Biomimetical catalytic activity of iron(III) porphyrins encapsulated in the zeolite X

The approach adopted for the obtention of zeolite-encapsulated FeP led to clean syntheses of biomimetical catalyst. The catalysts were obtained through the zeolite synthesis method, where NaX zeolite was synthesised around one of the cationic FePs: iron(III) 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (FeP1) or iron(III) 5-mono(2,6-dichloro-phenyl)10,15,20-tris(4-N-methylpyridyl)porphyrin (FeP2). The syntheses yielded pure FeP1NaX and FeP2NaX catalysts without any by-products blocking the zeolite nanopores. FeP1NaX and FeP2NaX efficiently catalysed the epoxidation of (Z)-cyclooctene by iodosylbenzene (PhIO) in DCE, giving rise to cis-epoxycyclooctane yields of 85% and 95%, respectively. Hydroxylation of adamantane shows a preferable alkane oxidation at the tertiary C---H bond, indicating a hydrogen abstraction through the Fe^IV(O)P^·+species in the initial step. The total adamantanol yields were 52% and 45% for FeP1NaX and FeP2NaX, respectively. Concerning selectivity, FeP1NaX and FeP2NaX gave an 1-adamantanol (Ad-1-ol)/2-adamantanol (Ad-2-ol) ratio of 20:1 and 11:1, respectively (after statistical correction). Therefore, these results indicate a free radical activation of the C---H bonds of adamantane as expected for P-450 models. In the cyclohexane oxidation catalysed by FeP1NaX in DCE, a cyclohexanol (C₆-ol) yield of 50% and an alcohol/ketone ratio of 10 was obtained. The hydroxylation occurs according to the so-called oxygen rebound mechanism, as expected for a P-450 model system. FeP2NaX is less selective (C₆-ol yield=25% and alcohol/ketone=1.2). One possible explanation is that a Russell-type mechanism involving O₂ imprisoned within the zeolite cages may be operating parallelly, generating both C₆-ol and cyclohexanone.     

Modeling alcohol + water + hydrocarbon mixtures with the group contribution with association equation of state GCA-EoS

The growing interest on first- and second-generation biofuels requires the development of thermodynamic tools with predictive capacity for mixtures containing a wide variety of organo-oxygenated compounds, water and hydrocarbons. Modeling this type of mixtures is challenging due to the presence of association and solvation effects. In this work, we present a revision of the group contribution with association equation of state (GCA-EoS) parameters, with the purpose of extending and improving the predictive capacity of the model for systems containing water, alcohols and hydrocarbons.     

修武盆地构造热演化史对下寒武统页岩含气性的影响

构造热演化史可以确定泥页岩在不同地质时期的成熟度状态及构造演化特征,对页岩含气性研究和资源评价都具有重要意义。综合运用包裹体测温法、构造热演化法以及盆地模拟软件Petromod对修武盆地的热演化史和埋藏史进行研究和重建。修武盆地JY1井的剥蚀厚度计算结果为4 142.75 m;自晚古生代以来热流值经历了低—高—低的变化过程;王音铺-观音堂组页岩在早志留世(434 Ma)进入生烃门限,早志留世-中志留世(434~422 Ma)为生油阶段,晚志留世-早二叠世(422~265 Ma)为生湿气阶段,早二叠世-晚侏罗世(265~145 Ma)为生干气阶段;王音铺组-观音堂组页岩早期大量生烃、长期深埋、生气时间早和抬升时间早,使得JY1井王音铺组-观音堂组页岩含气量(0.28~0.93 m3/t)并不理想。     

Experimental and simulated propene isotherms on porous solids

The lack of treatment capacity of hydrocarbons by three-way catalysts during the “cold start” period creates an important environmental problem. During this period, the temperature of the three-way catalyst is too low for effective operation and cannot convert the hydrocarbons in the exhaust. 50-80% of the total hydrocarbon emissions are produced in this phase that accomplishes the first 60-120 s of the engine operation. In this study, the technology chosen to treat these emissions is the use of HC-traps, and molecular simulations are tested as a tool to reproduce the experimental adsorption behaviour of porous solids. Therefore, experimental and simulated adsorption isotherms of propene (model hydrocarbon) have been obtained for four different crystalline materials with distinctive framework structures (3D and 1D) and a variety of Si/Al ratios and cations (three zeolites: ZSM-5, BETA and Mordenite; and a silicoaluminophosphate molecular sieve: SAPO-5).     

