Application of backflush and micro-flow techniques to the analysis of C5—C13 hydrocarbons in crude oils and its geochemical significance

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C₅—C₁₃ hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C₅—C₁₃ compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograms (MID and full scan) could be obtained at the same time. The retension time differences of nC₆—nC₁₃ alkanes between GC and TIC were in the range of 0.02—0.58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C₆—C₁₃ hydrocarbon group composition could be used in oil-oil correlation studies.     

Application of backflush and micro-flow techniques to the analysis of C_5—C_(13) hydrocarbons in crude oils and its geochemical significance

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C5—C13 hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C5—C13 compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograms (MID and full scan) could be obtained at the same time. The retension time differences of nC6—nC13 alkanes between GC and TIC were in the range of 0.02—0.58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C6—C13 hydrocarbon group composition could be used in oil-oil correlation studies.     

Application of C5—C13 light hydrocarbons in depositional environment diagnosis

Based on the geological background and Gammacerane/C31H（S ＋ R） ratios, source rock depositional environments of the studied oil samples （194） from 13 oilfields were classified into three groups according to salinity： saline-lacustrine facies, fresh to brackish lacustrine facies （including limnetic facies）, and semi-saline to saline facies （including marine facies of the Tarim Basin）. C5-C13 compound groups in the crude oils were separated by GC, and about 286 compounds were qualitatively analyzed. The geochemical application of the C6- C13 compound groups and their ratios between each group with individual carbon number was investigated. Our studies show that （1） C6-C13 compound groups and their ratios in the crude oils could serve as new reliable parameters for oil-oil correlation because the C6- C13 light fractions are the major oil component, especially in light oil or condensate, in which they account for almost 90% of the whole oil; （2） the compound groups of C7 light hydrocarbons in oils derived from different depositional environments with different salinity have different characteristics; （3） C6-C13 compound groups and ratios may be affected by other factors such as maturity, but they are mainly controlled by salinity of depositional waters.     

High molecular weight (C35 +) n-alkanes of Neogene heavily biodegraded oil in the Qianmiqiao region, North China

With wax content of 1.62%, heavy oil has been produced from the sandstone reservoirs of Neogene Guantao Formation (Ng1^Ⅲ). In the GC and GC-MS RIC profiles of its aliphatic fraction, n-alkanes are totally lost, which shows the result of heavy biodegradedation. However, the remaining trace C₁₃－C₃₆ n-alkanes can be still seen from its m/z 85 mass chromatogram. In addition, a complete series of C₃₅－C₇₃ high molecular weight (HMW) n-alkanes was detected by high-temperature gas chromatography (HTGC). The HMW n-alkane series shows a normal distribution pattern, a major peak at nC₄₃, obvious odd-carbon-number predominance, CP_I37—55 and OEP_45—49 values up to 1.17 and 1.16—1.20 respectively. The present study not only has conformed the strong resistibility of HMW n-alkanes to biodegradation in crude oils as concluded by previous researchers, but also has provided some significant information on source input and maturity for the heavily biodegraded oil in the Qianmiqiao region.     

Pool-formation and secondary change of biodegraded viscous oils: Case study of reservoir section in the Zhengjia-Wangzhuang Oilfield, Jiyang Depression

It is demonstrated by various geochemical indexes that the Zhengjia-Wangzhuang Oilfield with viscous crude oil in the Jiyang Depression has been sourced from the contribution of matured source rocks in the upper Es4. The principal cause leading to the densification of crude oils would be biodegradation, with the degradation level of crude oils being ranked as 2-8; vertically, the biodegradation level increases from the top to bottom of the oil column, with a distinctive biodegradation gradient occurring. Calculated parameters of sterane, terpane and methyl-phenanthrene have indicated that the source-rock's maturity of crude oils and asphaltic sands ranges from 0.7 to 0.9, and based on the calculation of Easy Ro model, the temperature of hydrocarbon generation in the source rock would be within 120-140℃, which coincides with the measurements of reservoir inclusions. The measured homogenization temperature would represent the generation temperature of the source rock, and be fairly different from that of reservoir while being charged with hydrocarbons, which reflects the hydrocarbon-charging to be a fast process, and the period of pool-formation to be consistent with that of peaked generation. According to the evaluation of generation history, the pool-formation could have been occurring in 7-15 Ma. And the biodegradation of crude oils in the study area would be considered to take place in 4-15 Ma based on the examination of biodegradation order and dynamic calculations.     

Microstructure and wear resistance of PTA clad Cr7C3/γ-Fe ceramal composite coating

A wear resistant Cr₇C₃/γ-Fe ceramal composite coating was fabricated on substrate of the hardening and tempering C degree steel by PTA (plasma transferred arc) cladding with (wt%) Fe-25Cr-7C elemental powder blends. Microstructure of the coating was characterized by OM, SEM, XRD and EDS. Wear resistance of the coating was tested under dry sliding wear condition at room temperature. The results indicate that the PTA clad ceramal composite coating has a rapidly solidified fine microstructure consisting of Cr₇C₃ primary particles uniformly distributed in the γ-Fe matrix and is metallurgically bonded to the C degree steel substrate. The PTA clad Cr₇C₃/γ-Fe ceramal composite coating has high hardness and excellent wear resistance under dry sliding wear test conditions. The excellent wear resistance of the Cr₇C₃/γ-Fe ceramal composite coating is attributed to the coating’s high hardness, strong covalent atomic bonding and refined microstructure.     

