喀斯特流域风化成土作用及其矿质元素行为与环境质量

岩石风化成土作用是生态系统矿质元素的重要来源，也是全球矿质元素生物地球化学循环的重要环节。因此，岩石风化成土过程中矿质元素的行为与环境质量研究有助于我们深入了解矿质元素的生物地球化学循环及其生态环境效应，同时对农业生产和环境保护也具有重要意义。选择乌江流域沉积岩-土壤-植被-河流系统作为研究对象，采集了多个小流域盆地岩石、土壤、植物及溪水样品。通过测试样品的矿物、元素组成以及元素存在形态等，分析了喀斯特流域的矿物学与地球化学特征，研究了喀斯特流域的成土物源、风化成土方式及风化成土作用的控制因素，探讨了风化成土过程中矿质元素的行为与环境质量，为进一步进行喀斯特地区土壤-植被系统矿质元素的生物地球化学循环研究奠定基础，为喀斯特地区生态环境保护和修复以及稀土等矿质元素的农业利用提供科学依据，同时为核废料的地质处置提供参考。通过研究，取得了如下一些成果和认识： (1) 提出了弱淀积元素的概念，改进了侵蚀前后风化剖面中元素的演化模型。 (2) 硅酸盐岩地区土壤来源于下伏基岩的风化成土作用，其风化成土过程中存在脱硅富铝作用。 (3) 连续碳酸盐岩地区土壤最终来源于碳酸盐岩的风化成土作用，其风化成土作用存在四种方式和两个阶段。脱钙(镁)富铝硅和脱硅富铝两个阶段的研究结果，支持了王世杰等(1999)提出的碳酸盐岩两阶段风化成土模式。 (4) 岩性和地形是研究区风化成土作用的主要控制因素，植被和其它因素只是对其风化成土产物的理化性质进行了一些改造。 (5) 由于侵蚀、脱钙和元素本身的淀积作用，相对于研究区黄壤、中国土壤(CS)和世界土壤(WS)，研究区石灰土富集Mn、V、P、REE 和U 等矿质元素。风化成土过程中矿质元素的行为主要受岩性和地貌部位控制，还受元素性质、土壤pH 值、氧化还原条件、铁锰(氢)氧化物和有机质含量、粘土矿物组成以及植被条件等的影响。 (6) 石灰岩等岩石风化成土作用可以通过植物营养供给和元素相互作用影响土壤质量和植物生长。 (7) 石灰岩等岩石风化成土作用控制着溪水和乌江河流的pH 值以及Mg、Ca、P、Mn 和U 等矿质元素的分布特征。 (8) NH4Ac-HAc单一提取法可用于评价石灰土中Mg、Ca、K、Mn和P等多数矿质元素的植物可利用性。与何子平等(2001)的研究结果不同，石灰土中多数矿质营养元素对植物的供给能力高于其它土壤。

Partial oxidation of ethane to syngas in an oxygen-permeable membrane reactor

A perovskite-type oxide of Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) with mixed electronic and oxygen ionic conductivity at high temperatures was used as an oxygen-permeable membrane. A tubular membrane of BSCFO made by extrusion method has been used in the membrane reactor to exclusively transport oxygen for the partial oxidation of ethane (POE) to syngas with catalyst of LiLaNiO/gamma-Al2O3 at temperatures of 800-900 degreesC. After only 30 min POE reaction in the membrane reactor, the oxygen permeation flux reached at 8.2 ml cm(-2) min(-1). After that, the oxygen permeation flux increased slowly and it took 12 h to reach at 11.0 ml cm(-2) min(-1). SEM and EDS analysis showed that Sr and Ba segregations occurred on the used membrane surface exposed to air while Co slightly enriched on the membrane surface exposed to ethane. The oxygen permeation flux increased with increasing of concentration of C2H6, which was attributed to increasing of the driving force resulting from the more reducing conditions produced with an increase of concentration of C2H6 in the feed gas. The tubular membrane reactor was successfully operated for POE reaction at 875 degreesC for more than 100 h without failure, with ethane conversion of similar to 100%, CO selectivity of >91% and oxygen permeation fluxes of 10-11 ml cm(-2) min(-1). (C) 2002 Elsevier Science B.V. All rights reserved.

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Application of CO2-TPD in the synthesis of composite oxides from metal-organic precursors

CO2-TPD was demonstrated an effective way to investigate the phase formation during pyrolysis for the preparation of composite oxides using metal-organic molecules as precursors. Based on the CO2-TPD results, it was found that calcination condition had deep effect on the carbonate formation and the minimum firing temperature to acquire pure phase composite oxide. An optimized calcination schedule was then developed.

Syngas production using an oxygen-permeating membrane reactor with cofeed of methane and carbon dioxide

CH4-CO2-O-2 reforming to syngas in a never Ba0.5Sr0.5Co0.8Fe0.2O3.delta oxygen-permeable membrane reactor using LiLaNiO/gamma-Al2O3 as catalyst was successfully reported. Excellent reaction performance was achieved with around 92% methane conversion efficiency, 95% CO2 conversion rate, and nearly 8.5mL/min.cm(2) oxygen permeation flux. In contrast to the oxygen permeation model with the presence of large concentration of CO2 (under such condition the oxygen permeation flux deteriorates with time), the oxygen permeation flux is really stable under the CH4CO2-O-2 reforming condition.

