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1.
生油岩产生低分子量有机酸的模拟实验研究 总被引：7，自引：1，他引：7
通过对低成熟的生油岩样岩样品进行有水和无水热解实验，在不同温阶下的水溶液产物中均检测到低分子量有机酸。把这些有机酸的分布与油田水样品相比较，发现两者在组成上很近似。再加入不同矿物的样品，热解后的有机酸组成与干酷根单热解样品有较大差别，这表明产酸过程中水和无机矿物起了重要作用。 相似文献
2.
原油的有水热解产生低分子量有机酸的研究 总被引：5，自引：0，他引：5
用原油及其族组分加入矿物和不同离子浓度的水进行了有水热解，对热解后的水溶液做了低分子量有机酸分析。实验表明，储集层中的原油在热作用下能产生有机酸，但不同条件下，生成的量有所不同。高浓度的卤水对产酸有利，加入不同矿物，砂岩对热解有微弱催化作用，而氧化性矿物能提高产酸量。就原油中不同族组分而言，沥青质生成有机酸的贡献最大。 相似文献
3.
用石英、微斜长石和方解石混合颗粒模拟碎屑组分分别与不同有机酸水溶液进行溶蚀实验,以比较储集层内不同矿物在含低分子量有机酸地层水中溶解的速率,并试图探讨矿物溶蚀的微观机理。结果表明：①所有矿物颗粒都发生了不同程度的溶解,表现为颗粒失重,溶液中SiO2和金属阳离子含量增加,pH值上升。②优先溶解的是方解石,其次是硅酸盐矿物。③温度增加,硅酸盐矿物在水中的溶解度明显增加,而方解石的溶解度基本不变。④由于不同有机酸与二氧化硅和金属阳离子生成的络合物稳定性不同,因此,在不同有机酸水溶液中,矿物的溶蚀速率有较大差别。多官能团有机酸的水溶液中,不同矿物有更大的溶解;但在含有丰富Ca2＋的草酸水溶液中,由于矿物颗粒表面难溶草酸钙的沉淀,方解石的溶解变得更加困难。⑤多官能团有机酸与SiO2形成的多环螯合物由于完全取代了硅氧四面体的氧原子,在水中具有高度稳定性,可能有助于(铝)硅酸盐的溶蚀和硅元素的迁移 相似文献
4.
采用热重与测汞仪联用技术,对5种不同煤化程度的煤进行氧化热解实验,研究不同煤化程度煤的热解过程及煤中汞的释放规律。结果表明:X射线衍射（XRD）曲线中衍射峰的特征可反应煤化程度,衍射峰的高度越高,宽度越窄,煤化程度就越高。不同煤化程度的煤在氧气中热解,质量损失随煤化程度的加深而增大,且随着煤化程度的加深,氧化热解的起始温度、最大热分解温度、终止温度也逐渐升高。随着煤化程度的升高,煤中汞释放所需的时间逐渐增加,且汞释放最大值所对应的热重（TG）曲线热解率最大的温度随煤化程度的加深而升高。 相似文献
5.
本文运用热解技术对采自准噶尔盆地风城地区6个重度生物降解稠油进行沥青质热解实验。通过分析沥青质热解产物中生物标志化合物组成和单体正构烷烃碳同位素组成,探索其在降解稠油油源研究中的应用。研究结果显示,沥青质热解产物中生物标志化合物组成特征易受热解温度的影响,指示母质沉积水体环境的参数 Pr/Ph比值随热解温度升高逐渐增大,在较高的温度下,高碳数、高环数的生物标志化合物易裂解生成低碳数、低环数的化合物,导致C20三环萜烷/C30 藿烷和孕甾烷/αααC29R甾烷两个参数的比值随热解温度升高逐渐增大,表明利用沥青质热解产物生物标志化合物组成进行降解稠油油源判识易出现偏差。而沥青质热解产物单体正构烷烃碳同位素组成随热解温度升高并没有明显的变化, 6个降解稠油沥青质热解产物单体正构烷烃碳同位素分布曲线呈水平分布,与来自风城组烃源岩的典型原油基本相似,说明沥青质热解产物中单体烃碳同位素组成特征可用于重度降解稠油油源分析。另外,通过对比稠油与其沥青质热解产物中单体正构烷烃单体碳同位素组成差异,可用于研究多油源以及后期混入的问题。 相似文献
6.
《吉林大学学报(地球科学版)》2015,(Z1)
<正>环境中芳烃的来源比较复杂,多环芳烃的分布广泛。芳烃相对于饱和烃更易溶于水,因而更容易在水体中保存下来;也就是说,一旦有外源污染,更易通过芳烃化合物表现出来。不同成因的PAHs具有结构和组分差异,并且在迁移和沉积过程中保持相对稳定。多环芳烃在环境中的组成分布取决于其来源和传输过程。通常,低分子量/低环PAHs主要来源于石油类产品、化石燃料的不完全(低至中等温度)燃烧或天然成岩过程,而高温热解主要生成高分子量/稠环PAHs。因此,可以运用多环芳烃特征组分的分子指标来判断沉积 相似文献
7.
