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

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Progress in Natural Science:Materials International 2007年第11期17卷 1382-1387页

作者： Wang Peirong1,2. Zhao Hong2.3, Xu Guanjun1,4, Zhu Cuishan2.3, Xiao Tingrong4, Zhang Min2.3 and Zhang Bin1,4(1. Key Laboratory of Petroleum geochemistry, china National Petroleum Corporation, Beijing 100083, china 2. geochemistry department of yangtze university, jingzhou 43.02., china 3. Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, yangtze university, jingzhou 43.02., china 4. Petroleum Geology Central Laboratory, Research Institute of Petroleum Exploration and Development, Petrochina, Beijing 100083, china) Key Laboratory of Petroleum geochemistry China National Petroleum Corporation Beijing 100083 China geochemistry department of {2. university Jingzhou 434023 China Key Laboratory of Exploration Technologies for Oil and Gas Resources Ministry of Education Yangtze University Jingzhou 434023 China Petroleum Geology Central Laboratory Research Institute of Petroleum Exploration and Development PetroChina Beijing 100083 China

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 2.6 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.

关键词： GC analysis GC/MS analysis backflush micro-flow controller light fraction in crude oil

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Geochemical characterization of aromatic hydrocarbons in crude oils from the Tarim,Qaidam and Turpan Basins,NW china

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Petroleum Science 2010年第4期7卷 448-457页

作者： Zhang Min Paul Philp department of geochemistry Yangtze University Jingzhou Hubei 434023 China The Key Laboratory of Oil ＆ Gas Resources and Exploration Technology Ministry of Education Yangtze University Jingzhou Hubei 434023 China School of Geology and Geophysics University of Oklahoma Norman OK 73019 USA

Based on the systematic study of aromatic hydrocarbons in over 100 crude oil samples collected from the Tabei and Tazhong uplifts in the Tarim Basin,the western depression area in the Qaidam Basin and the Tabei depression in the Turpan Basin,the geochemical characteristics of the marine（Tarim Basin）,saline lacustrine（Qaidam Basin）,and swamp（Turpan Basin） oils were *** marine oils from the Tarim basin are characterized by relatively low abundance of diaromatic hydrocarbons such as biphenyl and naphthalene,and relatively high abundance of triaromatic hydrocarbons including phenanthrene,dibenzothiophene and *** contrast,the swamp oils from the Turpan Basin are dominated by the highest relative abundance of diaromatic hydrocarbons and the lowest relative abundance of triaromatic hydrocarbons in all the oil samples in this *** relative abundance of diaromatic and triaromatic hydrocarbons in the saline lacustrine oils from Qaidam Basin is between that in Tarim oils and Turpan *** parameters based on the isomer distributions of dimethylnaphthalenes（DMN）,trimethylnaphthalenes（TMN）,tetramethylnaphthalenes（TeMN） and methylphenanthrenes（MP）,i.e.,1,2.5-trimethylnaphthalene（TMN）/1,3,6-TMN ratio,1,2.7-TMN/1,3,7TMN ratio,（2.6-＋2.7-）-dimethylnaphthalenes（DMN）/1,6-DMN ratio,1,3,7-TMN/（1,2.5-＋1,3,7-）TMN,1,3,6,7-TeMN/（1,3,6,7-＋1,2.5,6-＋1,2.3,5-）-TeMN ratio and MP index,may reflect the diversity of organic source input,thermal maturity and depositional *** addition,the dibenzothiophenes（DBTs）/fluorenes（Fs） and dibenzofurans（DBFs）/Fs ratios were found to the very useful and effective in determining genetic types of crude oils for the marine,saline lacustrine,and swamp depositional environments,and for oil-oil correlations.

