Lewis acidity as an explanation for oxide promotion of metals: implications of its importance and limits for catalytic reactions

Sub-monolayer quantities of metal oxides are found to influence CO hydrogenation, CO₂ hydrogenation, acetone hydrogenation, ethylene hydroformylation, ethylene hydrogenation, and ethane hydrogenolysis over Rh foils. The metal oxides investigated include AlOx, TiOx, VOx, FeOx, ZrOx, NbOx, TaOx, and WOx. Only those reactions involving the hydrogenation of C-O bonds are enhanced by the oxide overlayers. The coverage at which maximum rate enhancement occurs is approximately 0.5 ML for each oxide promoter. Titanium, niobium, and tantalum oxides are the most effective promoters. XPS measurements after reaction show that of the oxides studied titanium, niobium, and tantalum oxide overlayers are stable in the highest oxidation states. The trend in promotion effectiveness is attributed to the direct relationship between oxidation state and Lewis acidity. For the oxide promoters, bonding at the metal oxide/metal interface between the O-end of adsorbed CO and the Lewis acidic oxide is postulated to facilitate C-O bond dissociation and subsequent hydrogenation.     

Study of different effect on foaming process of biodegradable bionolle in supercritical carbon dioxide

Microcellular foaming of biodegradable Bionolle in supercritical CO₂ has been produced. The effects of a series of variable factors, such as saturation temperature, saturation pressure, and depressurization time and step on the foam structures and density, were studied through measurement of density and SEM observation. The experimental results show that higher saturation temperatures lead to an increase in bulk densities; and different depressurization time and step result in different product cell morphology. In addition, at some saturation temperature, the orientation of the cells can be found in the product morphology. XRD experimental results show that the foaming treatment with SC CO₂ increased the crystallinity of Bionolle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2901–2906, 2006     

Possible Energy Network with polygeneration system and CCS for China

On basis of adopting polygeneration systems for power and alternative fuels,capturing CO2 with near zero energy penalties,and storing CO2 on sites,a new kind of Energy Network can integrate energy utilization,CO2 capture,transportation and storage synthetically.Techno-economic analysis of this solution focusing on Inner Mongolia and the Yangtze River Delta districts had been carried with comparison to the chain method for energy utilization and CO2 sequestration.This solution can save 21.5% of energy,and re...     

CO2 gasification of wood charcoals derived from vacuum and atmospheric pyrolysis

The gasification of biomass derived char obtained via vacuum and atmospheric pyrolysis of Populus tremuloides has been studied in the ranges of 725–960°C and 0.1 to 6 MPa. CO₂ was used as the oxidizing gas. The results show that char reactivity is influenced by the preheating rates and that pressure effects are significant between 850°C and 950°C. A correlation based on the expression: df/dt = k₀{exp(-E/RT)}(1 - f)^af^βP^yCO₂ was used to fit the experimental data. In general, vacuum pyrolysis derived char showed a higher reactivity than atmospheric pyrolysis chars. An explanation based on a higher oxygen content of the vacuum pyrolysis char is suggested.     

Silver catalysts supported over activated carbons for the selective oxidation of CO in excess hydrogen: effects of different treatments on the supports

Commercial activated carbon (AC) was used as a support either in its original form or after various modifications, giving diverse textural and surface chemical characteristics. The changes of these properties were monitored by N₂ adsorption–desorption isotherms, temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Ag catalysts were prepared over the AC supports by a conventional wet impregnation method. The catalytic performances of supported Ag/AC catalysts in the selective oxidation of CO in excess H₂ were tested. The results indicate the textural and surface chemical characteristics are responsible for the different catalytic performances.     

