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1.
硫酸盐热化学还原作用对原油裂解成气和碳酸盐岩储层改造的影响及作用机制 总被引：4，自引：3，他引：1
硫酸盐热化学还原作用(Thermochemical sulfate reduction, TSR)是发生在油气藏中复杂的有机-无机相互作用,它不仅会引起含H2S天然气的富集,其产生的酸性气体对碳酸盐岩储层还具有明显的溶蚀改造作用。本文基于黄金管热模拟实验,研究了TSR反应对原油裂解气的生成的影响,发现这种氧化还原反应的存在能明显降低原油的稳定性,促进具高干燥系数的含H2S天然气的生成。结合原位激光拉曼实验结果,证实了实际油藏中启动TSR反应的最可行的氧化剂应该是硫酸盐接触离子对(CIP)。全面探讨了影响TSR反应的地质和地球化学因素,提出除了初始原油的组分特征、不稳定含硫化合物(LSC)的含量外,地层水的含盐类型及盐度同样是控制TSR反应的关键因素。同时,基于大量地质分析,发现TSR对碳酸盐岩储层具有明显的溶蚀改造作用。结合溶蚀模拟实验,提出了酸性流体对碳酸盐储层溶蚀改造的机制,且深层碳酸盐岩层存在一个由TSR作用形成的次生孔隙发育带。研究认为,烃类与硫酸盐矿物的氧化还原反应与其产物对碳酸盐岩储层的改造是TSR作用的两个不可分割的部分,它们相互依存和制约。 相似文献
2.
为了研究碳酸盐岩储层原油裂解过程中硫、钙元素赋存状态的变化,采集塔河油田TK772井奥陶系鹰山组产层的原油,通过半开放实验体系"地层孔隙热压生排烃模拟仪"开展仿真地层条件的成气模拟实验,利用同步辐射X射线吸收近边结物(XANES)技术对固体产物中的硫、钙元素的化学赋存状态进行精确检测。结果表明,原油直接裂解(原油+灰岩实验(系列1))固体产物中含硫化合物以噻吩类和硫酸钙为主,是原油裂解过程中部分噻吩类物质被氧化的结果;含钙化合物以碳酸钙为主。有溶解硫酸盐存在的原油裂解(原油+灰岩+硫酸镁实验(系列2))固体产物中含硫化合物以硫酸钙为主,噻吩类为辅,可能是溶解硫酸盐(硫酸镁)的加入、硫酸盐热化学还原反应(TSR)和溶蚀-沉淀作用共同作用的结果。系列2中伴随着温压的升高,H2S的生成和硫酸钙相对百分含量增加,指示原油裂解过程中发生了硫酸盐热化学还原反应(TSR);硫酸钙的生成和富集表明,TSR过程产生的酸性流体可以对碳酸盐岩储层产生明显的溶蚀作用,同时可能会生成次生膏盐。 相似文献
3.
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 总被引：1，自引：0，他引：1
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。 相似文献
4.
对四川盆地东部50个天然气样品组分和碳、氢同位素组成分析结果显示,天然气以烃类气体为主,干燥系数高(C1/C1+=0.975~1.0),H2S含量变化较大(H2S=0.00%~16.89%)。利用烷烃气碳、氢同位素组成和判识油型气热演化程度图版,确定四川盆地东部天然气主要为原油裂解气,且热演化程度已处于油气裂解阶段。在四川盆地东部,烷烃气碳、氢同位素组成普遍存在局部倒转现象,即δ13C1δ13C2δ13C3和δD1δD2,这主要与研究区域不同硫酸盐热化学还原作用(TSR)强度有关,因为在该反应过程中不仅会产生大量的CH4,其碳同位素较重,同时,水参与了硫酸盐与烃类的化学还原反应使得水中的H+与烃类中H+发生同位素交换,从而引起TSR生成CH4的氢同位素分馏大于干酪根直接生烃过程造成的氢同位素分馏。异常δ13CCO2值与TSR反应过程中部分碳同位素较轻的CO2与硫酸盐中金属离子(Mg2+、Fe2+、Ca2+等)以碳酸盐的形式沉淀后,导致气藏中残余重碳同位素组成的CO2与酸性气体腐蚀碳酸盐岩储集层形成的CO2相混合有关。 相似文献
5.
