原油中芳香硫化合物形态分布的研究

建立了原油中多环芳香硫化合物形态分布的研究方法。采用氯化钯/硅胶配位交换色谱分离原油中的芳香硫化合物,并用气相色谱/质谱分析、气相色谱-硫化学发光检测法结合色谱保留指数,鉴定出原油中的100多个多环芳香硫化物,包括含烷基取代基的苯并噻吩和二苯并噻吩类硫化物。定量分析表明,二苯并噻吩类化合物的含量占芳香硫化合物总量的91%左右。该方法可用于不同来源的原油中芳香硫化合物的形态分布研究。     

美国Sunniland等地原油和油源岩中噻吩类化合物的对比研究

本文用色谱-质谱分析了美国南佛罗里达盆地Sunnliland原油和油源岩抽提物中的噻吩类化合物,并将它们与源自页岩的原油进行了对比,发现源自碳酸岩与页岩的原油有着不同的噻吩类化合物分布。结合其他地球化学参数,如:正烷烃、甾烷和萜烷,噻吩类化合物将是很有用的油-油和油-源对比工具。     

2-取代苯并噻吩类化合物合成研究进展

2-取代苯并噻吩广泛的存在于天然产物中,独特的分子结构使其表现出了较高的药理和生物活性,常被用于药物化学和材料化学中。已有多种具有苯并噻吩骨架药物用于临床,故具有极高的研究价值。本文结合国内外学者对这方面的相关研究,重点对2-苯基苯并噻吩、2-酰基苯并噻吩和2-氨基苯并噻吩类化合物的合成方法进行了综述。     

全二维气相色谱分析直馏柴油中含硫化合物

采用全二维气相色谱-硫化学发光检测器,以直馏柴油为研究对象,考察了一维色谱柱初始温度、升温速率及两维柱温温差等条件对含硫化合物分离的影响,建立了直馏柴油中含硫化合物的分析方法。本方法对基质复杂的直馏柴油中含硫化合物的分离,并定性分析或归类了直馏柴油中的主要含硫化合物。以苯并噻吩为测试样,以峰面积对浓度作图,硫的浓度在1～100mg/kg范围内,峰面积与硫的浓度呈线性关系,相关系数大于0.999。与传统一维气相色谱相比,全二维气相色谱技术除可检测到苯并噻吩类、二苯并噻吩类等含硫化合物外,还可检测到直馏柴油中的硫醚类化合物;苯并噻吩类和二苯并噻吩类化合物也可得到较好分离。     

离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐的合成及在油品中的脱硫应用

合成并表征了一类新型离子液体1-烷基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐,将其与双氧水组合用于脱除模型油中的硫化物.结果表明,当模型油与萃取/催化剂1-辛基-3-羧甲基苯并咪唑双三氟甲磺酰亚胺盐([C_2O_2OBIM][Tf2N])的质量比为5∶1,H_2O_2/S摩尔比为5∶1,于75℃反应1 h后,模型油中二苯并噻吩(DBT)脱硫率为98.8%;脱硫过程符合一级动力学方程,5种硫化物的脱硫速率大小顺序为二苯并噻吩(DBT)4,6-二甲基二苯并噻吩(4,6-DMDBT)苯并噻吩(BT)2,5-二甲基噻吩(2,5-DMT)噻吩(T),其中脱除DBT和BT的反应表观活化能分别为44.16和52.10 k J/mol.该离子液体循环再生使用14次,脱硫率无明显下降.该深度脱硫方法具有操作简便及条件温和的特点.     

综合模拟风化条件下渤海原油中生物标志物及多环芳烃风化规律研究

该文以渤海原油SZ36-1为研究对象进行综合模拟风化实验,探讨了原油中生物标志物及5类多环芳烃(PAHs)组分的分布情况及风化规律。结果表明:经过30 d风化,渤海原油SZ36-1中大部分生物标志物表现出强的稳定性,部分PAHs的分布发生较大改变,其中萘系列化合物损失最严重,相对浓度的损失达80.34%;菲、二苯并噻吩、、芴系列则相对稳定;经t检验分析风化样品测试数据,生物标志物诊断比值表现出良好的稳定性,所选取多环芳烃新诊断比值中,菲和系列、烷基取代二苯并噻吩类、烷基取代芴类的抗风化能力较强,可用于油源鉴别。     

哈萨克斯坦及俄罗斯渣油馏分中的硫化物裂解色谱分析

采用裂解气相色谱接脉冲火焰光度检测器（PY-GC-PFPD）,研究了哈萨克斯坦原油及俄罗斯减压原油渣油及其馏分的裂解硫化物的组成分布。依据渣油高温裂解硫化物的主要类型：H2S、噻吩类、苯并噻吩类及二苯并噻吩类,选择噻吩、苯并噻吩（BT）和二苯并噻吩（DBT）模型化合物,考察裂解温度400℃-1000℃及时间5 s-10 s的反应产物及转化率,以证明渣油裂解硫化物基本可反映其在渣油中的结构。采用超临界流体萃取分馏,将俄罗斯和哈萨克斯坦渣油分别分割成18和19个窄馏分,在裂解温度1000℃及10 s条件下,获得了两种渣油及其馏分中H2S、噻吩、BT和DBT的含量分布,推断了渣油中硫化物噻吩类和硫醚类分布规律。     

