生烃化学动力学在川东北普光气田的应用

普光气田是四川盆地近期发现的规模最大、埋藏最深、资源丰度最高的气田。通过认识普光气田各个烃源岩层的贡献量、生烃关键期与构造演化的关系、油气成藏具体模式等，建立生烃化学动力学模型、标定参数，结合地区烃源岩参数和地史、热史资料，定量描述该地区的生烃过程及油裂解成气过程。认为：普光地区的主力烃源岩为下志留统泥岩；主要干酪根生油期为早二叠世末到早三叠世末期（距今286Ma至240Ma）；主要干酪根生气期为中三叠世（距今240Ma至230Ma）；主要气源是原油后期热裂解气，原油裂解成气的时间比较晚，主要油裂解成气期为早白垩世（距今144Ma至97．5Ma），从而决定了普光气田的成藏模式为“多期成藏，油气转化，晚期定位”。图2表3参33     

Surface tension as a limiting factor for aerobic n-alkane biodegradation

A new mathematical model for n-alkane biodegradation in crude oil, heavy oil and paraffinic mixtures is described. The pattern of n-alkane degradation as a function of the inverse of hydrocarbon chain length reported in this paper can be considered as general behaviour for many aerobic n-alkane biodegradation processes. A new interpretation of n-alkane biodegradation as a function of surface tension, is given. A mathematical expression was obtained starting from the degradation values of n-alkane and relative surface tension, which is a parameter independent of fermentation conditions. An interesting parameter, b, was identified which represented the accelerating conversion factor for n-alkane biodegradation. The findings suggested that the n-alkane biodegradation. The findings suggested that he n-alkane biodegradation rate may be affected by the fermentation condition (agitation, aeration, etc.) and by the strain of microorganism, while the behaviour pattern of n-alkane degradation was essentially linked to the substrate characteristics (molecular structure, molecular weight and density).     

海洋丝状真菌转化石油烃的研究

研究从湄洲湾海域分离的4株丝状真菌MF1，MF2，MF3，MF4的生长特性及去除油污的过程，观察在温度26℃，初始油浓度在3g/l,培养12d的过程中培养液的变化，分析培养液的pH值及原油的去除率与时间的关系，结果表明，丝状真菌去除原油的[过程是生物吸附与生物降解相结合的生物转化过程，比较革兰氏阴性细菌与丝状真菌细胞壁组成，结构，得出海洋微生物的脱油作用与其细胞壁有直接的关系。     

Zirconium-based intermetallics as heterogeneous catalysts for the fischer-tropsch reaction: I. Zr-Ni-Co catalysts

Alloys of the general formula Zr₅₀Ni_xCO_50-x, where 0 ≦x≧ 50, have been prepared and used in the temperature range 300–400°C, in the pressure range 1–9 barg in a microtubular reactor for the reaction of hydrogen with carbon monoxide to give hydrocarbons. The alloys or intermetallic materials were prepared by argon arc melting, powdered by hydrogen decrepitation and characterised by means of optical microscopy (metallography), scanning electron microscopy with surface analysis and magnetic susceptibility measurements. The selectivity towards higher hydrocarbons increased with (i) increase in the total pressure and (ii) decrease in hydrogen content of the feed gases. The kinetics were found to be of the form: where m = 1.0 ± 0.2 and n = 0. The apparent energy of activation (E_a) lay in the range of 80–130 kJ mole^?1 and there appeared to be a compensation effect between E_a and the pre-exponential factor A. The turnover numbers for the reaction exhibited an activity maximum for alloys of composition around Zr₅₀Ni₄₀Co₂₀ and Zr₅₀Ni₃₀Co₂₀. Magnetic susceptibility measurements indicated that alloys changed their nature from moderately paramagnetic to strongly paramagnetic or even ferromagnetic after use and this is attributed to the conversion of zirconium to zirconium oxide during reaction with the attendant production of free 3d-transition metals. Derived catalysts prepared by air treatment of the hydrogen-decrepitated intermetallics behaved almost identically to the latter materials and gave similar magnetic susceptibility values to used hydrided materials.     

Viscosities of nonelectrolyte liquid mixtures. I. binary mixtures containing p-dioxane

Viscosity measurements are reported for p-dioxans with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, tetrachloroethane, chloroform, pentachloroethane, and ethyl acetate at 303.15 K. Excess Gibbs energies of activation G ^*E of viscous flow have been calculated with Eyring's theory of absolute reaction rates. The deviations of the viscosities from a linear dependence on the mole fraction and values of G ^*E for binary mixtures have been explained in terms of molecular interactions between unlike pairs. The Prigogine-Flory-Patterson theory has been used to estimate the excess viscosity, ln , and corresponding enthalpy ln _H, entropy ln _S, and free volume ln _v terms for binary mixtures of p-dioxane with cyclohexane, n-hexane, benzene, toluene, carbon tetrachloride, and chloroform. Estimates of excess viscosities from this theory for p-dioxane with benzene, toluene, and carbon tetrachloride are good, while for the other three mixtures they are poor. The local-composition thermodynamic model of Wei and Rowley estimates the excess viscosity quite well even for p-dioxane mixtures with cyclohexane and n-hexane.     