综合分析四川盆地高石梯—磨溪地区(高-磨地区)震旦系—寒武系天然气、储层沥青及膏盐分布等,发现高-磨地区天然气发生过不同程度硫酸盐热化学还原作用(TSR)反应。主要基于:①天然气中含一定丰度H_2S,震旦系灯影组H_2S含量为0.6%～3%,寒武系龙王庙组为0.2%～0.8%;其δ~(34)S值普遍较重(21‰～23‰),为TSR反应产物;②储层沥青S/C原子比介于0.06～0.4之间,远远超过有机质裂解生成沥青中S/C比的最高上限(0.034),峰值甚至超过了TSR反应强烈的川东北普光气田飞仙关组储层沥青的比值(0.06～0.12),为TSR过程无机S加入所致;③四川盆地寒武系底部发育膏盐类沉积,为TSR反应提供了SO_4~(2-)和Mg~(2+)等物质,灯影组发育富Ca~(2+)/Mg~(2+)、贫Na~+/K~+型地层水,证明盐、膏类溶解的普遍性。地层水中相对缺乏SO_4~(2-),应为TSR反应消耗所致。TSR反应明显氧化乙烷,导致天然气干燥系数增加、δ~(13)C_2变重;TSR反应程度不同造成了龙王庙组和灯影组天然气特征的差异,龙王庙组TSR反应程度相对较弱,天然气甲乙烷碳同位素明显倒转;而灯影组TSR反应程度相对要强,甲乙烷同位素正序分布。考虑TSR效应,恢复原始组成,高-磨地区寒武系—震旦系天然气应有明显的甲烷、乙烷碳同位素倒转现象,这种倒转跟该盆地及世界高—过成熟页岩气特征高度一致,暗示高-磨地区主力气源可能为源岩晚期所成天然气。这一认识可以很好诠释甲烷δ~(13)C_1值较重、普遍低于储层沥青这一为现在主流认识(高-磨地区主体为原油裂解气)所不好解释的现象。对于重新认识天然气成藏聚集规律具有重要意义。 相似文献
6.
传统认为TSR成因的固态沥青(焦沥青)属于热化学反应的终端产物,不会对TSR的反应进程起到重要作用.本文以活性炭作为固态沥青(焦沥青)的模型化合物,开展了CaSO4-C-H2O体系的热模拟实验研究,探讨了CaSO4-C-H2O体系发生TSR的热力学特征.实验结果表明,CaSO4-C-H2O体系在300℃时即可启动TSR,主要生成CaCO3、H2S和CO2等产物.这一TSR门限温度要远低于以往室内利用气态或液态烃类进行的TSR模拟实验温度范围,与热力学计算结果一致.利用HSC Chemistry 5.0软件进行TSR过程模拟,发现25～200℃时CaSO4-C-H2O体系发生的TSR完全受动力学控制,在温度保持不变情况下,压力增大不利于CaSO4-C-H2O体系发生TSR.较少的含水量对TSR有一定促进作用,而含水量过多则可能抑制TSR的进行,含水量对TSR的影响可能与CaSO4在水中的饱和浓度有关.在一定的温度下,当体系pH≤2时,随着pH逐渐降低,CaSO4的量呈线性递减,但在沉积盆地地层水pH范围内(pH＞4),pH对TSR的作用可以忽略不计.CaSO4-C-H2O体系发生的TSR反应是一个放热过程,并且随着温度升高,反应热逐渐增大.在25～200℃范围内,TSR反应热为12.9～133 J/molCaSO4.热力学计算以及模拟实验结果均暗示,固态沥青(焦沥青)可能比烃类更容易参与TSR. 相似文献
7.
川东北元坝气田是中国南方大型油气田之一,通过对元坝224井上二叠统储层溶洞石英及白云石中包裹体的岩相学、激光拉曼以及显微测温分析发现,溶洞石英中包裹体类型复杂,主要由气液两相包裹体、气体包裹体以及含子矿物包裹体组成,包裹体的气相组分主要由CH4、H2S以及CO2组成,包裹体的子矿物为单质硫以及沥青,包裹体共生组合关系复杂,不同类型包裹体常叠加在一起,气液两相包裹体均一温度以及含单质硫三相包裹体的气液均一温度范围相似,分别为161.5~220.6℃以及168.2~218.6℃,二者的盐度分布范围差别较大,分别为7.45%~10.36%NaCl以及8.68%~21.11%NaCl;溶洞白云石中包裹体类型单一,由气液两相包裹体组成,个别包裹体的气相中含有CH4,包裹体的均一温度为102.4~132.1℃。包裹体的古温度古压力分析表明,溶洞石英中包裹体捕获于中—晚侏罗世,包裹体捕获时地层流体为超压,捕获于原油大量裂解生成天然气阶段。溶洞石英中不同类型包裹体的组合关系以及温压特征记录了储层中TSR反应的过程,即硫酸盐先与重烃反应生成H2S以及单质硫,然后硫酸盐以及生成的单质S再与CH4继续反应生成H2S以及CO2,随着TSR反应的进行,储层中的压力逐渐增大。TSR反应生成的H2S以及CO2流体可能与储层发生了较强烈的水-岩反应,造成了储层的硅化以及溶洞中石英、白云石的沉淀。 相似文献
8.