EMIES/p-TsOH型低共熔溶剂的合成及其氧化脱硫性能的研究

通过1-乙基-3-甲基咪唑硫酸乙酯离子液体（EMIES）和对甲苯磺酸（p-TsOH）的混合物制备EMIES/p-TsOH型低共熔溶剂。其结构特征通过红外光谱、氢谱和热重技术进行了分析。并以EMIES/p-TsOH作为催化剂与萃取剂,H₂O₂作为氧化剂研究了其对模拟油中的硫化物的脱除性能。考察了反应温度、n（H₂O₂）/n（S）比、低共熔溶剂加入量及硫化物类型对脱硫效果的影响。在最佳的条件下,模拟油中二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）和苯并噻吩（BT）的脱除率分别为96.2%、92.2%和88.8%。经过五次循环使用后,DBT的脱除率仍达到93.6%。对该脱硫体系进行了动力学分析,其表观活化能为66.4kJ/mol。     

H2WO4/GO的制备及其超声-氧化脱除模拟油中的硫化物

以钨酸和氧化石墨烯为原料,利用浸渍法将钨酸负载到氧化石墨烯上制得H₂WO₄/GO。采用XRD、FT-IR、SEM、BET表征确定H₂WO₄/GO的形态及其结构。以H₂WO₄/GO作为催化剂,H₂O₂作为氧化剂,乙腈作为萃取剂超声氧化脱除模拟油中的二苯并噻吩（DBT）。实验表明,在模拟油为5 mL,钨酸的负载量为30%（质量分数）,催化剂为0.02 g,乙腈为1 mL,H₂O₂/S（mol ratio）为8,反应温度为50℃,超声功率为150 W的最佳反应条件下,二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）、苯并噻吩（BT）的脱除率分别达到96.6%、81.2%、72.8%。同时,考察了催化剂的循环使用性能,并对超声氧化脱硫机理进行了研究。     

二苯并噻吩类硫化物在非负载型NiMoW催化剂上加氢脱硫反应机理

研究了二苯并噻吩(DBT)、4-甲基二苯并噻吩(4-MDBT)和4,6-二甲基二苯并噻吩(4,6-DMDBT)在非负载型NiMoW催化剂上的加氢脱硫反应产物分布及反应机理,给出了它们在非负载型催化剂上加氢脱硫反应网络.研究发现,由于甲基的空间位阻效应,二苯并噻吩类化合物加氢脱硫转化率顺序为4,6-DMDBT≈4-MDBT＜DBT,而非负载型NiMoW催化剂具有很高的芳环加氢活性,有利于烷基取代的芳环加氢,减弱空间位阻效应,使烷基取代的二苯并噻吩类化合物得到有效脱除.DBT的脱硫产物会被进一步加氢,其产物分布与联苯加氢产物相似.4-MDBT有两种预加氢脱硫反应路径,甲基取代的苯环由于甲基的供电子效应会被优先加氢.非负载型催化剂存在的L酸中心会使部分4-MDBT和4,6-DMDBT通过脱甲基反应生成DBT再进行脱硫反应.     

GEOCHEMISTY OF BICYCLIC ALKANES IN SEDIMENTS, COAL AND CRUDE OILS

By using GC-MS to analyze the extracts of source rocks, coal and crude oil samplesformed in different sedimentary environments in China, New Zealand and Australia, twenty-two compounds of five types of bicyclic alkanes have been dis covered in the samples. Thispaper makes an exposition of stereochemical structure, abundance and distributive features ofthese compounds and their relation to sedimentary environments and thermal evolution. Furt-thermore, it demonstrates how the abundance ratios of bicyclic alkanes to steranes and ter-panes, drimane to homodramane and the relative abundance of C_(15),C_(16),C_(12)-C_(14) series of bicyclic-alkane compounds can be used to judge and determine types of oil and gas forming environ-ments (the depositive environments of source rocks from which the oil and gas wereformed), characteristics of source rocks and degree of maturation.     

气相色谱法测定催化柴油中硫化物类型分布及数据对比

采用气相色谱-氢火焰离子化检测器-硫化学发光检测器（GC—FID—SCD）联用技术,建立了催化柴油中各种硫化物类型分布的分析方法。考察了色谱条件对催化柴油中各种硫化物分离的影响,定性了某催化柴油中的120多个硫化物,该方法还可以同时提供催化柴油中正构烷烃含量的分布信息。硫化物中的硫在1．5—700mg／L时其峰面积与质量浓度呈较好的线性关系,相关系数达0．9999,响应与硫化物的类型无关。催化柴油中苯并噻吩、4-甲基苯并噻吩、二苯并噻吩、4-甲基二苯并噻吩和4,6-二甲基二苯并噻吩等主要硫化物浓度测定的相对标准偏差（RSD）均小于5．0％。当信噪比（S／N）为3时,测得苯并噻吩硫的检出限为0．1mg／L。将该方法用于不同来源柴油中各种硫化物类型分布的研究,并与气相色谱一原子发射光谱检测器（GC—AED）测硫的数据进行了对比,两种检测器的定量结果大多数具有较好的相关性,相关系数大于0．95。     