关键词： china Tarim Basin Qaidam Basin Turpan Basin marine oil saline lacustrine oil coal-derived oil depositional environment aromatic hydrocarbons

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Environmental records of lacustrine sediments in different time scales:Sediment grain size as an example

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Science china Earth Sciences 2004年第10期47卷 954-960页

作者： CHEN Jing’an1, WAN Guojiang1, David Dian Zhang2. ZHANG Feng1 & HUANG Ronggui1 1. State Key Laboratory of Environmental geochemistry, Institute of geochemistry, Chinese Academy of Sciences, Guiyang 550002.{2. 2. department of Geography and Geology, university of Hong Kong, Pokfulam Road, Hong Kong,{2. 1. State Key Laboratory of Environmental geochemistry Institute of Geochemistry Chinese Academy of Sciences 550002 Guiyang China 2. department of Geography and Geology University of Hong Kong Pokfulam Road Hong Kong China

Sediment grain size is a conventional proxy of climatic changes. Larger sediment grain size is often interpreted to indicate dry climate during lower lake level while smaller sedi- ment grain size implies wet climate during higher lake level. Through detailed study on sediment grain sizes in Lake Erhai and Lake Chenghai, this paper reveals the different indication signifi- cances of sediment grain sizes in different time scales, different resolution investigations. For long time-scale and low resolution (102. or 103a) studies, larger sediment grain size indicates lower lake level, smaller lake area and drier climate while smaller sediment grain size indicates higher lake level, larger lake area and wetter climate. For short time-scale and high resolution (a or 10a) studies, larger sediment grain size reflects more rainfall and wetter climate while smaller sediment grain size reflects less rainfall and drier climate. Environmental information revealed by lacustrine sediment records is often different in different time scales because of the variance of sedimentation resolution, sampling resolution and dating precision. Therefore, paleoclimate im- plications of environmental proxies in long time-scale and low resolution investigations could not be mechanically applied to short time-scale and high resolution studies. Only after synthetically analyzing the influence manner and extent of all factors on the sediment records in different time scales, can credible conclusions be obtained.

关键词： lacustrine sediment, environmental record, grain size, time scale.

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Composition of substituents on pyrrole ring of high-carbon-number geoporphyrins and its dealkylation

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Chinese Science Bulletin 1999年第3期44卷 267-269页

作者： ZHANG Chunming and LIN Renzi geochemistry Research Center, Jianghan Petroleum Institute, jingzhou 434102.{2. department of Geoscience, university of Petroleum , Beijing 100083,{2. geochemistry Research Center Jianghan Petroleum Institute Jingzhou China department of Geoscience University of Petroleum Beijing China

Geoporphyrins, isolated from source rock, were analyzed on electron ionization mass spectrometry （EIMS） and Tandem mass spectrometry （MS/MS）. The spectrum of ElMS shows that the geoporphyrins are mainly composed of two types: DPEP and eito. Most of the porphyrin carbon numbers are greater than C32./sub>. The daughter spectra of the molecular ions (C34-36DPEPs) display the loss of methyl and ethyl groups, which indicate there are ethyl and propyl groups in the mother ions. The average condensed structural formulae, derived from the data of the spectra on MS/MS, have clearly shown the composition of the substituents on the porphyrin pyrrole ring, and the regular changes of the substituents reveal the characteristics of the dealkylation of the porphyrins in the geosphere.

关键词： Tandem mass spectrometry geoporphyrins condensed structural formula dealkylation.

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Dehydration melting of solid amphibolite at 2.0 GPa: Effects of time and temperature

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Science china Earth Sciences 2005年第8期48卷 1120-1133页

作者： ZHOU Wenge1, XIE Hongsen1, LIU Yonggang1, ZHENG Xiaogang1, ZHAO Zhidan2.& ZHOU Hui3 1. Laboratory of Material in the Earth’s Interior, Institute of geochemistry, Chinese Academy of Sciences, Guiyang 550002. china 2. {2. of Geology, china university of Geosciences, Beijing 100083, china 3. {2. of Geology, Peking university, Beijing 100871, china 1. Laboratory of Material in the Earth’s Interior Institute of Geochemistry Chinese Academy of Sciences 550002 Guiyang China 2. department of Geology China University of Geosciences 100083 Beijing China 3. department of Geology Peking University 100871 Beijing China