川东北飞仙关组鲕滩天然气地球化学特征与成因 总被引：29，自引：3，他引：26
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,C2 含量很少,为0%～0.15%,干燥系数为0.997 0～0.999 8,是典型的干气;非烃气体以H2S和CO2为主,含量分别为4.21%～16.24%和0.97%～10.41%.天然气δ13C1值为-29.0‰～-31.5‰,δ13C2值为-29.4‰～-32.4‰.多参数表明鲕滩气藏天然气是以腐泥型为主的高过成熟天然气.高含H2S的天然气分布区域与含石膏地层分布基本一致,这些H2S为飞仙关组气藏附近的石膏经热化学硫酸盐还原作用(TSR)而生成,CO2是其主要的副产物.在TSR过程中,C2 重烃气体比甲烷更容易与硫酸盐发生反应,也就是C2 重烃气体的消耗速率大于甲烷,从而导致发生TSR反应的天然气C2 含量低、H2S和CO2含量高.天然气δ13C1值与甲烷含量之间具有很好的负相关关系,而与天然气酸性系数[H2S/(H2S CnH2n 2)]具有正相关关系.根据同位素动力学的分馏效应,随着TSR的进行,烃类分子中的12C损耗速率大于13C,残留下来的烃类分子中则更加富集13C,也就是TSR反应使天然气碳同位素变重. 相似文献
9.
甲烷和固态硫酸钙的热化学还原反应模拟实验初步研究 总被引：14，自引：4，他引：14
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。 相似文献
10.
顺北地区4号断裂带奥陶系油气藏相态复杂，自NE向SW,油气藏相态的变化情况是挥发油藏—低气油比凝析气藏—高气油比凝析气藏—中等气油比凝析气藏。使用地球化学分析方法研究了顺北4号断裂带油气藏的地球化学特征，分析了相态差异性的成因。4号断裂带原油生标含量低甚至缺失，原油生源与1号断裂带原油生源相同。4号断裂带原油成熟度高于1号断裂带原油，等效反射率为1.14%～1.60%。4号断裂带天然气干燥系数由NE向SW方向渐进增大，天然气成熟度为1.30%～1.70%。天然气中H2S、CO2含量由NE向SW方向呈现增加的趋势。全油色谱正构烷烃摩尔分数对数与正构烷烃碳数的关系表明，4号断裂带原油未遭受蒸发分馏作用；4号带原油金刚烷含量分布范围为27.26～523.31μg/g,原油裂解作用程度为20.5%～95.8%,裂解程度较1号断裂带原油裂解作用高；SB4、SB41X-C和SB42X井原油硫代金刚烷含量为33.76～76.92μg/g,表明这些油气藏发生了硫酸盐热化学还原(TSR)作用。顺北4号断裂带奥陶系油气藏相态变化与两个因素有关：一是4号断裂带地温... 相似文献
11.
Organic sulfur compounds are ubiquitous in natural oil and gas fields and moderate-low temperature sulfide ore deposits. Previous studies have shown that organic sulfur compounds are important in enhancing the rates of thermochemical sulfate reduction (TSR) reactions, but the details of these reaction mechanisms remain unclear. In order to assess the extent of sulfate reduction in the presence of labile sulfur species at temperature conditions near to those where TSR occurs in nature, we conducted a series of experiments using the fused silica capillary capsule (FCSS) method. The tested systems containing labile sulfur species are MgSO4 + 1-pentanethiol (C5H11SH) + 1-octene (C8H16), MgSO4 + 1-octene (C8H16), MgSO4 + 1-pentanethiol (C5H11SH), 1-pentanethiol (C5H11SH)+H2O, and MgSO4 + 1-pentanethiol (C5H11SH) + ZnBr2 systems. Our results show that: (1) intermediate oxidized carbon species (ethanol and acetic acid) are formed during TSR simulation experiments when 1-pentanethiol is present; (2) in the presence of ZnBr2, 1-pentanethiol can be oxidized by sulfate to CO2 at 200 °C, which is within the temperature range observed in natural TSR; and (3) the precipitation of sulfide minerals may significantly promote the rate of TSR, indicating that the rates of in situ TSR reactions in ore deposits could be much faster than previously thought. This may be important for understanding the possibility of in situ TSR as a mechanism for the precipitation of metal sulfides in some ore deposits. These findings provide important experimental evidence for understanding the role of organic sulfur compounds in TSR reactions and the pathway of TSR reactions initiated by organic sulfur compounds under natural conditions. 相似文献
12.