Application of solid‐phase microextraction to the determination of polycyclic aromatic sulfur heterocycles in Bohai Sea crude oils

A simple and rapid solid‐phase microextraction approach for the isolation of polycyclic aromatic sulfur heterocycles from the aromatic fraction of crude oil is described. 8‐Hydroxyquinoline silica gel impregnated with palladium chloride was used as a sorbent material for extraction. Operational parameters of the extraction solvents have been evaluated and optimized. Benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene and their C₁–C₄ alkyl derivatives were identified and quantified by GC–MS. Under optimum conditions, the limits of detection for benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene were 0.277, 0.193, and 0.597 μg/g oil, respectively. The recoveries for the polycyclic aromatic sulfur heterocycles ranged from 81.5 to 92.1%, and the linear dynamic range was from 10 to 1000 ng/mL. The developed methodology was tested in the characterization of crude oil samples collected at the DY, SZ, ZH, and HC petroleum oil fields of the Bohai Sea. The results proved that SPE coupled with GC–MS is a promising tool for the quantitative analysis of polycyclic aromatic sulfur heterocycles in crude oils, especially for oil samples with low concentrations of polycyclic aromatic sulfur heterocycles.     

SPORES AND POLLEN IN CRUDE OILS AND PETROLEUM SOURCE OF TARIM BASIN

One hundred and forty-seven species of spores and pollen referred to 77 genera found in the crudeoil samples taken from four petroliferous provinces of the Tarim Basin of Xinjiang Provincehave been studied in this paper. By means of these spore and pollen fossils, the geological ages anddistribution of the petroleum source rocks of the basin are judged. Also, the principles and methodsto judge the petroleum source of a petroleum province by spore/pollen and other microfossils in crudeoils are explained.     

Determination of trace elements in crude oils and organic materials extracted from oil-forming source rocks in China by INAA

A combination of Soxhlet extraction, column chromatography and INAA with GC and GC-MS was used in this work for the study of the abundance patterns of 36 trace elements and their correlation in nearly 100 samples of crude oil and organic materials extracted from oil-forming source rocks from 10 main Chinese oilfields. The low V/Ni ratios of 0.01 to 0.3 state the oil-forming continent environment. The geochemical significance hinted from other trace element abundances is also briefly discussed.     

BIOMARKERS INDICATING SEDIMENTARY PALEOENVIRONMENTS

Samples involved in this paper are 35 pieces of crude oils and 43 pieces of source rocks, from which a series of biomarkers, capable of indicating paleoecology and paleoenvironment. This will provide a scientific basis for tracing back to sedimenta-y paleoenvironment and paleoecology.     

NH2-SEP-PAK cartridges for enrichment of Aromatic Sulfur Compounds from sea water: determination by GC-FID and GC-MS

The Aromatic Sulfur Compounds (ASCs) are considered as "markers" of the crude oil age. In this frame, we have considered ASCs as "markers" of remote crude oil sea water pollution for their chemical characteristics, good solubility in water and resistance to the biodegradation. Gas chromatography of ASCs in distilled water and sea water samples has been performed after adsorption from a 80 mL water sample on to a cartridge containing 100 mg NH2-bonded porous silica. The ASCs are desorbed with 2 mL acetone-trichloromethane (1:1), which is concentrated and analysed by GC-FID or GC-MS in SIM mode. The average recovery of 0.1 microg mL(-1) of each ASC from distilled water and 0.04-0.2 microg mL(-1) from sea water samples is > or = 96.3% with a standard deviation < or = 2.2. The limits of detection are 0.06-0.05 ng mL(-1) for thiophen-2-carboxaldehyde and benzothiophene, and 0.006-0.004 ng mL(-1) for dibenzothiophene and thiantrene in GC-FID whereas they are 0.02 ng mL(-1) for thiophen-2-carboxaldehyde and benzothiophene, and 0.003 ng mL(-1) for dibenzothiophene and thiantrene in GC-MS (SIM) with a relative standard deviation < or =7.     

IDENTIFICATION OF LANOSTANES AND THEIR POSSIBLY GEOCHEMICAL SIGNIFICANCE IN BIYANG DEPRESSION

In the study, a series of C_(30)-C_(32) lanostane homologs have been identified from Eogene source rocks and crude oils of Biyang depression in Henan Province, China. Based upon the geochemical investigations and simulating experiments, the idea that the generation of lanostane may mainly be related to the specific original organic inputs and low maturity has been proposed.     

原油中含氧化合物的质谱分析

本文介绍自原油分离含氧化合物,酯化混合酸和用毛细管气相色谱-质谱(GC-MS)鉴定其组分的方法。色谱-质谱分离并鉴定出C_8—C_(30)的脂肪酸、分子量为484和498的二对藿烷酸的立体异构体,烷基酚,邻苯二甲酸酯等,并首次发现石油中含有癸二酸二异辛酯类组分。