TSR(H2S)对石油天然气工业的积极性研究--H2S的形成过程促进储层次生孔隙的发育

TSR(硫酸盐热化学还原反应)是高含硫化氢天然气形成的重要途径,是指烃类在高温条件下将硫酸盐还原生成H2S、CO2等酸性气体的过程。由于硫化氢的剧毒和强腐蚀性,在石油天然气行业的钻井、完井、修井、净化加工以及运输等各个方面的危害一直备受人们的关注,对硫化氢和TSR的评价一直是负面的,在油气勘探中更多是在回避。最近研究发现,TSR作用对石油天然气工业具有重要的积极作用。TSR的发生,首先需要硫酸盐类溶解提供SO42-,储集空间得到初步改善;其次TSR反应形成的硫化氢,溶于水后显示出较强的酸性溶蚀作用,对白云岩储层具有最佳的溶蚀效果。在高温条件和储层中地层水的作用下,硫化氢与白云岩发生较强烈的酸性流体-岩石相互作用(水岩反应),促进了白云岩次生孔洞的发育和高孔高渗优质储集层的形成,使油气储层保存下限增大和深部天然气聚集成藏成为可能。而目前飞仙关组高含硫化氢气藏普遍压力系数小、充满度低,这与TSR及硫化氢对储层溶蚀导致储集空间增容有关。四川盆地油气勘探结果证实,所有高含硫化氢天然气藏均对应了次生孔隙十分发育的优质储层,岩性主要以白云岩为主,储层埋藏深度超过8 000 m时依然发育优质储层。     

甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究

碳酸盐岩地层中常伴有硫酸盐岩的沉积，在一定的温度和压力条件下，干酪根热降解生成的气态烃与硫酸盐岩接触后发生热化学还原反应(简称为TSR反应)，使气态烃消失，这可能是造成生气死亡线的主要原因之一。本文对CH4-CaSO4热化学还原反应的热力学问题进行了探讨，发现该反应能够自发进行，而且升高温度对反应有利。利用高温高压模拟装置对CH4-CaSO4反应体系进行了初步的模拟实验研究，通过微库仑、气相色谱和傅里叶变换红外光谱(FT-IR)等分析手段对实验结果进行了进一步验证。结果表明，甲烷和固态硫酸钙能够发生热化学还原反应，生成硫化氢、碳酸钙和水。最后，将CH4-CaSO4反应体系同国内外的研究工作进行了对比，认为本实验研究能够更好地补充和完善TSR反应体系，解释地质条件下工业气藏的死亡线问题。     

四川盆地飞仙关组气藏硫化氢成因及其依据

四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%～90%之间,C2＋含量为0～0.15%;非烃气体以H2S和CO2为主,含量分别为5%～20%和1%～10%。已有观点认为H2S为飞仙关组气藏附近的石膏经硫酸盐热化学还原作用（TSR）而成。随着川东北气区大中型高含硫化氢气田的发现,硫化氢成因机理的研究备受关注。应用金管、高压釜和石英管等实验方法模拟了硫化氢气体的生成,同时检测了模拟生成的硫化氢和石膏、硫磺等硫化物的硫同位素。实验结果表明:硫磺与正己烷在较低温度即可生成大量的硫化氢气体,而正己烷与硫酸钙的反应总体上比较困难,且生成的H2S量较少;富含黄铁矿的低成熟泥灰岩模拟生烃过程中可以生成与甲烷相当,甚至超过甲烷含量的硫化氢气体;含硫化合物与烃类反应生成的硫化氢的硫同位素值比原始物质的硫同位素值重。地层中的SO2－4是海相地层中H2S气体形成的最初来源。含硫烃源岩直接生成高硫化氢天然气和储层中单质硫与烃类的反应是川东北飞仙关组天然气中硫化氢形成的主要原因。     