Hong LuPaul Greenwood Tengshui ChenJinzhong Liu Ping’an Peng 《Organic Geochemistry》2011,42(6):700-706
The mechanism of thermochemical sulfate reduction (TSR) was investigated by separately heating n-C24 with three different sulfates (CaSO4, Na2SO4, MgSO4) in sealed gold tubes at 420 °C and measuring the stable carbon isotope values of hydrocarbon (C1-C5) and non-hydrocarbon (CO2) products. Extensive TSR was observed with the MgSO4 reactant as reflected by increasing concentrations of H2S, 13C depleted CO2 and relatively low concentrations of H2 (compared to the control). H2S yields were already very high at the first monitoring time (12 h) when the temperature had just reached 420 °C, suggesting that TSR had commenced well prior to this temperature. Only trace amounts of n-C24 and secondary C3-C5 alkanes were detected at 12 h, reflecting the efficient TSR utilization of the reactant and lower molecular weight alkane products. Ethane levels were still relatively high at 12 h, but declined thereafter as it was subject to TSR in the absence of higher molecular weight alkanes which had already been utilized. Methane yields were consistently high throughout the 48 h MgSO4 treatment. The temporal decrease in the concentrations of alkanes available for TSR may also contribute to the sharp enhancement of CO2 after 36 h. Absence or dampening of the molecular and isotopic trends of MgSO4 TSR was observed with Na2SO4 and CaSO4 respectively, directly reflecting the levels of TSR reached using these sulfate treatments.For all treatments, the δ13C values of C1-5n-alkanes showed an increase with both molecular weight and treatment time. MgSO4 TSR led to a 5-10‰ increase in the δ13C values of the C1-C5 hydrocarbons and a 20‰ decrease in the δ13C value of CO2. The significant 13C depletion of the CO2 may be due to co-production of 13C enriched MgCO3, although this remains unproven as the δ13C of MgCO3 was not measured. The difference in the δ13C values of ethane and propane (Δδ13CEP) increased in magnitude with the degree of TSR, and this trend could be used to help evaluate the occurrence and extent of TSR in subsurface gas reservoirs. 相似文献
13.
The yields and stable C and H isotopic composition of gaseous products from the reactions of pure n-C24 with (1) MgSO4; and (2) elemental S in sealed Au-tubes at a series of temperatures over the range 220–600 °C were monitored to better resolve the reaction mechanisms. Hydrogen sulfide formation from thermochemical sulfate reduction (TSR) of n-C24 with MgSO4 was initiated at 431 °C, coincident with the evolution of C2–C5 hydrocarbons. Whereas the yields of H2S increased progressively with pyrolysis temperature, the hydrocarbon yields decreased sharply above 490 °C due to subsequent S consumption. Ethane and propane were initially very 13C depleted, but became progressively heavier with pyrolysis temperature and were more 13C enriched than the values of a control treatment conducted on just n-C24 above 475 °C. TSR of MgSO4 also led to progressively higher concentrations of CO2 showing relatively low δ13C values, possibly due to input of isotopically light CO2 derived from gaseous hydrocarbon oxidation (e.g., more depleted CH4). 相似文献
14.