有机岩石学及其在油气勘探中的应用

有机岩石学主要研究沉积有机质的成因、产状、结构和演化历史。有机岩石学在油气勘探，特别是在烃源岩评价中的作用。已从仅是研究的工具发展为常规的手段。其最大特点在于从显微层次来认识和分析非均质性的沉积有机质特征、成因和演化与烃类形成的关系。文章综合评述了有机岩石学在研究有机质赋存形式、有机成熟度、有机质类型、生烃组分和成烃作用、烃类排出、运移和聚集等方面的现状和发展方向。     

用烃组成分析方法对加氢润滑油的两种氧化方式进行比较研究

通过利用烃组成分析的方法对氧化前后以及热、光两种氧化的研究 ,发现在加氢润滑油老化实验研究中 ,光氧化的强度远远大于热氧化     

东濮凹陷东南部下第三系地震地层学研究

依据地震反射终止关系和地震反射波特征，将东濮凹陷东南部下第三系划分成两个地震层序和九个亚层序。在近万公里的地震剖面上，依据可信度较高的地震反射内部结构和外部形态，识别出前积反射等地震相类型，在综合考虑盆地结构和古地理背景的基础上，利用地质、测井等资料确定了地震相和沉积相之间的对应关系，得出了沉积体系的平面分布和垂向演化规律。结合现今勘探现状，指明了今后有利的油气勘探方向。     

Transition metal-catalyzed borylation of alkanes and arenes via C---H activation

Since 1999, direct borylation of hydrocarbons catalyzed by a transition metal complex has been extensively studied by several groups and has become an economical, efficient, elegant, and environmentally benign protocol for the synthesis of a variety of organoboron compounds. Re-, Rh-, Ir- and Pd-catalyzed C---H borylation of alkanes, arenes and benzylic positions of alkylarenes by bis(pinacolato)diboron or pinacolborane provide alkyl-, aryl-, heteroaryl- and benzylboron compounds, respectively. In this review, seminal early works and exciting recent developments in the area of direct borylation of hydrocarbons via C---H activation are summarized.     

Cu、K助剂对FeMn/SiO2催化费托合成的影响

研究了Cu、K助剂对共沉淀型FeMn/SiO2催化剂还原行为、吸附行为及费托(F-T)合成活性和选择性的影响. Cu助剂以与Fe、Mn、SiO2共沉淀的方式引入, 而K助剂是在喷雾干燥前均匀加入沉淀浆料引入的. 结果表明, Cu可明显提高催化剂的还原性能, K助剂能促进催化剂在CO中的还原但抑制在H2中的还原, 而同时加入Cu和K会进一步促进催化剂在H2或CO中的还原; Cu助剂能促进H2吸附而K助剂对H2吸附无明显影响; Cu在一定程度上提高了F-T合成活性, 缩短了反应诱导期, K明显促进了CO的转化而相对抑制了H2的转化, 并且延长了反应的诱导期, Cu与K协同作用不仅提高反应的转化率而且缩短了反应的诱导期; K使得烃产物平均分子量增加, Cu单独对烃产物分布影响不明显, 而与K共同作用会进一步增加烃产物的分子量.     

Studies of the adsorption of oligomers and surfactants on carbon and steel surfaces in a hydrocarbon medium

The adsorption isotherms for an (amino) terminally functionalised, oligomeric polyisobutylene and for a series of alkylpropoxylate or alkylbutoxylate surfactant molecules on carbon particles, in isooctane, have been obtained. The isotherms on carbon show that the oligomer is the most strongly adsorbing species. The surfactants show some evidence of forming aggregates on the carbon surface at higher concentrations. Analysis of the adsorption isotherms indicate that the size of these aggregates is similar on the carbon particles and on steel balls, reported previously, but that in some cases the actual adsorbed amounts on the two surfaces differ considerably. Ellipsometric studies carried out in situ on steel surfaces in isooctane show that only the polymer gives a relatively thick adsorbed layer. Addition of surfactant reduces the adsorption of the oligomer. There are some differences between the thickness values reported previously using AFM, compared to those found in the current work using ellipsometry, but in both cases it would seem that some degree of multilayer adsorption is occurring for the oligomer on steel in isooctane.