise to stable activity with high CO₂ selectivity in selective oxidation of CO in H₂-rich stream.     

高气速选择性分离氨碳混和气模拟实验

采用二级串联鼓泡吸收器对NH3／CO2摩尔比为2：1的混和气体进行高气速选择性吸收，获得氨的总吸收率为96．7％，二氧化碳的总吸收率为33．1％，二级吸收器出口气相CO2摩尔含量达90．9％，液相氨碳摩尔比为5．85。将此吸收液在加压下精馏分离氨，基本可以把吸收液中游离氨回收。分离游离氨后的溶液在常压下进行解吸，蒸馏塔出口液体含NH3和CO2量仅为0．014％和0．006％，解吸气回串联吸收器进行循环吸收分离。对预计工业分离过程进行物料和能量衡算，分离1kg液氨需1MPa的蒸汽约3.2kg。     

新型CO耐硫变换催化剂QDB-04的开发及应用

介绍了新型CO耐硫变换催化剂QDB-04的性能特点及工业应用情况，对Shell粉煤气化煤气第一变换炉反应深度的问题及控制第一变换炉“床层飞温”的办法进行了讨论，提出了ODB-04催化剂应用于低水气比Shell粉煤气化制氨变换工艺的设计方案。