深盆气藏勘探开发现状及发展趋势

深盆气藏是发育在构造下倾方向或下部层位、气源岩与致密储层邻接的天然气聚集。其成藏机理表现为天然气从构造下倾部位或致密储层底部对储层中原始地层水的活塞式推进,而常规圈闭气藏则表现为天然气与地层水的置换式运移,两者在成藏机理上形成了鲜明对比。在调研大量国内外深盆气藏勘探开发实践的基础上,对深盆气藏的地质条件、成藏主控因素以及勘探开发现状进行了系统研究,结合四川盆地川西坳陷的石油地质特点进行类比,认为川西坳陷可能存在深盆气藏。     

四川盆地高含H2S天然气的分布与TSR成因证据

四川盆地是中国高含硫化氢天然气分布最集中的地区,目前已在震旦系(威远气田)、下三叠统飞仙关组(罗家寨、普光、渡口河、铁山坡、七里北)、嘉陵江组(卧龙河)和中三叠统雷口坡组(磨溪、中坝)发现了近10个高含硫化氢的大中型气田(藏),探明储量5000×108 m3.这些高含硫化氢气藏普遍经历过较大的埋深过程(储层经历过较高温度),储层上下或储层中间均发育有膏质岩类,且气源充足,具备硫酸盐热化学还原反应(Thermochemical Sulfate Reduction,TSR)发生的物质基础和热动力条件.从气藏地质特征以及天然气组成和碳、硫同位素等方面的证据表明,四川盆地中、下三叠统和震旦系气藏的硫化氢属于TSR成因.而且TSR对烃类的大量选择性消耗一方面导致天然气干燥系数增大,另一方面导致气藏充满度降低,气藏压力系数变小.     

TSR对深部碳酸盐岩储层的溶蚀改造——四川盆地深部碳酸盐岩优质储层形成的重要方式

四川盆地海相层系发现的大气藏部含或高舍硫化氢,都发育一定厚度的优质储层,而且优质储层与硫化氢分布具有密切的关系,即气藏硫化氢含量越高,储层性质越好,气藏产能也越大。研究发现,在 TSR(硫酸盐热化学还原反应)过程中,随着膏质岩类的溶解(为 TSR 反应提供 SO_4~(2-)),使储集孔隙初步得到改善;而 TSR 产生的硫化氢溶于水形成的氢硫酸,具有强烈腐蚀性,加速了储层中白云岩的溶蚀,形成孔隙极其发育的海绵状孔洞体系,并呈层状分布。电镜下可以清晰看到白云石晶面的溶蚀坑及溶孔中 TSR 产生的硫磺晶体。溶孔中自生碳酸盐的碳同位素在-10.3‰～18.2‰,而地层碳酸盐的碳同位素在 3.7‰～ 0.9‰,证实了 TSR 过程中有机-无机的相互作用,即有机成因烃类中的碳转移到次生碳酸盐岩中。包裹体分析表明,次生方解石中的包体富含硫化氢,且均一温度多数在160℃以上,具备 TSR 发生的温度条件;硫化氢和硫磺的硫同位素比地层硫酸盐的硫同位素偏轻8‰左右,是 TSR 作用的证据。因此高含硫化氢气藏的优质储层是在早期埋藏溶蚀作用的基础上,后期发生 TSR 及其形成的酸性流体对深埋碳酸盐岩储层再次进行深刻改造和强烈溶蚀作用的结果;同时可以运用硫化氢来预测碳酸盐岩优质储层的分布。     

硫化氢形成与C2+气态烷烃形成的同步性研究几个模拟实验的启示

硫酸盐热还原（TSR）是高含硫天然气形成的主要原因,但是参与TSR反应的主要烃类组分仍存在争议。在对比分析湿气—硫酸镁反应体系、甲烷—硫酸钙反应体系以及重烃—硫酸镁反应体系模拟实验的基础上,通过对TSR化学反应表达式的分析以及化学动力学、热力学等理论的探讨,结合实际地质资料,认为甲烷是C₂₊烃类参与TSR反应的产物,TSR的发生与C₂₊气态烷烃的产生具有同步性,TSR的反应速率随着C₂₊气态烷烃的增加而加快,当湿气裂解为干气后,硫化氢含量几乎不再增加,从而形成干气伴生硫化氢。根据油气生成演化阶段分析,认为TSR主要发生在热裂解生凝析气阶段,原油裂解为硫化氢伴生天然气后,压力系统发生改变,天然气重新聚集成藏,如果构造环境发生改变就会进一步调整成藏。因此,天然气中硫化氢含量不仅受生成条件控制,还受运移通道、保存条件等因素控制。     