Ion-dipole interactions between adsorbed CO and support cations in Pt/K-LTL

The adsorption of carbon monoxide on a non-acidic Pt/K-LTL catalyst has been studied by diffuse reflectance and transmission IR spectroscopy. The CO spectrum is strongly dependent on the experimental conditions. Adsorption on the small Pt clusters in the presence of water gives linear-CO bands between 2060 and 1990 cm^–1 and a bridging-CO band around 1800 cm^–1. In the absence of water, the linear bands are red shifted to about 1940 and 1720 cm^–1, respectively. The frequency shift is attributed to an ion-dipole interaction between adsorbed CO and support cations. The ion-dipole interaction is screened by the adsorbed water leading to a smaller red shift in the CO stretching frequency.     

The mechanism of CO oxidation over Cu(110): Effect of CO gas energy

The effect of the temperature of gas phase CO upon the kinetics of the oxygen titration reaction: CO_g +O_a CO_2,g, has been studied. It is found that the reaction's rate is independant of CO gas temperature between 300 and 623 K. The activation energy (6.5 kcal/mole), dependence upon CO pressure (first-order), and independence upon oxygen coverage for 0.1 _o 0.4 are all independant of the CO gas phase temperature. This result rules out any Eley-Rideal type mechanism whereby CO reacts directly from the gas phase with an oxygen adatom without first being accommodated to the surface temperature in an absorbed state. The result is instead interpretable in terms of a Langmuir-Hinshelwood mechanism.Camille and Henry Dreyfus Foundation Teacher-Scholar Fellowship.     

5Cr套管钢在不同CO2分压下高温高压腐蚀特性研究

为了研究5Cr套管钢在不同CO₂分压下的腐蚀特性,进行了5Cr套管钢高温高压腐蚀失重和高温高压电化学试验,并采用XRD、SEM和EDS等手段对其腐蚀产物进行微观分析。结果表明,在高温高压腐蚀环境下随着CO₂分压从低到高,其表面点蚀坑的深度和直径均无明显变化,而点蚀速率则出现逐渐减小的趋势;其腐蚀产物膜由Cr(OH)₃、FeCO₃和CaCO₃共同组成,且随着CO₂分压的升高Cr的富集量逐渐增加;在电化学测试中,随着CO₂分压的不断升高,5Cr套管钢表现出半钝化特征,产物膜逐渐增厚且致密,且极化电阻逐渐增大,阳极反应受到抑制,电化学反应阻力增大,其抗局部腐蚀能力不断提高。     

高温-超压-高CO2背景下致密砂岩储层成岩作用特征——以莺歌海盆地LD10区新近系梅山组-黄流组为例

利用薄片鉴定、扫描电镜、阴极发光及碳氧同位素分析等手段,对莺歌海盆地LD10区新近系梅山组-黄流组高温-超压-高CO₂背景下的储层成岩作用特征及其对孔隙的影响进行了系统研究。研究结果表明: ①莺歌海盆地LD10区新近系梅山组-黄流组储层发育重力流沉积,岩性以中-细粒长石岩屑石英砂岩为主,储层物性以特低-低孔、特低渗特征为主。②压实、胶结和溶蚀作用是研究区主要的成岩作用类型。超压对黏土矿物的转化及石英次生加大具有明显抑制作用,并在一定程度上保护了原生孔隙。富含CO₂的高温流体不仅造成了黏土矿物的异常转化,同时促进了溶蚀作用发生,增加了次生孔隙。③研究区黄二段储层的成岩演化序列为: 菱铁矿胶结→石英次生加大→绿泥石胶结→长石淋滤溶蚀→高岭石形成→早期方解石胶结→早期白云石胶结→长石溶蚀→方解石溶蚀→伊利石大量生成→晚期铁方解石、铁白云石形成。④总体上,压实作用使孔隙度减少了45.30%～62.93%,胶结作用使孔隙度减少了1.65%～35.01%,溶蚀作用使孔隙度增加了0.72%～8.00%。其中,黄流组中下部砂岩储层受到了超压保护和CO₂溶蚀作用的双重影响,物性较好,钻井过程中应考虑高CO₂风险。