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1.
在ｐＨ５．６－６．４的缓冲介质中，Ｓｃ－埃铬菁Ｒ（ＥＣＲ）－氯化十六烷基吡啶－乳化剂ＯＰ形成蓝色配合物，基组成比ｎｓｃ：ｎＥＣＲ：ｎＣＰＣ＝１：２：２。配合物的最大吸收长在６１０ｎｍ处，表观摩尔吸光系数为１．７１×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。 相似文献
2.
天然气组分的溶解特征及其意义 总被引：24，自引：0，他引：24
通过模拟实验方法研究了天然气组分在地层水中的溶解特征。发现在多组分体系中，重烃气的溶解度随矿化度的增大出现先增后减现象；环烷酸类有机物对长链烃气组有明显的增溶作用，分压及其他条件相同时，天然气组分的溶解能力顺序为：ＣＯ２〉ＣＨ４〉Ｎ２〉Ｃ２Ｈ６〉Ｃ３Ｈ８〉ｎ－Ｃ４Ｈ１０〉ｉ－Ｃ４Ｈ１０〉ｎ－Ｃ５Ｈ１２〉ｉ－Ｃ５Ｈ１２。 相似文献
3.
2-〔2-(6-甲基苯并噻唑)偶氮〕-5-二乙氨基苯甲酸与钴的显色反应及其应用 总被引：4，自引：0，他引：4
在十二烷基硫酸钠存在下，于ｐＨ４．８￣７．４的缓冲溶液中，２－〔２－（６－甲基苯并噻唑）偶氮〕－５－二乙氨基苯甲酸（６－Ｍｅ－ＢＴＡＥＢ）与Ｃｏ（Ⅱ）发生显色反应，形成稳定的蓝紫色络合物，其组成为ｎＣｏ（Ⅱ）：ｎ６－Ｍｅ－ＢＴＡＥＢ＝１：２，最大吸收波长为６５０ｎｍ，ε为１．３８×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，Ｃｏ（Ⅱ）质量浓度在０￣０．３２ｍｇ／Ｌ时服从比尔定律。方法可直接用于维生素Ｂ１ 相似文献
4.
在ｐＨ５６～６４的缓冲介质中，Ｓｃ（Ⅲ）埃铬菁Ｒ（ＥＣＲ）氯化十六烷基吡啶（ＣＰＣ）乳化剂ＯＰ形成蓝色配合物，其组成比ｎＳｃ∶ｎＥＣＲ∶ｎＣＰＣ＝１∶２∶２。配合物的最大吸收波长在６１０ｎｍ处，表观摩尔吸光系数为１７１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。Ｓｃ质量浓度为０～０２４ｍｇ／Ｌ时遵守比尔定律。拟定的方法结合ＰＭＢＰ萃取分离，测定钨矿及其浸出渣中的微量Ｓｃ，可获满意结果 相似文献
5.
样品经ＨＦ－ＨＮＯ３－ＨＣｌＯ４分解，在２ｍｏｌ／ＬＨＮＯ３介质中，采用感耦等离子体光电直读光谱法对铀矿石尾标准物质中的Ａｓ、Ｂａ、Ｂｅ、Ｃｄ、Ｃｒ、Ｎｉ、Ｐｂ等和Ｓｎ进行定值分析。同一样品平行测定６次，其各元素的相对标准偏差在２％－１０％。分析结果均落在标准值的置信区间。 相似文献
6.
阳极溶出伏安法同时测定痕量锡和镉 总被引：4，自引：1，他引：4
在ＨＣｌ－ＮＨ＿４Ｃｌ底液中，电解时间６０ｓ、电镀时间５ｓ、除氧３０ｓ的条件下，Ｓｎ和Ｃｄ有稳定的溶出峰。Ｓｎ和Ｃｄ的检出限分别为６．５μｇ／Ｌ和３．０μｇ／Ｌ，测定范围分别为１０～２００μｇ／Ｌ和５～１８０μｇ／Ｌ。对含Ｓｎ和Ｃｄ为２０μｇ／Ｌ的试液测定１０份，ＲＳＤ分别为５．６１％和４．８３％。方法用于实际样品测定，结果与文献方法相符。 相似文献
7.