四川盆地H2S的硫同位素组成及其成因探讨

四川盆地天然气绝大部分含有硫化氢,部分含量高达15%以上。其中高含硫化氢天然气主要分布在三叠系飞仙关组、雷口坡组和嘉陵江组;震旦系、石炭系、二叠系属于低含硫化氢,上三叠统须家河组和侏罗系属于微含硫化氢或不含硫化氢天然气藏。研究表明,三叠系飞仙关组、雷口坡组和嘉陵江组、震旦系、石炭系储层中发育的膏质岩类为TSR形成硫化氢提供了物质基础;富含有机硫源岩的高温裂解是二叠系低含硫化氢天然气的主要成因。硫同位素组成表明,高含硫化氢天然气的硫同位素比储层硫酸盐硫同位素δ34S亏损7‰～11‰;而低含硫化氢天然气硫同位素分布区间较宽,在0‰～20‰之间,大部分比同期硫酸盐的硫同位素轻15‰左右。四川盆地三叠系膏岩的硫同位素值分布较宽,并呈现阶梯状变化,而硫化氢的硫同位素则呈现出相似的分布规律,表明各气层硫化氢中的硫来自于本层系的硫酸盐,即TSR发生在各自的储集层中;另外四川盆地三叠系TSR发生时各气藏的温度条件相近,即各气藏的硫化氢在大致相同的温度条件下发生;同时也说明TSR过程中硫同位素的分馏过程与硫酸盐本身硫同位素数值的高低无关,而与TSR反应的温度条件和反应程度有关。还建立了运用硫化氢的硫同位素和含量判识硫化氢成因类型的模式。     

子洲气田山2气藏气井产水成因研究

在岩性气藏开发过程中,气井产水存在多种类型,气水分布在纵向和横向上都相对复杂.以子洲气田山 2 气藏为例,根据试气、测井和生产动态资料,将气井产水划分为纯水层、致密水层和气层产水 3 种类型,每种类型都受成藏环境、构造条件、储层岩性与物性等方面控制.除正常边底水类型的纯水层外,在岩性气藏部分井区中,由于储层条件变差,气体驱替能量不足,造成孔隙中水未受到天然气的大规模排驱而残留了大量地层水;形成致密水层和气层产微量地层水.     

松南气田火山岩气藏产水特征和控水策略

基于天然气单次闪蒸实验、气藏水化验分析两种方法,区分松辽盆地松南气田气井产水类型;结合气藏精细描述,分析不同气井的产水机理;进一步利用数值模拟,探索火山岩气藏控水策略。松南气田产水可分为凝析水和地层水两种类型,构造高部位火山机构气井产凝析水,构造低部位火山机构气井产地层水。断层引起的底水上窜是造成构造高部位钻井产少量地层水的主要原因。通过数值模拟发现,采气速度越高,边底水锥进越快。松南气田火山岩气藏最优采气速度约在3.6%。根据高部位高配、低部位低配的控水原则,明确了不同类型、不同构造部位火山岩气井合理产量,可有效控制火山岩气井出水,实现气藏稳产。     

