川东H2S气体分布特征及对储层的后期改造作用

研究高H2S天然气形成与分布对于认识有地下有机流体的地球化学行为及其成藏演化规律有较重要的科学意义。通过对川东H2S气体分布进行分析,认为本区天然气中H2S有两个高含量区:开江-梁平海槽以东的蒸发台地相区和处于开江-梁平海槽以西的开阔台地相区的部分井区。在侏罗世—早白垩世,富含SO42-的地层水不断沿原有溶孔、溶缝以及断裂进入古油藏;此外,发生TSR反应,同时产生大量酸性气体H2S和CO2。而这些酸性气体对早期方解石胶结物产生溶蚀作用,使得原有的孔隙不断扩大,对储层有改造作用。     

溶液中反应的热力学

通过几种溶液中的反应,并结合热力学函数的数据进一步阐释了中反应的自发性及反应的程度。     

谈热力学方法估算化学反应的反应温度

对环已醇催化脱氢制备环己酮的反应进行了热力学分析,利用热力学数据估算了谈反应的最低反应温度,综合考虑反应转化率,反应速平以及能耗问题,确定了适宣的反应温度范围为220～240℃;并结合生产实际,指出环己醇催化脱氢反应的生产工艺有待进一步改进。     

过氧化钠与二氧化碳、水反应顺序的热力学分析

本文对过氧化钠(Na2O2)在空气中先转化为白色固体而不是潮解,进行了热力学探讨,通过计算说明过氧化钠在空气中首先和二氧化碳反应,而不是和水反应。     

H2O2分解反应的不可逆过程热力学

扩展现行的线性不可逆过程热力学理论到远离平衡又没有产生耗散结构的体系,建立非均相体系只存在一个化学反应的反应速率通用方程,并将此反应速率方程应用于H2O2催化分解反应这个经典的动力学问题,分别得到了298K及308K条件下和实测数据吻合的四次关系式·结果表明考虑了高次项后,不可逆过程热力学可以用于远离平衡体系的化学反应·高次近似时,取多少次方对不同的化学反应条件是不同的,这决定于其远离平衡的程度,并且通过对线性不可逆过程热力学扩展的应用为远离平衡的化学反应的研究提供了一种新的方法·     

等离子体反应的统计热力学分析

通过热力学及统计力学分析，在定量、定压条件及局域平衡近似下，得出了体系各组分的分布与他们配分函数之间的关系；在此基础上，以煤等离子体热解反应制乙炔中起重要作用的物质氢为例，计算了不同温度下该物质组分H2，H2＋，H和H＋的分布；基本正确地描述了在氢在等离子体反应发生器及等离子体反应器的状态，为进一步深入研究提供了参考。     

La和Ni氢化反应热力学函数

在La和Ni原子相对论有效原子实势和基函数SDD下,使用密度泛函理论B3LYP方法计算得到LaH2和NiH2分子的结构、光谱数据、内能E、熵S等性质.计算固体LaH2和NiH2的E和S时,近似以气体分子的电子能和振动能代替固体分子的E,用电子熵和振动熵代替固体分子的S.在此近似下,计算了不同温度下La和Ni金属原子与氢气反应的热力学函数,得到La氢化反应温度与平衡压力的关系式.     

成岩作用的热力学分析及应用实例

介绍了通过热力学计算来绘制热力学相图的基本原理,采用从多维相图中切取不同平面的方法来研究多组分体系中各变量的影响关系.并应用此方法对江汉盆地西南缘砂岩的成岩作用进行了分析,指出其成岩作用发生的主要控制因素,并估算出其发生硬石膏胶结与交代作用时的环境介质条件:pH值应该在4—5之间,[Ca2 ]在10-3—10-2mol.L-1之间,[HCO3-]在10-3—10-1mol.L-1之间,[SO42-]在10-2.9—10-1mol.L-1之间,[Ca2 ]/[Mg2 ]<5.     

化学热力学关系式中反应进度的引入

反应进度概念(ζ）已引入到反应热的计算、化学平衡及反应速率的定义式中，但ζ没有普遍地被引入其它热力学关系式。因此，经过具体推证，将ζ系统地引入了热力学基本方程、对应系数关系式、化学平衡条件、自发方向的判据和平衡移动原理关系式中。并且推出化学亲和势的其它表示形式，从而使主要公式的应用更加规范。     

