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1.
Characterization of solid bitumens originating from thermal chemical alteration and thermochemical sulfate reduction 总被引：1，自引：0，他引：1
Simon R. Kelemen Peter J. Kwiatek Mobae Afeworki William A. Lamberti Hans G. Machel Trudy Bolin 《Geochimica et cosmochimica acta》2010,74(18):5305-4687
Solid bitumen can arise from several reservoir processes acting on migrated petroleum. Insoluble solid organic residues can form by oxidative processes associated with thermochemical sulfate reduction (TSR) as well as by thermal chemical alteration (TCA) of petroleum. TCA may follow non-thermal processes, such as biodegradation and asphaltene precipitation, that produce viscous fluids enriched in polar compounds that are then altered into solid bitumens. It is difficult to distinguish solid bitumen formed by TCA from TSR since both processes occur under relatively high temperatures. The focus of the present work is to characterize solid bitumen samples associated with TSR- or TCA-processes using a combination of solid-state X-ray Photoelectron Spectroscopy (XPS), Sulfur X-ray Absorption Near Edge Structure Spectroscopy (S-XANES), and 13C NMR. Naturally occurring solid bitumens from three locations, Nisku Formation, Brazeau River area (TSR-related); La Barge Field, Madison Formation (TSR-related); and, the Alaskan North Slope, Brooks Range (TCA-related), are compared to solid bitumens generated in laboratory simulations of TSR and TCA.The chemical nature of solid bitumens with respect to organic nitrogen and sulfur can be understood in terms of (1) the nature of hydrocarbon precursor molecules, (2) the mode of sulfur incorporation, and (3) their concentration during thermal stress. TSR-solid bitumen is highly aromatic, sulfur-rich, and nitrogen-poor. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (S/C atomic ratio >0.035) into aromatic structures and to initial low levels of nitrogen in the unaltered petroleum. In contrast, TCA-solid bitumen is derived from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. TCA-bitumens from the Brooks Range have <75% aromatic carbon. TCA-bitumens exposed to greater thermal stress can have a higher aromaticity, like that observed in TSR-bitumens. Organic sulfur in TCA-organic solids remains relatively constant with increasing maturation (S/C atomic ratio <0.035) due to offsetting preservation and H2S elimination reactions. Although S-XANES and 13C NMR provide information needed to understand changes in structure and reactivity that occur in the formation of petroleum solids, in some cases XPS analysis is sufficient to determine whether a solid bitumen is formed by TCA or TSR. 相似文献
2.
H. H. Li H. Yu M. T. Sun K. A. Alamry A. M. Asiri S. H. Wang 《International Journal of Environmental Science and Technology》2018,15(6):1193-1200
Hydrogen sulfide is a flammable and poisonous gas pollutant often emitted to air as a by-product of water supply, chemical, petroleum and coal industries. It can be transferred into sulfur dioxide in the air under some meteorologic conditions. Herein, a novel functional copper complex is reported which can selectively absorb hydrogen sulfide and subsequently release a highly fluorescent molecule. The copper complex is functionalized with a benzoxadiazole moiety as a fluorescence reporter, and the copper center serves as the recognition and binding site for sulfide. The application of the copper complex has been demonstrated for sensitive and selective measurement of hydrogen sulfide on the basis of “turn-on” fluorescence method, and the limit of detection is determined to be 0.1 μM. Other relevant anionic ions such as bisulfite, sulfate and mercapto compounds showed no interference for the detection of sulfide. These results suggest that the compound and method can be potentially applied for on-site measurement and effective removal of sulfide from environment. 相似文献
3.
Physical separation of bitumen from low-grade Utah tar sand deposits containing a relatively high viscosity bitumen phase (Sunnyside and Tar Sand Triangle deposits) has been accomplished by traditional size reduction and froth flotation techniques. At appropriate experimental conditions more than 90% of the bitumen can be recovered in a concentrate, containing more than 20 wt. % bitumen, which should be a suitable feed material for subsequent hot water or thermal processing. The efficiency of bitumen recovery depends on the extent of size reduction, as well as promoter and dispersant addition. Rejection of greater than 60% of the sand at ambient temperature and ease of water removal from the concentrate make such a process strategy both energy and cost effective. The energy required to achieve effective separation by the ambient temperature process is significantly less than the energy required for the recently developed hot water process which is being evaluated in a 100-tpd pilot plant this year.The flotation behaviour of the tar sand in this ambient temperature process has been correlated with contact angle measurements and the apparent point-of-zero-charge of the bitumen. The best flotation response at pH 7.8 to 9.0 occurs when the contact angle between the air bubble and bitumen surface is a maximum, corresponding to the apparent point-of-zero-charge of the bitumen as determined by titration. 相似文献
4.