Microstructure and wear resistance of PTA clad Cr7C3/γ-Fe ceramal composite coating

A wear resistant Cr₇C₃/γ-Fe ceramal composite coating was fabricated on substrate of the hardening and tempering C degree steel by PTA (plasma transferred arc) cladding with (wt%) Fe-25Cr-7C elemental powder blends. Microstructure of the coating was characterized by OM, SEM, XRD and EDS. Wear resistance of the coating was tested under dry sliding wear condition at room temperature. The results indicate that the PTA clad ceramal composite coating has a rapidly solidified fine microstructure consisting of Cr₇C₃ primary particles uniformly distributed in the γ-Fe matrix and is metallurgically bonded to the C degree steel substrate. The PTA clad Cr₇C₃/γ-Fe ceramal composite coating has high hardness and excellent wear resistance under dry sliding wear test conditions. The excellent wear resistance of the Cr₇C₃/γ-Fe ceramal composite coating is attributed to the coating’s high hardness, strong covalent atomic bonding and refined microstructure.     

Peat molecular fossils recording paleoclimatic change and organism replacement

The occurrence of the dominant C₂₃ n-alkane derived from bryophyte was demonstrated to be related to the cold climate, based on the GC and GC/MS analyses on a 40-cm long peat core, in which this compound exponentially varies in abundance with the depth corresponding to the well-known second Little Ice Age. Both the variation of the chemical components of modern bryophyte resulted from climatic change and the ecological data about the biological growth influenced by climate shed light on the point that the variation of this compound in the peat was related to the cold climate. This was also evidenced by the previously-reported lacustrine data. In addition, the variations of the ratios of ketones/esters and C₂₄ n-alkene/n-alkane (C_24︰1/C_24︰0) display the trend identical with that of organisms, implicating the replacement between bryophyte and monocotyledon occurring in the peat core.     

Fabrication of MgB2 superconducting films by different methods

MgB₂ superconducting films have been successfully fabricated on single crystal MgO(111) and c-AL₂O₃ substrates by different methods. The film deposited by pulsed laser deposition is c-axis oriented with zero resistance transition temperature of 38.4 K, while the other two films fabricated by chemical vapor deposition and electrophoresis are c-axis textured with the zero resistance transition temperature of 38 K and 39 K, respectively. Magnetization hysteresis measurements yield critical current density J_c of 10⁷ A/cm² at 15 K in zero field for the thin film and of 10⁵ A/cm² for the thick film. For the thin film deposited by chemical vapor deposition, the microwave surface resistance at 10 K is found to be as low as 100 μΩ, which is comparable with that of a high-quality high-temperature superconducting thin film of YBCO.     

采用气相色谱“反吹、微流控”技术分析原油C5—C13轻馏分及其地球化学意义初探

采用装有程序升温（PTV）进样器、“反吹”、“微流控”装置和FID检测器的Agilent5975MSD，用HP PONA色谱柱，对油样进行反吹切割分离，利用“微流控”调节色谱柱出口连接的两根毛细柱的分流比，可同时获得色谱、色质全扫描和多离子检测3种分析结果. 对比平湖4井油样色谱和色质分析的总离子色谱图，nC₆至nC₁₃各正构烷烃的保留时间相差仅0.02—0.58min，使同一样品的化合物诸峰几乎一一对应，为吸收、应用和发展石油化工界对汽油组成的研究成果，提供了新的有力的色质定性工具. 用115个标样，汽油中烃类的色谱分析文献和色质分析Nist 0.5谱库检索等方法，对C₅—C₁₃轻馏分约286个谱峰进行了族组成定性，尚发现有不少混合峰存在. 对CNPC KLPG的原油样品库中8个烃源岩沉积水体盐度分别为盐湖、半咸咸、淡微咸的典型油样的研究结果，显示原油C₆—C₁₃馏分的族组成分布，有可能用于油油对比的研究.     

Fabrication of MgB2 superconducting films by different methods

MgB₂ superconducting films have been successfully fabricated on single crystal MgO(111) and c-AL₂O₃ substrates by different methods. The film deposited by pulsed laser deposition is c-axis oriented with zero resistance transition temperature of 38.4 K, while the other two films fabricated by chemical vapor deposition and electrophoresis are c-axis textured with the zero resistance transition temperature of 38 K and 39 K, respectively. Magnetization hysteresis measurements yield critical current density J_c of 10⁷ A/cm² at 15 K in zero field for the thin film and of 10⁵ A/cm² for the thick film. For the thin film deposited by chemical vapor deposition, the microwave surface resistance at 10 K is found to be as low as 100 μΩ, which is comparable with that of a high-quality high-temperature superconducting thin film of YBCO.     