使用ＣＯ２激光器与ＩＣＰ－ＡＥＳ联接，实现了地质样品的固体采样分析，加入一定量的聚三氟氯乙烯，可基本消除样品组成及元素赋存状态的影响，改善了分析结果的准确度。测定了地质样品中的Ｂａ，Ｃｅ，Ｃｕ，Ｃｒ，Ｌａ，Ｍｎ，Ｎｂ，Ｓｃ，Ｓｒ，Ｔｉ，Ｙ，Ｙｂ和Ｚｒ等１４种元素，检出限０．１×１０＾－６至１０×１０＾－６，ＲＳＤ一般在３％－７％，最大为１０％，。 相似文献
8.
在十二烷基硫酸钠存在下，于ｐＨ４８～７４的缓冲溶液中，２＿〔２＿（６＿甲基苯并噻唑）偶氮〕＿５＿二乙氨基苯甲酸（６＿Ｍｅ＿ＢＴＡＥＢ）与Ｃｏ（Ⅱ）发生显色反应，形成稳定的蓝紫色络合物，其组成为ｎＣｏ（Ⅱ）∶ｎ６＿Ｍｅ＿ＢＴＡＥＢ＝１∶２，最大吸收波长为６５０ｎｍ，ε为１３８×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，Ｃｏ（Ⅱ）质量浓度在０～０３２ｍｇ／Ｌ时服从比尔定律。方法可直接用于维生素Ｂ１２和含钴分子筛中微量Ｃｏ（Ⅱ）的测定，结果与原子吸收法相符。对于ｗ（Ｃｏ）＝０．８２％的含钴分子筛测定８次，其ＲＳＤ为１３４％。 相似文献
9.
辉碲铋矿单矿物的化学分析 总被引：1，自引：1，他引：1
辉碲铋矿物经ＨＮＯ３－ＫＣｌＯ３溶解，用火焰原子吸收法或乙二胺四乙酸二钠事滴定法测定Ｂｉ，火焰原子吸收法测定Ｔｅ、Ｆｅ、Ｃｕ，３，３＇－二氨基联苯胺光度法测定Ｓｅ，硫酸重量法测定Ｓ。其结果与矿物化学成分理论值十分接近，主、次量元素平行测定６次，其ＲＳＤ小于０．８％，痕量元素ＲＳＤ（ｎ＝６）小于１０％。 相似文献
10.
浙江泰顺洋滨黄玉斑岩地球化学特征和成因 总被引：9，自引：3，他引：9
浙江泰顺洋滨斑岩锡矿成矿母岩为黄玉斑岩类岩脉，长约２ｋｍ，宽２－２０ｍ，岩性可分黄玉钾长花岗斑岩、黄玉二长花岗斑岩和黄英斑岩三种。黄玉含量占１０％－２０％，具火成斑状结构。岩石为强过铝质（Ａ／ＮＫＣ＝１．５７４－１２．９４），高Ｆ／Ｃｌ值（１４６－３０３），高Ｒｂ／Ｓｒ值（５－１２２），高的不相容元素丰度（Ｓｎ＝３１３×１０－６－１０４２×１０－６）而相容元素丰度较低（Ｓｒ＝１０×１０－６－２８×１０－６），稀土配分呈海鸥型，成因上应是Ｓ型含锡斑岩。 相似文献
11.
Anke Putschew Christine Schaeffer-Reiss Philippe Schaeffer Martin P Koopmans Jan W de Leeuw Michael D Lewan Jaap S Sinninghe Damsté James R Maxwell 《Organic Geochemistry》1998,29(8):1875-1890
An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAlH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments. 相似文献
12.
13.
珠江口盆地番禺低隆起-白云凹陷北坡干酪根热演化模拟与生烃 总被引：1，自引：0，他引：1
通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。 相似文献
14.
D. A. Bushnev 《Lithology and Mineral Resources》2005,40(1):21-29
Compositions of organic matter in the bituminous shale accumulated under anoxic conditions and in the underlying clay deposited in aerated basin are noticeably different. Organic matter (OM) of the clay is depleted in hydrogen and kerogen of the clay during pyrolysis produces 2.5 times less aliphatic hydrocarbons than kerogen, which is separated from the bituminous shale, and dozens of times less sulfurous compounds, such as thiophenes and benzothiophenes. Accumulation of OM in the clay was primarily related to the direct inheritance of polymeric lipid biochemical components of the initial OM and lignin included in the higher plants. Changes of gas regime in the basin and sediments, expressed in the origin of anoxic conditions during the accumulation of bituminous shales, intensified the early diagenetic sulfuration and the consequent formation of sulfur- and hydrogen-rich kerogen in the shales. At the same time, less stable lipids and, possibly, carbohydrates were also conserved.Translated from Litologiya i Poleznye Iskopaemye, No. 1, 2005, pp. 25–34.Original Russian Text Copyright 2005 by Bushnev. 相似文献
15.