云南金顶超大型铅锌矿床沥青Re-Os法测年及地质意义 总被引：6，自引：3，他引：3
油气藏与金属矿床在世界许多沉积盆地内共存,油气成藏与金属成矿的动力学关系备受关注。云南兰坪金顶产有中国目前最大铅锌矿床,也是世界上唯一陆相沉积岩容矿、且形成于新生代的超大型铅锌矿床。矿床中常见沥青、重油等有机质,它们的形成早于或晚于铅锌硫化物成矿存在明显分歧,限制了对油气成藏与铅锌成矿关系的认识。本文针对金顶超大型矿区以古新统云龙组含砾砂岩和砂砾岩为主岩铅锌矿石中沥青,开展了Re-Os法同位素测年,获得68±5Ma的等时线年龄(MSWD=9.2,n=6),指示金顶古油气成藏形成于古新世,先于铅锌硫化物大规模成矿;烃类物质具有通过热化学还原硫酸盐提供铅锌成矿所需硫化氢的客观条件;油气成藏与铅锌成矿在云南金顶矿区很可能是一个先后发生的连续地质过程,成藏为成矿奠基,成矿伴随着油气藏的破坏。 相似文献
5.
四川赤普MVT铅锌矿床成矿与古老油气藏关系密切。通过对矿床不同成矿阶段硫化物硫同位素和热液碳酸盐碳、氧同位素系统研究,结合沥青有机质的有机地球化学特征,探讨油气参与金属成矿的详细过程。取得主要认识如下：(1)油气系统中先存的H2S是成矿早阶段主要的硫源, TSR作用启动后还原硫酸盐,为成矿提供另一硫源。Mg2+可能是控制成矿过程中TSR作用的一个因素;(2)热液碳酸盐矿物碳(氧)同位素组成指示了 TSR 作用氧化的有机碳与流体溶解围岩碳酸盐岩中碳的不均匀混合作用;(3)矿床中与成矿作用有关的有机质(沥青)具有高-过成熟度特征和低芳烃含量,或是其参与了 TSR 作用的一个标志;(4)川滇黔地区油气成藏-破坏和赤普铅锌成矿可能是盆山演化过程中不同阶段或是同一阶段不同时代的产物,铅锌矿床形成与古老油气藏破坏密切相关。 相似文献
6.
A sample preparation technique was developed to isolate and separate two classes of combustion-produced pollutants: three- to six-ring polycyclic aromatic hydrocarbons (PAH) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), from sediment samples for interference-free analyses by gas chromatography/mass spectrometry (GC/MS). The method involves soxhlet extraction with methylene chloride, sulfur removal with activated copper powder, gel filtration chromatography with Sephadex LH-20, polarity separations of PAH and PCDD/F with prepacked silica gel solid-phase extraction columns, and isolation of PCDD/F from polychlorinated biphenyls with microalumina columns. Stringent procedural controls were established to achieve clean isolations and recoveries of 70% or better for each step in the method. The prepared sample extracts were analyzed by capillary GC and GC/MS. Electron impact ionization was used for PAH, and negative chemical ionization with methane as a reagent gas was used for PCDD/F. Reproducible results were obtained. The method is simple and has the advantage of conserving sample consumption since two classes of compounds can be analyzed from the same sample. This can be critical in sediment core analyses where sample size is usually limited. 相似文献
7.
滇黔交界地区玄武岩铜矿中有机质的生物标志物特征及其地质意义 总被引：7，自引：1，他引：6
滇黔交界地区玄武岩中赋存的自然铜矿化与沥青密切相伴,玄武岩层间含碳沉积岩中的自然铜矿化发育大量碳质。本文采用有机质抽提、族组分定量及饱和烃色-质分析等方法对这两种产状的铜矿石中有机质的族组分含量和生物标志物进行了研究,并对其地质意义进行了探讨。通过研究取得如下认识：①含沥青铜矿石和含碳质铜矿石虽然产状明显不同,其有机质成因有明显差异,但其有机质族组分含量及生物标志物特征十分类似,反映它们经历了类似的地质作用;②有机质族组分及其生物标志物提供的来源信息较混乱,这可能是成矿流体循环改造导致的;③生物标志物特征表明,含沥青铜矿石及含碳质铜矿石中有机质经历了类似的较还原的高盐度环境,这可能是高盐度成矿流体及还原的成矿条件的指示;④生物标志物特征及氯仿沥青“A”低含量特征表明两类铜矿石中有机质成熟度高,这可能是成矿流体的热力对有机质改造的结果;⑤有机质生物标志物特征显示两类铜矿石中有机质生物降解作用不强,表明沥青的形成是原油受成矿热液热力影响发生热裂解的结果。 相似文献
8.