Two sets of dehydration-melting with a natural solid amphibolite, collected from North Himalayan structure zone, Tibet, have been carried out in multi-anvil apparatus at 2.0 GPa and 800―1000℃, for 12.2.0 h. One is keeping the pressure at 2.0 GPa and the annealing time of 12.h, changing the temperature (800―1000℃). The other is keeping the pressure at 2.0 GPa and temperature at 850℃, varying the annealing time (12.2.0 h). The products are inspected with microscope and electron probe. The results indicate that at 2.0 GPa, annealing time of 12.h, garnets, melts and clinopyroxenes occur in amphibolite gradually with increasing temperature and the chemical compositions of melt vary from tonalite to granodiorite, and then to tonalite. However, at 2.0 GPa and 850℃, with the annealing time increasing, the garnets, melts and cli-nopyroxenes also occur in amphibolite gradually and the chemical compositions of melt vary from tonalite to granodiorite. In both cases, melts interconnect with each other when the contents of melt are over the 5 vol.%. the viscosities of the melt produced in amphibolite at temperature higher than 850℃ are on a level with 104 Pa·s. The interconnected melt with such a viscosity may segregate from the source rock and form the magma over reasonable geological time. Therefore, it is believed that at the lower part of the overthickened crust, the tonlitic and grano-dioritic magma may be generated through the dehydration melting of amphibolite.

关键词： solid amphibolite, high pressure, high temperature, time, partial melting.

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

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Chinese Science Bulletin 2004年第S1期49卷 39-49页

作者： WANG Zhenqi, PENG Ping’an, YU Chiling, LU Hong, ZOU Yanrong, ZHANG Linye & LIU Junmin State Key Laboratory of Organic geochemistry, Guangzhou Institute of geochemistry, Chinese Academy of Sciences, Guangzhou 510640,{2. department of Earth Science, yangtze university, jingzhou 43.02.,{2. Research Institute of Geology, Shengli Oilfield Co. Ltd., SINOPEC, Dongying 2.7015,{2. Chinese Acad Sci State Key Lab Organ Geochem Guangzhou Inst Geochem Guangzhou 510640 Peoples R China yangtze Univ Dept Earth Sci Jinzhou 434023 Peoples R China Shengli Oilfeld Co Ltd Res Inst Geol SINOPEC Dongying 527015 Peoples R China

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 12.-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

关键词： viscous oil biodegradation time of pool-formation time of degradation Jiyang Depression.

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Variation of the Fe/Mn ratio of ferromanganese crusts from the Central North Pacific: implication for paleoclimate changes

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Progress in Natural Science:Materials International 2005年第6期15卷 530-537页

作者： LU Zunli1**, LING Hongfei1*, ZHOU Feng1, JIANG Shaoyong1, CHEN Xiaoming1 and ZHOU Huaiyang2.1. State Key Laboratory for Mineral Deposits Research, department of Earth Sciences, Nanjing university, Nanjing 2.0093,{2. 2. Guangzhou Institute of geochemistry, Chinese Academy of Sciences, Guangzhou 510640,{2.)department of Earth & Environmental Science, university of Rochester State Key Laboratory for Mineral Deposits Research Department of Earth Sciences Nanjing University Nanjing 210093 China department of Earth & Environmental Science University of Rochester Guangzhou Institute of geochemistry Chinese Academy of Sciences Guangzhou 510640 China

Contents of Fe, Mn and other elements in four ferromanganese crusts recovered from the central North Pacific are analyzed at high depth-resolution by electron microprobe for reconstructing factors controlling their deposition. Manganese (IV) in hydrogenetic ferromanganese crusts is mainly supplied as colloidal precipitates from the Oxygen Minimum Zone (OMZ), which concentrates high amounts of dissolved Mn (II). The iron is derived from carbonate dissolution and silicate particles of eolian dust. An increase in paleoproductivity during cooler climate would potentially lead to a decrease in Mn deposition due to enlargement of the OMZ which has a “temporary storage” effect for Mn. On the other hand, not affected by the OMZ, the iron entering the Fe-Mn crust would likely increase with the eolian dust input and surface productivity at glacial stages. As a result, the increasing Fe/Mn ratio should indicate a cooling climate. This is supported by the following observations. In the profile of the past 1 Ma, the variations of Fe/Mn ratio coincide with benthic oxygen isotope fluctuation in glacial-interglacial cycles. Three episodes with high Fe/Mn ratios, approximately at 2.6, 1.8 and 0.8 Ma, are detected within the past 3 Ma and coincide with major climate transitions and cooling events. The secular evolution pattern of Fe/Mn ratio in the Cenozoic is similar to the Pb isotope evolution which is mainly controlled by eolian dust and related to climate. The Fe/Mn evolution pattern is also broadly consistent with the global deep-sea oxygen isotope records. Therefore, Fe/Mn ratio recorded in the ferromanganese crusts may be a new proxy for climate change.

