不同形态的硫与有机质的相互作用研究

发布时间：2018-05-24 03:03

本文选题：高硫有机质 + 热模拟实验　；参考：《中国科学院广州地球化学研究所》2017年博士论文

【摘要】：硫在自然界分布广泛,硫循环与生命活动密切相关,因此在生命遗体演化形成的各种化石能源中往往有大量硫的存在。硫的化学性质活泼,它的存在会腐蚀开采设备,增加化石能源开采成本;天然气气田中的硫化氢气体剧毒,会危害人类的生命安全;原油中含硫化合物降低原油品质,提高了石油炼化的难度。含硫或高硫是我国化石能源的一个重要特点:中、高硫煤可占所有煤炭资源的1/4以上;高硫原油占目前生产的原油30%以上,随着原油的进一步开采,高硫的趋势还将进一步扩大。这些化石能源中硫的存在形式、演化规律与有机质的热演化密切相关,因此,研究不同形态的硫与有机质的相互作用、硫在有机质热演化过程中进入有机质的途径及含硫化合物的迁移与演化,是解决化石能源高硫问题首先要回答的基础问题。本文利用金管限定体系反应装置,选取多种形态的硫和有机物进行热模拟实验,对生成的有机、无机气体进行产率和碳同位素分析,并对生成的液态烃和固体产物展开了定性分析,研究了不同含硫干酪根、原油的生烃特征,C7轻烃的TSR反应特征,硫酸亚铁的TSR反应以及后续黄铁矿的形成与演化,最后探索了烯烃硫化作用过程和可能的反应机理。本论文主要取得了以下成果和认识:1.本研究所选的油柑窝组低硫干酪根(含硫2.78%)与板9井高硫干酪根(含硫14.28%)具有较为相似的气态烃演化规律与动力学特征;本研究选用的丫角12-13高硫原油中硫的存在形式主要包括烷基四氢噻吩、苯并噻吩、二苯并噻吩三类,而长斜9-1低硫原油中硫的存在形式主要包括苯并噻吩和二苯并噻吩两类。两种原油中硫的含量与存在形式差异,共同导致了丫角12-13高硫原油热解产生了大量硫化氢气体而长斜9-1原油几乎不产生硫化氢气体。2.正庚烷和甲苯的轻烃TSR反应研究:高成熟条件下油气藏发生轻质化和芳香化明显,因此,以正庚烷和甲苯的C7轻烃开展了TSR模拟实验研究,结果表明轻烃中的饱和烃和芳香烃均可发生强烈的TSR反应,造成气态烃碳同位素变重。反应过程中甲烷未参加TSR反应,其产率的减少来自于更高碳数的甲烷前体物的影响。TSR反应过程中产生了一些有机硫化物,它们的存在可能促进了TSR反应的早期启动。3.硫酸亚铁与正构十八烷可发生强烈的TSR反应,导致甲烷产率上升和碳同位素变重,二氧化碳产率明显增加,其碳同位素明显变轻。亚铁离子的存在与硫化氢在350℃下反应形成黄铁矿,因而没有检出硫化氢;略高温450℃条件下,黄铁矿完全分解形成了磁黄铁矿与单质硫。反应过程中形成的单质硫,则大大促进了TSR反应的发生。4.硫磺、黄铁矿和硫氢化钠均可与正辛烯发生硫化反应形成有机硫化合物;硫磺系列中产物存在多硫化合物,可能是形成硫醇的关键中间产物;整个反应中2-辛硫醇的含量远高于1-辛硫醇,其反应机理既不是硫自由基的作用,也不是简单的硫化氢亲电反应,而是反应过程中产生的多硫化合物与双键的协同作用造成的。
[Abstract]:Sulfur is widely distributed in nature, and sulfur cycle is closely related to life activities. Therefore, a large amount of sulfur is often found in all kinds of fossil energy evolved from the remains of life. The chemical properties of sulfur are active. Its existence will corrode the mining equipment and increase the cost of fossil energy exploitation; the hydrogen sulfide gas in the gas field of Tian ran gas gas field will be harmful to human beings. The sulfur containing compounds in crude oil reduce the quality of crude oil and improve the difficulty of petroleum refining. Sulfur or high sulfur is an important feature of fossil energy in China: high sulfur coal can account for more than 1/4 of all coal resources; high sulfur crude oil accounts for more than 30% of the current crude oil. With further exploitation of crude oil, the trend of high sulfur will also be advanced. The existing forms and evolution laws of sulfur in these fossil fuels are closely related to the thermal evolution of organic matter. Therefore, the study of the interaction between different forms of sulfur and organic matter, the way to enter organic matter in the process of thermal evolution of organic matter and the migration and evolution of sulfur compounds in the process of thermal evolution of organic matter are the first to solve the problem of high sulfur in fossil energy. The basic problem of the answer. In this paper, a variety of forms of sulfur and organic matter are selected for thermal simulation experiments with various forms of sulfur and organic matter. The yield and carbon isotopes of the generated organic and inorganic gases are analyzed. The qualitative analysis of the generated