一种烷基转移反应体系的反应条件和热力学分析

对甲苯歧化与三甲苯烷基转移反应体系中不同温度和进料条件下的平衡组成，平衡转化率，平均选择论进行了详细计算，结果表明：（1）随温度的升高，甲苯与三甲苯的芳烃平衡转化率降低，二甲苯的平衡选择率亦降低；（2）降低进料中的甲苯与三甲苯摩尔比（Tol:TMB从9降到1），甲苯和三甲苯的芳烃平衡转化率降低，而二甲苯的平衡选择率明显上升，然后，在改性的β沸石催化剂上进行了不同工艺条件下的反应，通过对实验数据与平衡数据的比较和分析表明，反应温度升高，芳烃转化率上升且越来越接近平衡转化率，而二甲苯的选择率迅速下降；进料 中Tol:TMB存在一个最佳点，即60:40(m：m），此时芳烃转化率最高，二甲苯的选择率亦最高。     

The controlling factors and distribution prediction of H_2S formation in marine carbonate gas reservoir,China

Generally, there are some anhydrites in carbonate reservoir, as H2S is also familiar in carbonate oil and gas reservoirs. Nowadays, natural gas with high H2S concentration is usually considered as TSR origin, so there is close relationship between H2S and anhydrite. On the contrary, some carbonate rocks with anhydrite do not contain H2S. Recently, researches show that H2S is only a necessary condition of H2S formation. The reservoir porosity, sulfate ion content within formation water, reservoir temperature, oil/gas and water interface, hydrocarbon and some elements of reservoir rock have great controlling effects on the TSR occurrence. TSR deoxidizes hydrocarbon into the acidic gas such as H2S and CO2, and the H2S formation is controlled by TSR occurrence, so the relationship among reaction room, the contact chance of sulfate ion and hydrocarbon, the reservoir temperature has great influence on the TSR reaction. H2S has relatively active chemical quality, so it is still controlled by the content of heavy metal ion. Good conditions of TSR reaction and H2S preservation are the prerequisite of H2S distribution prediction. This paper builds a predictive model based on the characteristic of natural gas reservoir with high H2S-bearing. In the porosity reservoir with anhydrite, the formation water is rich in sulfate and poor in heavy metal ion. Oil and gas fill and accumulate in the gas reservoir with good preservation conditions, and they suffered high temperature later, which indicates the profitable area of natural gas with high H2S-bearing.     

The controlling factors and distribution prediction of H2S formation in marine carbonate gas reservoir, China

Generally, there are some anhydrites in carbonate reservoir, as H2S is also familiar in carbonate oil and gas reservoirs. Nowadays, natural gas with high H2S concentration is usually considered as TSR origin, so there is close relationship between H2S and anhydrite. On the contrary, some carbonate rocks with anhydrite do not contain H2S. Recently, researches show that H2S is only a necessary condition of H2S formation. The reservoir porosity, sulfate ion content within formation water, reservoir temperature, oil/gas and water interface, hydrocarbon and some elements of reservoir rock have great controlling effects on the TSR occurrence. TSR deoxidizes hydrocarbon into the acidic gas such as H2S and CO2, and the H2S formation is controlled by TSR occurrence, so the relationship among reaction room, the contact chance of sulfate ion and hydrocarbon, the reservoir temperature has great influence on the TSR reaction. H2S has relatively active chemical quality, so it is still controlled by the content of heavy metal ion. Good conditions of TSR reaction and H2S preservation are the prerequisite of H2S distribu- tion prediction. This paper builds a predictive model based on the characteristic of natural gas reservoir with high H2S-bearing. In the porosity reservoir with anhydrite, the formation water is rich in sulfate and poor in heavy metal ion. Oil and gas fill and accumulate in the gas reservoir with good preservation conditions, and they suffered high temperature later, which indicates the profitable area of natural gas with high H2S-bearing.     

Detection of 2-thiaadamantanes in the oil from Well TZ-83 in Tarim Basin and its geological implication

Thermochemical sulfate reduction （TSR） causes increasing of sulfur content in the oils, reduction of oil quality, and produces a toxic and corrosive H2S which may take great adverse effect on health and equipment. Although there are several ways to identify presence of TSR in gas field, yet in the case of oil with low H2S content, it is still very difficult to identify TSR. 2-thiaadamantanes is one of the most effective indicators of TSR. This paper for the first time discovers 2-thiaadamantanes in the oil from Well TZ-83 in Tarim Basin. A silver nitrate silica gel chromatography was used to enrich the oil from low 2-thiaadamantanes content to the level that GC/MS and GC/MS/MS can detect. 2-thiaadamantanes were assigned by comparison of mass spectra with published data, and the fragmental ions in mass spectra were confirmed by MRM mode of GC/MS/MS. H2S gas produced in Tazhong area is thought to be generated from TSR since 2-thiaadamantanes were present in the oil.     