Easy fabrication of dense ceramic membrane for oxygen separation

A combined EDTA-citrate complexing method was developed for the easy preparation of mixed oxygen-ionic and electronic conducting dense ceramic membrane for oxygen separation. The nea method takes the advantage of lower calcination temperature for phase formation. lower membrane sintering temperature and higher relative density over the standard ceramic method.

Synthesis and gas permeation properties of an NaA zeolite membrane

A high quality NaA zeolite membrane, which shows a H-2/n-C4H10 permselectivity of 106, has been synthesized on a seeded alpha-Al2O3 support by a multistage synthesis method.

Fast formation of NaA zeolite membrane in the microwave field

NaA zeolite membrane was successfully synthesized on the porous alpha-Al2O3 support by microwave heating. The synthesis of NaA zeolite membrane in the microwave field only needs 15 min and the synthesis time is 10 times shorter than that by conventional heating. SEM characterization indicates that the zeolite crystals in the NaA zeolite membrane synthesized by microwave heating are uniform in size; the membrane thickness is about 4 mu m and is thinner than that of the NaA zeolite membrane synthesized by conventional heating. Gas permeation studies indicate that the permeances of the NaA zeolite membrane synthesized by microwave heating are 3-4 times higher than those of the NaA zeolite membrane synthesized by conventional heating, while their permselectivities are comparable.

Low temperature synthesis of perovskite oxide using the adsorption properties of cellulose

La-0.8Sr(0).2CoO(3) (LSCO) oxide powder was prepared using the adsorption properties of cellulose. The preparation process was studied by XRD, FTIR, TG-DTA and CO2-TPD techniques. The results of XRD, IR and TG-DTA testified that cellulose could successfully reserve the homogeneity of the solution system to the solid precursor. During the early stage of pyrolysis, cellulose was partially oxidized, and some COO- groups appeared in its texture, which were then complexed with the adsorbed metal ions, and effectively suppressed the aggregation of metal ions. Formation of a pure perovskite and the properties of the powder resulted were found to be significantly influenced by the cellulose to metal nitrate ratio. Also the properties of the resulting powder were greatly influenced by the calcination conditions. If the produced carbon dioxide could not be eluted in time, carbonate would be formed in the bulk. Hence, a high calcination temperature (> 800 degreesC) was needed to acquire a pure phase LSCO. At optimized conditions, nano-crystal LSCO could be obtained at as low as 500 degreesC.

Partial oxidation of methane to syngas in tubular oxygen-permeable reactor

A dense Ba0.5Sr0.5Co0.8Fe0.2O3-delta membrane tube was prepared by the extruding method. Furthermore, a membrane reactor with this tubular membrane was successfully applied to partial oxidation of methane (POM) reaction, in which the separation of oxygen from air and the partial oxidation of methane are integrated in one process. At 875degreesC, 94% of methane conversion, 98% of CO selectivity, 95% of H-2 selectivity, and as high as 8.8 mL/(min (.) cm(2)) of oxygen flux were obtained. In POM reaction condition. the membrane tube shows a very good stability.

Synthesis of a high-permeance NaA zeolite membrane by microwave heating

Zeolite membranes with high permeance and separation factors are highly desirable for practical applications. Although, in the past, very good separation factors have been obtained, it has proved difficult to achieve a high permeance. Ken a comparative study of microwave versus conventional heating in the hydrothermal synthesis of NaA zeolite membranes is made. It is demonstrated that membranes prepared by microwave heating have not only a higher permeance but also a considerably shorter synthesis time. These observations are rationalized by examining the mechanism of membrane formation.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

An in-situ modified sol-gel process for monolith catalyst preparation used in the partial oxidation of methane

An in-situ modified sol-gel method for the preparation of a Ni-based monolith-supported catalyst is reported. With the presence of a proper amount of plasticizer and binder, and at an optimized pH value, the stable boehmite sol was modified with metal ions (Ni, Li, La) successfully without distinct growth of the particle size. Monolith-supported Ni-based/gamma-Al2O3 catalysts were obtained using the modified sol as the coating medium with several cycles of dip-coating and calcination. Combined BET, SEM-EDS, XRD and H-2-TPR investigations demonstrated that the derived monolith catalysts had a high specific surface area, a relatively homogeneous surface composition, and a high extent of interaction between the active component and the support. These catalysts showed relatively stable catalytic activities for partial oxidation of methane (POM) to syngas under atmospheric pressure. The monolith catalysts prepared by this sol-gel method also demonstrated an improved resistance to sintering and loss of the active component during the reaction process.

Continuous oxygen ion transfer medium as a catalyst for high selective oxidative dehydrogenation of ethane

An oxygen permeable mixed ion and electron conducting membrane (OPMIECM) was used as an oxygen transfer medium as well as a catalyst for the oxidative dehydrogenation of ethane to produce ethylene. O2- species transported through the membrane reacted with ethane to produce ethylene before it recombined to gaseous O-2, so that the deep oxidation of the products was greatly suppressed. As a result, 80% selectivity of ethylene at 84% ethane conversion was achieved, whereas 53.7% ethylene selectivity was obtained using a conventional fixed-bed reactor under the same reaction conditions with the same catalyst at 800 degreesC. A 100 h continuous operation of this process was carried out and the result indicates the feasibility for practical applications.

High selectivity of oxidative dehydrogenation of ethane to ethylene in an oxygen permeable membrane reactor

An oxygen permeable membrane based on Ba0.5Sr0.5Co0.8-Fe0.2O3-delta is used to supply lattice oxide continuously for oxidative dehydrogenation of ethane to ethylene with selectivity as high as 90% at 650degreesC.