liquid hydrocarbon and solid products is carried out, and the different sulfur containing kerogen and crude oil are studied. The characteristics of the TSR reaction of C7 light hydrocarbons, the TSR reaction of ferrous sulfate and the formation and evolution of the subsequent pyrite. Finally, the sulfurization process and possible reaction mechanism of olefin were explored. The following achievements and understanding were obtained in this paper: 1. the low sulphur dried kerogen (sulfur 2.78%) and the high sulphur kerogen (sulfur 14) in well 9 well selected in the study were selected. .28%) has a relatively similar evolution and kinetic characteristics of gaseous hydrocarbons. The existing forms of sulfur in 12-13 high sulfur crude oil selected in this study include alkyl four thiophene, benzo thiophene and two benzo thiophene, while the existing forms of sulfur in the long slant 9-1 low sulfur crude mainly include two classes of benzo thiophene and two benzo thiophene. Two kinds of raw sulfur are the main forms of sulfur. The difference in the content of sulphur in the oil and its existing form leads to the study of the pyrolysis of 12-13 high sulfur crude oil produced by the Yok Jiao, which produces a large amount of hydrogen sulfide gas while the long slant 9-1 crude oil does not produce the light hydrocarbon TSR reaction of.2. n-heptane and toluene. TSR simulation experiments of C7 light hydrocarbons have been carried out. The results show that a strong TSR reaction can occur in the saturated and aromatic hydrocarbons in the light hydrocarbons, resulting in a heavy carbon isotope of gaseous hydrocarbons. Methane did not participate in the TSR reaction during the reaction, and the reduction of the yield of methane was derived from the effect of the higher carbon number of methane precursors in the.TSR reaction. Sulfides, their existence may promote the early start of the TSR reaction, which can lead to a strong TSR reaction between.3. sulphate and normal eighteen alkanes, resulting in a rise in methane yield and heavy carbon isotopes, a significant increase in carbon dioxide yield and a significant reduction in carbon isotopes. The existence of ferrous ions and the formation of pyrite at 350 C, Therefore, no hydrogen sulfide was detected; pyrite was completely decomposed into pyrrhotite and elemental sulfur under the condition of a slightly high temperature of 450. The formation of pyrrhotite and elemental sulfur in the reaction process greatly promoted the occurrence of.4. sulfur in the TSR reaction. Polysulfide compounds may be the key intermediates in the formation of mercaptan, and the content of 2- symphol in the whole reaction is much higher than that of 1- symphoxol. The reaction mechanism is neither the action of sulfur free radicals nor the simple hydrogen sulfide reaction, but the synergistic effect of the polysulfide and the double bonds in the reaction process.
【学位授予单位】：中国科学院广州地球化学研究所
【学位级别】：博士
【学位授予年份】：2017
【分类号】：P618.13

【相似文献】