Recovery of trace metals in formation waters using acid gases from natural gas

The maximum contents of Pb (360 mg l⁻¹), Zn (360 mg l⁻¹) and Ag (7.9 mg l⁻¹) in formation waters from the Alberta basin were high enough to suggest that it would be of interest to test the concept of recovering these metals by passing natural gas through the water, thereby precipitating the metal sulphides as the result of contact with hydrogen sulphide. The idea was to see if these metals could be recovered from formation water co-produced with crude oil prior to disposal of the water in deep formations, with the possibility of the sale of the metals partially offsetting the cost of disposal. It was proposed to use natural gas with a relatively small amount of hydrogen sulphide (insufficient for sulphur recovery) that must be removed by flaring before the gas is utilized. Accordingly, a database of 694 formation waters with major, minor and trace components was searched for appropriate analyses for detailed study. Of the nine analyses selected the majority were from Devonian and Granite Wash aquifers in the Peace River Arch area of northern Alberta, Canada. Modelling with PATH.ARC showed that there is a consistent set and order of precipitation reactions, in spite of the differences among the formation waters. As would be expected intuitively, acid gas addition makes the formation water more acidic, and metallic sulphide minerals are precipitated. Depending on the initial composition, the end minerals are any of galena, sphalerite, acanthite, covellite and pyrite. These are the minerals that must be beneficiated to recover the metals. A preliminary evaluation of the dollar value of the recovered metals shows that although the absolute values are low, there may be an advantage to recovering the metals if the waters are already being handled at the surface.     

Water Role and Its Influence on Hydrogen Isotopic Composition of Natural Gas during Gas Generation

In order to discuss the role and influence of water during the generation of natural gas, the participation mechanism of water during the evolution of organic matter and its influences were summarized. In addition, we carried out an anhydrous cracking experiment of oil extracted from the Feixianguan Formation source rock in a closed system, which led to the establishment of the kinetic models for describing carbon and hydrogen isotopic fractionation during gas generation from organic matter. The models were calibrated and then applied to the northeastern Sichuan Basin. By combining a series of gas generation experiments from octadecane pyrolysis without water or with distilled water in varying mass proportions, several results were proved: (1) the hydrogen isotopic composition of natural gas becomes lighter with the participation of formation water; (2) we can quantitatively study the hydrogen isotopic fractionation with the kinetic model for describing carbon isotopic fractionation; (3) more abundant and reliable geological information can be obtained through the combined application of carbon and hydrogen isotopic indices.     

Hydrogen from coal gasification: An economical pathway to a sustainable energy future

Although hydrogen is the most abundant element in the universe, it does not occur naturally in large quantities or high concentrations on Earth. Hydrogen must be produced from other compounds such as fossil fuels, biomass, or water and is therefore considered an energy carrier like electricity. Gasification of carbonaceous, hydrogen-containing fuels is an effective method of thermal hydrogen production and is considered to be a key technology in the transition to a hydrogen economy. However, for gasification to play a major role during the transition period, capital and operating cost must be reduced and reliability and performance must be improved.Analyses show that hydrogen produced from coal-based gasification can be competitive with production from natural gas provided the cost of natural gas remains above $4/10⁶ Btu and the high reliability of gasification-based processes can be demonstrated. But for coal to be considered in a carbon-constrained environment, the cost of natural gas would have to be greater than $5.50/10⁶ Btu. The development of advanced technologies, however, offers the potential for significant reductions in capital costs, improved thermal efficiencies, and increased reliability. If these advanced technologies are capable of achieving their goals, the cost of producing hydrogen from coal could be reduced by 25–50%, even with the capture and sequestration of CO₂. With these reductions, the cost of natural gas would have to be less than $2.50/10⁶ Btu to compete, a scenario that is very unlikely to occur in the future. This potential cost reduction provides considerable impetus for continuing research and development in the production of hydrogen from coal.     

高压釜对加水模拟实验中氢产物的影响

在对有机质进行加水高温高压热解实验时,经常会发现气体产物中的氢气含量非常高。通过大量的实验我们发现除了通常人们所认为的有机来源之外,还有很大一部分为无机成因,即不锈钢高压釜在高温高压条件下与水反应释放的氢气。在我们的实验中,无论是含有机质的还是仅含无机物的,产物中均有较大比例的氢气,其中在只有去离子水的模拟实验中也产生了一定量的氢气。这就证明不锈钢的高压釜确实参与了反应。这一因素必然会对模拟实验结果解释地质问题的有效性产生很大的影响.     