关键词： Fe/Mn ratio ferromanganese crust central North Pacific paleoclimate.

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Experimental study on the interaction between peat,lignite and germanium-bearing solution at low temperature

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Science china Earth Sciences 2005年第9期48卷 1411-1417页

作者： QI Huawen1,2. HU Ruizhong1 & QI Liang1 1. Key Laboratory of Ore Deposit geochemistry, Chinese Academy of Sciences, Guiyang 550002. china 2. {2. of Earth Science, Nanjing university, Nanjing 2.0093, china 1. Key Laboratory of Ore Deposit geochemistry Chinese Academy of Sciences 550002 Guiyang China 2. department of Earth Science Nanjing University 210093 Nanjing Chin

The interaction between peat, lignite and germanium(Ge)-bearing solution with an initial Ge concentration of 5 mg/L was studied at 2.―100℃ and at pH 2.96―12.08. The results show that the apparent transfer ratios of peat and lignite for Ge in the solution were positively correlated with temperature in acid environment (initial pH=2.96), and the ratios (up to 86.5%) of lignite were obviously higher than those (up to 58.5%) of peat, but the organic transfer ratios of lignite were lower than those of peat. The activation energy values for interaction between peat, lignite and Ge-bearing solution are 30.96 and 15.67 kJmol?1, respectively. The strong acid (initial pH=2.96) and the strong alkaline (initial pH=12.08) environment contribute to the transfer of Ge in the solution. At 4

关键词： low temperature, peat, lignite, Ge4+, complexation.

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Application of C5-C13 light hydrocarbons in depositional environment diagnosis

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Progress in Natural Science:Materials International 2008年第9期18卷 1129-1137页

作者： Peirong Wanga,b,, Guanjun Xu a,c, Tingrong Xiaoc, Dajiang Zhanga,c, Bin Zhanga,c a Key Laboratory of Petroleum geochemistry, china National Petroleum Corporation, Beijing 100083, china b department of Organic geochemistry, yangtze university, jingzhou 43.02., china c Central Laboratory of Petroleum Geology, Research Institute of Petroleum Exploration and Development, Petrochina, Beijing 100083, china Key Laboratory of Petroleum geochemistry China National Petroleum Corporation Beijing 100083 China department of Organic geochemistry Yangtze University Jingzhou 434023 China Central Laboratory of Petroleum Geology Research Institute of Petroleum Exploration and Development PetroChina Beijing 100083 China

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 2.6 compounds were qualitatively *** geochemical application of the C6-C13 compound groups and their ratios between each group with individual carbon number was *** 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 difierent depositional environments with difierent salinity have difierent characteristics;(3) C6-C13 compound groups and ratios may be afiected by other factors such as maturity, but they are mainly controlled by salinity of depositional waters.

关键词： Light hydrocarbons Crude oil Depositional environment Salinity

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Comprehensive evaluation of mechanism of "chimney effect" using principles of magnetism, geochemistry and mineralogy

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Chinese Science Bulletin 1998年第9期43卷 743-748页

作者： LIU Qingsheng 1, CHENG Tongjin 2.and LIU Shugen 3 1. department of Applied Geophysics, china {2. of Geosciences, Wuhan 430074, china 2. Center of Petroleum geochemistry, china National Star Petroleum Corporation, Hefei 2.002., china 3. The St department of Applied Geophysics China University of Geosciences Wuhan China Center of Petroleum geochemistry China National Star Petroleum Corporation Hefei China The State Key Laboratory of Oil/Gas Reservoir Geology and Exploitation of china Chengdu Institute of Technology Chengdu China

Study of forming mechanism of "chimney-effect" (CE) has important significance for basic theory and applications of non-seismic geophysical and geochemical methods locating oil/gas reservoirs. The theoretical basis of comprehensive evaluation of mechanism of CE using principles of magnetism, geochemistry and mineralogy has been reviewed, with the problems to be solved: (ⅰ) study for the relationship between process of oil/gas migration and geochemical field; (ⅱ) analysis of genesis of magnetic, geochemical and mineralogical anomaly; (ⅲ) interpretation of surface soil magnetism and geochemical anomaly combined with seismic data.

关键词： chimney effect (CE) hydrocarbon microseepage oil/gas accumulation.

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