碲镉汞吸收缘以上E1和E2峰的指认

The fundamental reflectivity spectrum of HgCdTe have been investigated.The feature of the spectra is the presence of E₁ and E₂ peaks in the fundamental absorption region.The lower energy peak can be split into a doublet (E₁ and E₁＋Δ₁）.A three-dimensional saddle point is used to fit the E₁ and E₁+Δ₁ critical point and some simulated calculation is done for E₂ at X point.The calculated results are compared with the measured results and prominent features of the dielectric spectra are identified with critical-point transitions at the Λ and X points in the Brillouin zone.     

An acidic polysaccharide with xylose branches fromPorphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8×10⁵ was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO₃-galactose (6-OSO₃-Gal) and xylose (Xyl) in an approximate molar ratio of 25︰15︰10︰1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and ¹H and ¹³C NMR, the most probable repeating unit of PY3 could be proposed as [(1→3)β-D-Gal(1→4)α-L-3,6-AnGal]₃-[(1→3)β-D-Gal(1→4)α-L- 6-OSO₃-Gal]₂ with a xylose moiety at the C₆ of one of every twenty-five β-D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Measurements and analysis of force and moment of caudal fin model in C-start

The unsteady hydrodynamic forces and moments acting on caudal-fin models of fish with different shapes and different swing durations were experimentally measured to simulate the fish C-starts. The motion of models was characterized by rotating the model to a maximum deflection angle in an excursion time T_u and back to the initial position in a return time T_d around its root-axis. Studies show that the caudal-fin plays an important role in fish C-starts and the caudal-fins with different shapes and different swing durations generate different forces and moments. In addition, the hydrodynamic forces and moments acting on the models with different shapes can be normalized by the 2nd and 3rd moments of area, respectively. The forces and moments acting on the models with different swing durations, but the same ratio of T_u to Td can also be scaled.     

Research progress in studies on the coalbed gas geochemistry

The current situation of geochemical studies on coalbed gas is reviewed in this paper. Generally, coalbed gas is compositionally dominated by methane with δ¹³C₁ values ranging approximately from -80‰ to -10‰. However, few isotopic studies have been carried out on other components of coalbed gas except for hydrogen and carbon dioxide, whose δD_CH4 values available for utilization vary from -333‰ to -117‰, and δ¹³C_CO2 values from -29.4‰ to +18.6‰. Two major types of coalbed gas, thermogenic gas and secondary biogenic gas, have been identified, and there are also some other classification criteria. Compared with conventional natural gases, coalbed gas has a wide distribution range of δ¹³C₁ and δ¹³C_CO2 values, especially possessing some extremely heavy values. Current problems that remain unsolved in the coalbed gas geochemistry include the variation mechanism, controlling factors and application of carbon and hydrogen isotopes of methane, the relation between the values of δ¹³C₁ and Ro, the systematic classification scheme and criterion of genetic types, and the application of the coalbed gas geochemistry in evaluating target districts of the coalbed gas exploration.     

Density functional theory study of the reaction paths of reactions of CH3C(O)O2 radicals with HO2 in the gas phase

A DFT study on the reactions between CH₃C(O)O₂ and HO₂ radicals has been carried out. It is suggested that both the triplet and singlet potential surfaces involve a complex mechanism with the formation of loosely bound intermediate complexes of reactants and products. The reaction prefers to occur on the triplet surface to produce peracetic acid (CH₃C(O)O₂H) and triplet O₂ molecule. The CH₃C(O)O₂H can further convert into CH₃C(O)O and HO radicals.     

Density functional theory study of the reaction paths of reactions of CH3C(O)O2 radicals with HO2 in the gas phase

A DFT study on the reactions between CH₃C(O)O₂ and HO₂ radicals has been carried out. It is suggested that both the triplet and singlet potential surfaces involve a complex mechanism with the formation of loosely bound intermediate complexes of reactants and products. The reaction prefers to occur on the triplet surface to produce peracetic acid (CH₃C(O)O₂H) and triplet O₂ molecule. The CH₃C(O)O₂H can further convert into CH₃C(O)O and HO radicals.     

Phase-selection and metastable phase formation in highly undercooled eutectic Ni78.6Si21.4 alloys

A large undercooling (250 K) was achieved in eutectic Ni_78.6Si_21.4 melt by the combination of molten-glass denucleation and cyclic superheating. The metastable phase formation process in the bulk undercooled eutectic Ni_78.6Si_21.4 melts was investigated. With the increase of undercooling, different metastable phases form in eutectic Ni_78.6Si_21.4 melts and part of these metastable phases can be kept at room temperature through slow post-solidification. Under large undercooling, the metastable phases β₂-Ni₃Si, Ni₃₁Si₁₂ and Ni₃Si₂ were identified. Especially, the Ni₃Si₂ phase was obtained in eutectic Ni_78.6Si_21.4 alloy for the first time. Based on the principle of free energy minimum and transient nucleation theory, the solidification behavior of melts was analyzed with regard to the metastable phase formation when the melts were in highly undercooled state.