Solid bitumen occurs extensively in the paleo-reservoirs of marine sequences in southern China. The fluids in these paleo-reservoirs have usually experienced severe secondary alteration such as biodegradation and/or thermal maturation. The concentrations of extractable organic matter (EOM) in the resulting solid bitumens are too low to satisfy the amount required for instrumental analysis such as GC–MS and GC–IRMS. It is also difficult to get enough biomarkers and n-alkanes by dry pyrolysis or hydrous pyrolysis directly because such solid bitumens are hydrogen poor due to high maturities. Catalytic hydropyrolysis (HyPy) can release much more EOM from solid bitumen at mature to highly over-mature stages than Soxhlet extraction, dry pyrolysis and hydrous pyrolysis. However, whether the biomarkers in hydropyrolysates can be used for bitumen-source or bitumen–bitumen correlations has been questionable. In this study, a soft biodegraded solid bitumen sample of low maturity was thermally altered to various maturities in a closed system. HyPy was then employed to release bound biomarkers and n-alkanes. Our results show that the geochemical parameters for source and maturity based on biomarkers released from these thermally altered bitumen residues by HyPy are insensitive to the degree of thermal alteration. Furthermore, the maturity parameters are indicative of lower maturity than bitumen maturation products at a corresponding temperature. This suggests that biomarker source and maturity parameters, based on the products of HyPy, remain valid for bitumens which have suffered both biodegradation and severe thermal maturation. The distributions of δ13C of n-alkanes in hydropyrolysates are also insensitive to the temperature used for bitumen artificial maturation. Hence, the δ13C values of n-alkanes in hydropyrolysates may also provide useful information in bitumen–bitumen correlation for paleo-reservoir solid bitumens. 相似文献
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10.
四川赤普铅、锌矿床生物标志化合物特征研究 总被引：3，自引：0，他引：3
赤普铅、锌矿床的矿体中发育大量沥青,铅、锌矿化形成与沥青密切相关。应用族组分分离和定量及饱和烃色—质分析等方法对铅、锌矿中的沥青族组分和生物标志物进行了研究,并对其地质意义进行了探讨。通过研究取得如下认识:（1）铅、锌矿床内有机质主要来自碳酸盐岩,其次来自页岩,没有陆源有机质的加入;这种混合来源特征受到不同来源成矿流体作用的影响。（2）矿区内有机质反映了热液流体经历了还原、高盐度的物理化学过程。（3）矿区内有机质成熟度高,主要为炭质沥青,反映有机质的演化程度较高;矿体内有机质与围岩内有机质成熟度类似,反映它们经历了类似的地质作用过程。（4）有机质还原碳酸盐岩中的硫酸盐岩,产生还原硫,为铅、锌等硫化物的沉淀创造条件。（5）成矿流体中烃类含量比较高,推断已经演化到高成熟阶段的有机质可能以古油气藏的形式参与了成矿作用;有机质在与含矿流体混合过程中扮演着还原剂的角色。 相似文献
11.
目前对铅锌矿中高含量硫的测定主要采用传统的重量法和容量法,但由于铅锌矿基体复杂,干扰较多,造成操作步骤繁琐;而采用湿法仪器分析又受制于样品的前处理等问题使得测定结果的准确度较差。本文建立了应用元素分析仪测定铅锌矿中的高含量硫(1.0%~32.0%)的分析方法。将样品磨制成粒度小于0.075 mm的粉末,样品制备时加入高纯二氧化硅作为稀释剂以降低铅锌矿的含硫量,仪器测量时加入线状氧化铜作为添加剂以提高硫的氧化效果,优先选用与实际测定样品相同性质的铅锌矿国家标准物质GBW07287(硫的标准值为10.76%)建立标准曲线以减小基体效应。方法精密度(RSD,n=12)小于1%,实际样品分析的测定值与重量法的相对误差小于1%。本方法比化学分析方法的操作简单,几乎没有干扰;比湿法仪器分析方法的样品前处理步骤少,待测元素硫的损失少,测定结果可靠度高。 相似文献
12.
The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen. 相似文献
13.