Pyrite-induced hydroxyl radical formation and its effect on nucleic acids

Background  

Pyrite, the most abundant metal sulphide on Earth, is known to spontaneously form hydrogen peroxide when exposed to water. In this study the hypothesis that pyrite-induced hydrogen peroxide is transformed to hydroxyl radicals is tested.     

Textural and fluid inclusion constraints on the origin of the banded-iron-formation-hosted gold deposits at Maevatanana,central Madagascar

The Maevatanana deposits consist of gold-bearing quartz–sulphide veins crosscutting banded iron formation (BIF) within a metamorphosed 2.5 Ga greenstone belt. The host rocks are dominated by a sequence of migmatites, gneisses, amphibolites, magnetite-rich quartzites and soapstones, intruded by large granitoid batholiths (e.g. the 0.8 Ga Beanana granodiorite). In the mineralised rocks, pyrite is the dominant sulphide, in addition to accessory chalcopyrite and galena. Outside the immediate ore zone, the BIF is dominated by quartz + magnetite ± hematite, accompanied by cummingtonite, albite and biotite. Gold occurs as globular grains (usually <500 μm) within quartz crystals close to the sulphides and as invisible inclusions within pyrite and chalcopyrite (up to 2,500 ppm Au content). Fluid inclusion textural and microthermometric studies indicate heterogeneous trapping of a low-salinity (∼3.6 wt.% eq. NaCl) aqueous fluid coexisting with a carbonic fluid. Evidence for fluid-phase immiscibility during ore formation includes variable L/V ratios in the inclusions and the fact that inclusions containing different phase proportions occur in the same area, growth zone, or plane. Laser Raman spectroscopy confirms that the vapour phase in these inclusions is dominated by CO₂ but shows that it may contain small amounts of CH₄ (<1 mol%), H₂S (<0.05 mol%) and traces of N₂. Fluid inclusion trapping conditions ranged from 220 to 380°C and averaged 250°C. Pressure was on the order of 1–2 kbar. The abundant CO₂ and low salinity of the inclusions suggest a metamorphic origin for the fluid. Likewise, the presence of H₂S in the fluid and pyritisation of the wall-rock indicate that gold was likely transported by sulphide complexing. Fluid immiscibility was probably triggered by the pressure released by fracturing of the quartzites during fault movements due to competence differences with the softer greenstones. Fracturing greatly enhanced fluid circulation through the BIF, allowing reaction of the sulphide-bearing fluids with the iron oxides. This caused pyrite deposition and concomitant Au precipitation, enhanced by fluid phase separation as H₂S partitioned preferentially into the carbonic phase.     

The Impact of Aqueous Medium on Gas Yields and Kinetic Behaviors of Hydrogen Isotope Fractionation during Organic Matter Thermal Degradation

In order to recognize the impact of aqueous medium on gas yields and the kinetic behaviors of hydrogen isotope fractionation during organic matter thermal degradation, the gold tube apparatus was used to conduct thermal simulation experiments by mixing the nC18 with the water of different properties and proportions. The yields of natural gas components, the relation among hydrogen isotope composition of each component and the experimental temperatures vs. heating rates have been obtained, and the results indicate that under the higher temperature conditions, the hydrous experiment has obvious impact on gas yields, such as when more water is added, higher amounts of hydrocarbon gas and H2 are yielded, and the existence of water obviously prolongs the temperature interval with the existence of heavy hydrocarbon gas. It also shows that the hydrogen isotope of hydrocarbon gas generated by the hydrous experiment is obviously lighter than that generated by the anhydrous experiment, and with the increasing amount of added water, the δD value of hydrocarbon gas gradually decreases. Compared with gas yields, the variation of δD value is more sensitive to aqueous medium in the thermal simulation experiment. However, compared with the amount of the added water, the aqueous medium property has smaller impact on the gas yields, which still shows the inherit effect on hydrogen isotope composition of aqueous medium. Through the model simulation and the isotope fractionation behavior analysis, it is validated that the hydrogen isotope fractionation process can be well described by the chemical kinetic model. The difference of reaction fraction of normal methane and D-containing methane is large, corresponding to the same activation energy. The content of normal methane is obviously higher in the part with lower activation energy, while the content of D-containing methane is higher in the part with higher activation energy. Therefore, it will result in larger hydrogen isotope fractionation amplitude, and the δD values will be more sensitive to the variation of maturity. Meanwhile, the average activation energy of methane generation from nC18 in the hydrous experiment is higher than that in the anhydrous experiment, and the greater amount of added water, the larger the average activation energy of methane generation reaction. This has laid foundation for its exploratory application in the study of gas reservoir forming history and the gas-source correlation, which indicates the research and application prospects in this orientation.     