Polycyclic Aromatic Hydrocarbons Activate the Aryl Hydrocarbon Receptor and the Constitutive Androstane Receptor to Regulate Xenobiotic Metabolism in Human Liver Cells

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants produced by incomplete combustion of organic matter. They induce their own metabolism by upregulating xenobiotic-metabolizing enzymes such as cytochrome P450 monooxygenase 1A1 (CYP1A1) by activating the aryl hydrocarbon receptor (AHR). However, previous studies showed that individual PAHs may also interact with the constitutive androstane receptor (CAR). Here, we studied ten PAHs, different in carcinogenicity classification, for their potential to activate AHR- and CAR-dependent luciferase reporter genes in human liver cells. The majority of investigated PAHs activated AHR, while non-carcinogenic PAHs tended to activate CAR. We further characterized gene expression, protein abundancies and activities of the AHR targets CYP1A1 and 1A2, and the CAR target CYP2B6 in human HepaRG hepatoma cells. Enzyme induction patterns strongly resembled the profiles obtained at the receptor level, with AHR-activating PAHs inducing CYP1A1/1A2 and CAR-activating PAHs inducing CYP2B6. In summary, this study provides evidence that beside well-known activation of AHR, some PAHs also activate CAR, followed by subsequent expression of respective target genes. Furthermore, we found that an increased PAH ring number is associated with AHR activation as well as the induction of DNA double-strand breaks, whereas smaller PAHs activated CAR but showed no DNA-damaging potential.     

Supramolecular Nanofibers from Collagen-Mimetic Peptides Bearing Various Aromatic Groups at N-Termini via Hierarchical Self-Assembly

Self-assembly of artificial peptides has been widely studied for constructing nanostructured materials, with numerous potential applications in the nanobiotechnology field. Herein, we report the synthesis and hierarchical self-assembly of collagen-mimetic peptides (CMPs) bearing various aromatic groups at the N-termini, including 2-naphthyl, 1-naphtyl, anthracenyl, and pyrenyl groups, into nanofibers. The CMPs (R-(GPO)_n: n > 4) formed a triple helix structure in water at 4 °C, as confirmed via CD analyses, and their conformations were more stable with increasing hydrophobicity of the terminal aromatic group and peptide chain length. The resulting pre-organized triple helical CMPs showed diverse self-assembly into highly ordered nanofibers, reflecting their slight differences in hydrophobic/hydrophilic balance and configuration of aromatic templates. TEM analysis demonstrated that 2Np-CMP_n (n = 6 and 7) and Py-CMP₆ provided well-developed natural collagen-like nanofibers and An-CMP_n (n = 5–7) self-assembled into rod-like micelle fibers. On the other hand, 2Np-CMP₅ and 1Np-CMP₆ were unable to form nanofibers under the same conditions. Furthermore, the Py-CMP₆ nanofiber was found to encapsulate a guest hydrophobic molecule, Nile red, and exhibited unique emission behavior based on the specific nanostructure. In addition to the ability of CMPs to bind small molecules, their controlled self-assembly enables their versatile utilization in drug delivery and wavelength-conversion nanomaterials.     

Ni/W比对NiWCx催化剂加氢性能的影响

过渡金属碳化物具有类似贵金属的电子结构和加氢性能。采用等体积浸渍法制备了不同Ni/W比的NiW/γ-Al₂O₃催化剂,以程序升温碳化法转化为NiW碳化物后对芳烃模型化合物和低温煤焦油中分离所得芳烃组分进行加氢处理。催化剂的N₂吸附、XRD、H₂-TPR和SEM表征表明,Ni的添加促进了载体表面WO₃物种的分散和还原,抑制了WO₃晶体的团聚和大晶粒的生成。萘的加氢实验表明,Ni/W原子比为0.6时催化剂的活性最佳,而添加苯酚和吡啶后的模型油加氢过程中萘的转化率和十氢萘的产率均明显下降,Ni/W原子比为0.47和0.6的催化剂性能相近,煤焦油中芳烃组分加氢后Ni/W原子比为0.47的催化剂性能更优。结果表明,Ni和W均具有良好的加氢活性,但Ni耐杂原子性能较差,二者存在一个最佳的配比以使加氢性能更优。有杂原子化合物存在时,如煤基芳烃组分的加氢,Ni/W原子比为0.47的NiW碳化物催化剂具有更好的加氢性能。     

Determination of heavy metals and volatile aromatic compounds in used engine oils and sludges

Assessment of contaminant releases during utilization of used oils is essential for the determination of environmental acceptability. These paper reports the results of the study examining a toxic metal leachability from used engine oil and sludge samples employing leaching test (TCLP). The leaching test indicated that lead in oil samples exceeded 5-ppm concentration level what qualified them as a toxic waste. The samples of contaminated sludge were found to contain high concentration of total lead, barium and chromium, but the leaching test showed concentration below regulatory limit. The total content of benzene, ethylbenzene, toluene, and xylenes (BETX), and naphthalene in used oil and sludge samples was also determined and was found not to be a significant factor to contamination.     

N-甲酰吗啉芳烃抽提塔试验研究

用小型碳钢筛板萃取塔进行了宽馏分重整脱庚烷油的N 甲酰吗啉抽提试验 ,考察了抽提温度、溶剂比、溶剂含水率对总芳烃收率及选择性的影响。结果表明 ,在抽提温度为 60℃、溶剂含水为 3 % (m )和溶剂比S/F =4(V)的抽提操作条件下 ,溶剂选择性较高 ,并可获得高的芳烃回收率