华仁民 《中国地球化学学报》1990,9(3):231-243
The Dongchuan-type copper deposits have long been studied and well reported because of their great economic significance.The present paper proposes a “sedimentation-reworking“ origin for this type of deposits to challenge the current “sedimentation-metamorphism“ model which has been widely asscpted since 1970s.According to the new idea,orebodies were not directly deposited in the Luoxue dolomite where they are hosted.Instead,copper was preliminarily concentrated in the Yinmin Formation.During or after diagenesis,copper in the Yinmin Formation was mobilized and leached by hydrothermal solutions derived from the interstitial water of sediments under the high geothermal gradient of rift environment,Thus,copper was transported from the source bed(the Yinmin Formation)upward to the Luoxue algal dolomite where sulfur was produced by the reduction of sulfates.The copper sulfides were formed through replacement of initial sulfides by Cu-bearing solutions. 相似文献
14.
目前虽认为元坝气田长兴组天然气主要为原油裂解气,但尚未进行该气田的古油藏的定量恢复并计算原油裂解气的资源量,并系统分析古油藏原油的来源.长兴组储层普遍可见固体沥青,是原油裂解的直接产物,且原油裂解在本区构造抬升变形前就已经完成,因此储层沥青可用来识别古油层的分布.根据储层沥青的纵向和平面分布,确定了7个可靠的古油藏和4个可能的古油藏,并运用容积法恢复出本区聚集的古原油为6.14×108 t,计算出相应的原油裂解气为3 807.08×108 m3,远大于现今气田的天然气探明储量,表明原油裂解气可以提供充足的气源,进一步证明了天然气主要为原油裂解气.通过长兴组储层沥青与不同层系烃源岩干酪根的碳同位素δ13C值对比,并结合烃源层分布和TOC等资料,确定古油藏原油主要来源于有机质类型以Ⅱ型为主的上二叠统吴家坪组烃源岩,其次为长兴组/大隆组烃源岩.后者主要分布在广元-南江-通江地区,该区的天然气勘探不能忽视该套烃源岩的生烃潜力与成藏贡献. 相似文献
15.
阿舍勒铜矿曾被认为是次火山热液矿床。根据岩芯观察研究和同位素、微量元素及稀土元素地球化学研究,认为该矿属海相火山喷气沉积成因,成矿作用与双峰式火山岩密不可分,细碧岩是成矿金属元素的主要来源,而作为沉淀剂的硫主要由酸性火山喷气作用提供。 相似文献
16.
高频燃烧-红外碳硫吸收仪快速测定含铜烧结物料中的高含量硫 总被引：3，自引：3，他引：0
应用高频燃烧-红外碳硫吸收法测定含铜烧结物中的高含量硫。对样品称样量、助熔剂的种类、加入顺序、用量等测定条件进行研究。由于样品含硫量的不同,根据矿石标准样品中含硫量的比例关系确定具体的称样量。以纯铁屑和钨粒作助熔剂,高温燃烧分解试样,红外检测可定量测定含铜烧结物样品中含量为1%~23%的硫。方法加标回收率为94%~113%,相对标准偏差(RSD,n=6)小于2%。与经典的硫酸钡重量法对比,相对误差小于4%。建立的方法解决了大宗含铜烧结物中硫快速、准确测定的问题,已应用于实际的日常检验工作。 相似文献
17.
福建紫金山铜金矿床类型与环太平洋浅成低温矿床的比较 总被引：8，自引：0，他引：8
福建省上杭紫金山铜金矿床是我国大陆发现的首例高硫型浅成低温热液矿床,在矿床深 继发现了斑岩型铜矿、中低温热液型铜矿和低硫浅成热液型银（金、铜）矿。可与环太平洋带上一系列特大型斑岩铜金和低温热液型金（铜）矿对比,它们有若干共同特征,但紫金山矿床与它们的一些不同之处,启示我们开拓找矿的新的时空领域。 相似文献
18.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite. 相似文献
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西藏冈底斯斑岩铜矿带成矿流体的扫描电镜（能谱）约束 总被引：7，自引：4，他引：7
文章通过对碰撞造山型斑岩铜矿床———冈底斯斑岩铜矿带中的2个典型矿床(驱龙和厅宫)早期钾化石英脉中多相包裹体的扫描电镜/能谱研究,有效地弥补了以往研究中遗漏的成矿流体中有用组分信息,对成矿流体性质及成矿过程有了更为清晰的认识。扫描电镜/能谱研究表明,驱龙、厅宫矿床中多相包裹体中的子矿物,除常见的石盐及钾盐外,还含有重晶石、方解石、黄铜矿、钛铁矿及其他以Fe、Cu_Fe为主要元素的未知矿物。这些结果表明,成矿流体为富含Cu、Fe、Ti、Mn、S等成矿元素的高氧化态岩浆热液;黄铜矿、钛铁矿、重晶石等子矿物与石盐、钾盐子矿物共同产出,暗示直接从斑岩岩浆中出溶的高盐度流体是成矿物质组分搬运的主要载体。 相似文献