我国生物气藏碳、氢同位素特征、形成途径及意义

生物气碳、氢同位素组成是探讨其形成途径和成藏特征的基本手段,研究基于我国10个生物气气藏31个气样的碳、氢同位素组成资料探讨了这些气藏的形成途径和成藏特征。研究表明:这些气藏的氢同位素组成可以分为三个区间,即δDCH4>-200‰;δDCH4值在-250‰～-200‰之间和δDCH4<-250‰。前人认为在陆相淡水条件下生物气的形成途径主要是乙酸发酵作用,我国10个气藏31个气样碳、氢同位素研究表明,海相及盐湖相条件下生物气形成途径为典型的CO2还原途径,具有重的氢同位素组成,其δDCH4>-200‰,而陆相条件下成藏的生物气也主要为CO2还原途径,但氢同位素组成较典型海相成因生物气轻,其δDCH4值在-250‰～-200‰之间。其值可能与古湖泊水介质的咸化程度有关。从柴达木的资料来看,随水介质咸度增大,生物甲烷氢同位素组成也具有相应增大趋势。陆相条件下有处于CO2还原和乙酸发酵两种作用过渡区形成的生物气气藏,其形成可能与古水介质无咸化过程和地温梯度较高有关,如保山盆地。该区形成的生物气具有轻的氢同位素组成,δDCH4<-250‰,碳同位素组成则相对较重,其碳、氢同位素组成之间具有较好的负相关。生物气碳、氢同位素组成的成气机理及途径有可能成为判识自然界采集的生物气气样是否具有工业意义,一般而言,乙酸发酵途径形成的生物气不利于成藏。     

A survey of pyritised animal,plant, and trace fossils and concretionary pyrites,Germav Formation,southeastern Turkey

The sulphide-bearing rocks of the Upper Cretaceous Germav Formation in southeastern Turkey (Bozova–Urfa) and the morphologically varied sulphide occurrences they contain have been investigated. Pyrite and marcasite are the main sulphide minerals; lesser bravoite and millerite also occur. Pyritised branches and leaves, trace fossils, and animal microfossils and macrofossils are abundant. Most of the concretionary and authigenic concretionary pyrite occurrences are probably related to burrows. The concretionary pyrites have low Co and high Ni contents and low Co:Ni ratios. The pyrite-rich lithostratigraphic sequences were deposited in a deep-sea environment, and pyrite mineralization developed in syn-sedimentary, early diagenetic and epigenetic stages under anoxic conditions. To cite this article: C. Bölücek, B. Ilhan, C. R. Geoscience 338 (2006).     

Pyrite-hydrocarbon Interaction under Hydrothermal Conditions: an Alternative Origin of H2S and Organic Sulfur Compounds in Sedimentary Environments

Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide(H_2S) in oil and gas reservoirs. However,a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H_2S generation,in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H_2S have not been evaluated. In this study,laboratory experiments were conducted from 200 to 450° C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results,preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H_2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H_2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However,much more organic sulfur compounds(OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally,most of sulfur liberated from pyrite at elevated temperatures was converted to H_2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H_2S,given the main hydrogen source derived from hydrocarbons. In addition,cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C,producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H_2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction(TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless,in some cases,OSCs and/or low contents of H_2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters(hydrocarbons),which still needs further investigation.