Sunil Bharati Richard L. Patience Steve R. Larter Guy Standen Iain J. F. Poplett 《Organic Geochemistry》1995,23(11-12)
The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (13C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. 13C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CHxO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (fa), O/C and relative proportions of various carbon types estimated by 13C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen. 相似文献
16.
Beukes NJ Klein C Kaufman AJ Hayes JM 《Economic geology and the bulletin of the Society of Economic Geologists》1990,85(4):663-690
The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations. 相似文献
17.
塔里木盆地哈拉哈塘凹陷天然气地球化学特征 总被引：2，自引：0，他引：2
哈拉哈塘凹陷位于塔里木盆地塔北隆起中部,具有良好的石油地质条件,是近期油气勘探的重点区带。天然气地球化学特征研究表明,该区天然气干燥系数较低,表现出典型湿气的特征,普遍含有微量的H2S;烷烃气δ13C1和δ13C2值分别为-50.5‰~-42.6‰和-40.2‰~-35.5‰,δD1值介于-262‰~-156‰之间,碳氢同位素系列表现出典型正序特征; C7轻烃组成具有正庚烷优势分布, C5~7轻烃组成以正构和异构烷烃为主。哈拉哈塘凹陷及周缘奥陶系天然气均为海相油型气,既有干酪根裂解气,也有原油裂解气,其中哈拉哈塘天然气中混入了相当比例的原油裂解初期形成的湿气,主要来自于南部阿满过渡带地区的中上奥陶统烃源岩,天然气中具有高δ13C值特征的CO2主要来自碳酸盐岩储层在酸性地层水作用下发生的溶蚀, H2S主要源自含硫化合物的热裂解。其中天然气发生的同位素部分倒转主要源自原油伴生气与原油裂解气的混合。 相似文献
18.
Research into the origin and the mode of entrapment and expulsion of natural gas from unconventional plays requires the isolation and separation of kerogen in its purest and most intact form from the rock matrix. This study expands on the comparative analysis of the effects that isolation methods, conservative closed system versus conventional open system, have on kerogen’s elemental, isotopic and physical properties. Four major gas shales, including the Barnett, the Marcellus, the Haynesville and a Polish gas shale, were chosen. In addition, the Monterey shale, though not strictly a gas shale, was included to address the effects on sulfur rich, Type II-S kerogen.Results indicate that the kerogen residues from the conventional open system method showed lower recovery and higher mineral content than those from the conservative closed system method. Differences were manifested in the elemental analysis data, where kerogens isolated using the open system method showed a significant deficit in the organic C, H, O, S and N material balance. Furthermore, the recovered residues show different sulfur content and δ34S composition, most likely attributable to differences in pyrite content. Nevertheless, the relative abundances of the various macerals in the kerogen residues from the same parent shale are not very different; neither was the bulk δ13C composition of the recovered residues. This is not particularly surprising, considering that in all the five cases examined in this study, the organic matter was fairly homogeneous. 相似文献
19.
Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350 °C for 72 h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350 °C than in kerogen decomposition to bitumen at 330 °C. At 350 °C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C15+ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen. 相似文献
20.
Light hydrocarbons in subsurface sediments 总被引：1，自引：0，他引：1
K.F.M Thompson 《Geochimica et cosmochimica acta》1979,43(5):657-672
The major features and numerous compositional details of the indigenous C2–C7 hydrocarbon suites of argillaceous sediments are systematically temperature dependent. The relative concentrations of alicyclic compounds exhibit a consistent maximum at subsurface temperatures close to 170°F (77°C) without regard to the chemical nature of the bulk of the kerogen, whether rich or poor in hydrogen, though this strongly affects the specific yield. A continuous increase in relative alkane content follows at higher temperatures. Indices of paraffinicity may be devised. One such, termed the ‘heptane value’ (essentially the percentage of n-heptane in the b.p. range 80.7–100.9°C), possesses a linear association with temperature, provides an index of catagenesis, and frequently provides a means of appraising paleotemperatures. Regressions of heptane value on temperature are compared in two composite stratigraphic sections dominated by kerogens representing two extremes of composition. The regression coefficients differ by 7%. Yields of light hydrocarbons increase exponentially in these sections by more than three orders of magnitude along sub-parallel, temperature-dependent curves. These similarities infer universally similar generating reactions and compositionally similar suites of light hydrocarbons at given subsurface temperatures, regardless of kerogen type, particularly for sections which underwent burial and heating during the Tertiary period. 相似文献