稠油硫酸盐热化学还原生成H2S实验研究

为了研究稠油注汽热采过程中生成H₂S机理，以Na₂SO₄，CaSO₄，MgSO₄，Fe₂（SO₄）₃，Al₂（SO₄）₃与稠油硫酸盐热化学还原（TSR）实验为基础，探究稠油TSR生成H₂S机理。实验表明，不同硫酸盐与稠油反应生成H₂S不尽相同，硫酸盐的阳离子所带电荷数决定TSR反应程度的难易，电荷数越多越容易进行反应，且H₂S生成量顺序为Al₂（SO₄）₃>Fe₂（SO₄）₃ > MgSO₄ > CaSO₄ > Na₂SO₄，但生成的烃量顺序为Fe₂（SO₄）₃ > Al₂（SO₄）₃ > MgSO₄ > CaSO₄ > Na₂SO₄。与其他硫酸盐不同的是，由于Fe₂（SO₄）₃的氧化性，Fe³⁺可能与生成的H₂S进一步反应。通过傅里叶红外变换光谱（FT-IR）对固相检测发现，不仅存在金属氧化物（CaO，MgO，Fe₂O₃，Al₂O₃）还存在FeS₂。最后，通过对MgSO₄油相硫含量的检测发现，反应后硫含量高于原油硫含量，证明了无机硫向有机硫的转化。     

2(5H)-呋喃酮的水相Diels-Alder反应

研究了2(5H)-呋喃酮、5-羟基-2(5H)-呋喃酮与环戊二烯发生Diels-Alder反应,产物用FT-IR、1HNMR、MS进行了表征。该反应在水相中进行时,反应时间为0.5 h,比在有机相反应的时间大大缩短。     

基于Ti-Nb-Zr三元系合金的相图优化

利用Pandat软件优化和计算了Ti-Nb-Zr三元系相图。采用SGTE(scientific group thermodata Europe)数据库中的表达式描述纯组元的吉布斯能,选取置换溶体模型和双亚点阵模型来描述液相和固溶体相。利用Pandat软件的PanOptimizer模块并结合文献中相平衡和热力学性质的实验数据,重新评估了Ti-Nb和Ti-Zr二元系的热力学参数以改善Ti-Nb-Zr三元系的热力学描述。利用优化得到的热力学参数进行相平衡和热力学性质的计算,计算结果与文献实验结果吻合较好,该结果对Ti-Nb-Zr三元系生物医学材料的开发有重要的指导意义。     

Simulation experiments on the reaction system of CH_4-MgSO_4-H_2O

H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction (TSR). In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃―525℃. The threshold temperature for initiating TSR is much lower than our previous studies (550 ℃ ). Properties of the reaction products were analyzed by microcoulometry, gas-chromatography (GC), Fourier transform-infrared spectrometry (FT-IR) and X-ray diffraction (XRD) methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon diox-ide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac-cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg2 may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.     

重氮去氮反应在S_N中的溶剂效应

以 2 ,4 二甲基 6 硝基乙酰苯胺为起始原料 ,用乙醇作还原剂合成了 3,5 二甲基硝基苯 ;给出　了产物光谱分析和高压液相色谱分析数据 ;分析重氮去氮反应在酸性介质中的溶剂效应并提出在浓酸溶液中 ,当　酸度函数H0 =- 3.5时生成物产率最好     

成岩体系中斜长石向浊沸石转变的热力学过程

许多含油气盆地碎屑岩储层中都观察到明显的浊沸石胶结现象.岩石学研究显示斜长石通常是埋藏成岩过程中自生浊沸石最主要的物质来源.本文从热力学的角度探讨了斜长石发生水-岩反应形成浊沸石的可能性及形成条件.与以往不同的是,计算的反应物对象不再是理想的端元长石矿物,而是通过实验数据和Darken's二次理论(DQF)利用不同组分斜长石进行计算.计算结果显示,斜长石向浊沸石的转变可以在成岩作用阶段发生,并且该反应趋势对温度的依赖性强,而对压力的依赖性弱.在埋藏成岩封闭环境中,温度越高,转变趋势越强烈.在开放环境存在额外的Na+条件下,浊沸石在低温条件下借助钙长石组分形成钠长石化的可能性更大.比较以不同比例的钙长石、钠长石组成的斜长石的蚀交反应后发现,富钙斜长石的稳定性低于富钠斜长石,并易造成选择性溶蚀.在与方解石竞争Ca2+的过程中,浊沸石能否形成主要取决于环境的温度、CO2分压、流体pH值以及流体中的离子类型和浓度.     

RECl3—SrCl2—LiCl三元系相图计算

基于对9个侧边二元系RECl2-SrCl2,RECl3-LiCl,SrCL2-LiCl(其中RE：La,Ce,Pr,Nd)，热力学数据和实验相图信息的优化，评估，以及三元系相关热力学性质的分析，计算并讨论了RECl3-SrCl2-LiCl系列4个三元系相图。