Experimental studies of the effects of thermochemical sulfate reduction (TSR) on light hydrocarbons were conducted in sealed gold tubes for 72 h at 400 °C and 50 MPa. A variety of pyrolysis experiments were carried out, including anhydrous, hydrous without MgSO4 (hydrous experiments) and hydrous with MgSO4 (TSR experiments). Common reservoir minerals including montmorillonite, illite, calcite and quartz were added to various experiments. Measurements of the quantities of n-C9+ normal alkanes (high molecular weight, HMW), n-C6-8 normal alkanes (low molecular weight, LMW), C7-8 isoalkanes, C6-7 cycloalkanes and C6-9 monoaromatics and compound specific carbon isotope analyses were made. The results indicate that TSR decreases hydrocarbon thermal stability significantly as indicated by chemically lower concentrations and isotopically heavier LMW saturated hydrocarbons in the TSR experiments compared to the hydrous and anhydrous experiments. In the LMW saturated hydrocarbon fraction, cycloalkanes tend to be more resistant to TSR than n-alkanes and isoalkanes. TSR promotes aromatization reactions and favors the generation of monoaromatics, resulting in higher chemical concentrations and isotopically equivalent compositions of monoaromatics in the anhydrous, hydrous and TSR experiments. This indicates that LMW monoaromatics are thermally stable during the pyrolysis experiments. Acid rather than basic catalyzed ionic reactions probably play a major role in TSR. This is suggested by the promotion effects of acid-clay minerals including illite and particularly montmorillonite. The basic mineral calcite retards the destruction of n-C9+ normal alkanes within the TSR experiments. Furthermore, clay minerals have a minor influence on the generation of LMW monoaromatics and play a negative role in regulating the concentrations of LMW saturated hydrocarbons; calcite does not favor the generation of LMW monoaromatics and plays a positive role in controlling the concentrations of LMW saturates relative to clay minerals. Quartz has a negligible role in the TSR experiments.Due to their differential responses to TSR, LMW hydrocarbon parameters, such as Schaefer [Schaefer, R.G., Littke, R., 1988. Maturity-related compositional changes in the low-molecular-weight hydrocarbon fraction of Toarcian Shale. Organic Geochemistry 13, 887-892], Thompson [Thompson, K.F.M., 1988. Gas-condensate migration and oil fractionation in deltaic systems. Marine and Petroleum Geology 5, 237-246], Halpern [Halpern, H., 1995. Development and application of light-hydrocarbon-based star diagrams. American Association of Petroleum Geologists Bulletin 79, 801-815] and Mango [Mango, F.D., 1997. The light hydrocarbons in petroleum: a critical review. Organic Geochemistry 26, 417-440] parameters and stable carbon isotopic compositions of individual LMW saturated hydrocarbons in TSR affected oils should be used with caution. In addition, water promotes thermal cracking of n-C9+ normal alkanes and favors the generation of LMW cycloalkanes and monoaromatics. The result is lower concentrations of n-C9+ HMW normal alkanes and higher concentrations of LMW cycloalkanes and monoaromatics in hydrous experiments relative to anhydrous experiments with or without minerals.This investigation provides a better understanding of the effects of TSR on LMW hydrocarbons and the influence of reservoir minerals on TSR in natural systems. The paper shows how LMW hydrocarbon indicators in TSR altered oils improve understanding of the processes of hydrocarbon generation, migration and secondary alteration in subsurface petroleum reservoirs. 相似文献
15.
Hydrogen sulfide (H2S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO4 in the presence of variable H2S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H2S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H2S concentrations. To investigate whether the reaction of H2S(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO4 and variable H2S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO4 reduction was not measurable in the absence of paraffin even with high H2S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H2S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H2S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H2S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H2S pressure. Thus, we propose that the LSC produced from H2S reaction with HC are most likely the reactive intermediates for H2S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content. 相似文献
16.
The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions () and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive.Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of relative to . However, in formation waters typically encountered in petroleum reservoirs, the concentration of is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as , aqueous calcium sulfate ([CaSO4](aq)), and aqueous magnesium sulfate ([MgSO4](aq)). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions () and/or magnesium sulfate contact ion-pairs ([MgSO4]CIP) rather than ‘free’ sulfate ions () or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR. 相似文献
17.
The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n-octane and CaSO4 in the presence of reduced sulfur (e.g. H2S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H2S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n-octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H2S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H2S. Second, we considered the generation of olefines in association with the elimination of H2S during thermal degradation of thiols because olefines are much more reactive than n-alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S-O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H2S accumulation in petroleum reservoirs. 相似文献
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19.
Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry 总被引：1，自引：0，他引：1
XIANG Caifu PANG Xiongqi WANG Jianzhong LI Qiming WANG Hongping ZHOU Changqian YANG Haijun 《《地质学报》英文版》2010,84(2):358-369
<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district. 相似文献