酸性流体对碳酸盐岩储层的改造作用 总被引：13，自引：1，他引：12
普遍认为CO2、有机酸及H2S是碳酸盐岩储层溶蚀作用的酸性流体。CO2对碳酸盐岩储层的溶蚀作用已有不少学者进行了研究,本文则以一个全新的模拟实验方式对不同类型碳酸盐岩在有机酸和H2S水溶液中的相对溶蚀能力进行了研究,结果发现随温度从常温升高至200℃,有机酸对碳酸盐岩的溶蚀能力由弱变强再变弱,在90℃左右溶蚀能力最强。而H2S水溶液对碳酸盐岩的溶蚀作用则明显不同,60℃时基本达到最大溶蚀率,温度继续升高后,溶蚀能力一直维持在较高的水平并略有增加,150℃后突然降低。由于H2S主要是硫酸盐高温热还原产物（TSR）,因而在碳酸盐岩成岩早期阶段,溶蚀作用的流体可能主要是有机酸和C02,而在深埋阶段,H2S水溶液则可能是溶蚀作用的主要流体。 相似文献
8.
低分子有机酸是对流层大气的重要组成成分,采用离子色谱法测定了贵阳市大气降水中的有机酸浓度.结果表明,气象因素是影响贵阳市大气降水中有机酸浓度的重要因素.其中,降雨系统对雨水中有机酸浓度的影响显著.大气有机酸主要是在降雨初期进入降水并被清除的,降雨初期对大气有机酸的清除量占总清除量的50%-70%.随着降雨的进行,雨水中的有机酸浓度逐渐降低,降雨后期略有升高,大降雨量对雨水中有机酸浓度起稀释的作用.雷雨和台风雨中有机酸浓度明显偏低,降雪中有机酸浓度也远远低于雨水中有机酸浓度,暗示贵阳市雨水中有机酸主要是在云下过程进入降水的.天气因素是通过影响大气中有机酸浓度进而影响雨水中有机酸浓度的,如气温对雨水中有机酸浓度的影响远没有降雨量明显.不同来源气团雨水中有机酸浓度明显不同,其中以北面方向气团降水中有机酸浓度最高,与我国内陆大气污染较重有关,而源于海洋方向的东南气团雨水中有机酸浓度最低. 相似文献
9.
烃源岩—流体相互作用模拟实验研究 总被引：2，自引：0，他引：2
为了探讨烃源岩与孔隙流体之间相互作用过程和机理以及有机酸的生成及其影响因素,我们开展了烃源岩-流体相互作用模拟实验研究。实验结果表明：Ⅱ型干酪根形成有机酸的能力大于Ⅰ型干酪根,水的矿化度对有机酸的形成影响甚微,随着温度升高,流体中有机酸的含量也随之增大。pH值对有机酸形成的影响非常明显,中性和碱性条件更有利于生成有机酸。其中乙酸的形成有利于碳酸盐矿物的溶解,而草酸的形成不利于碳酸盐的溶解。温度对烃源岩的影响与烃源岩的矿物组成有很大的关系,对于富碳酸盐烃源岩,Ca、Mg、Na三元素在水中的溶解量,与温度呈反相关的关系,对于贫碳酸盐烃源岩,与反应温度之间则呈现出正相关的关系。而无论碳酸盐含量高低,Si在溶液中的含量都会随着温度的升高而增大。酸性溶液对烃源岩的溶解能力最强,无论原始反应溶液的酸碱性,反应结果都最终趋于弱碱性。流体的含盐量对烃源岩中Mg的溶解影响差异较大,低盐度的流体有利于Mg溶解。 相似文献
10.
为了探讨烃源岩与孔隙流体之间相互作用过程和机理以及有机酸的生成及其影响因素,我们开展了烃源岩-流体相互作用模拟实验研究。实验结果表明：Ⅱ型干酪根形成有机酸的能力大于Ⅰ型干酪根,水的矿化度对有机酸的形成影响甚微,随着温度升高,流体中有机酸的含量也随之增大。pH值对有机酸形成的影响非常明显,中性和碱性条件更有利于生成有机酸。其中乙酸的形成有利于碳酸盐矿物的溶解,而草酸的形成不利于碳酸盐的溶解。温度对烃源岩的影响与烃源岩的矿物组成有很大的关系,对于富碳酸盐烃源岩,Ca、Mg、Na三元素在水中的溶解量,与温度呈反相关的关系,对于贫碳酸盐烃源岩,与反应温度之间则呈现出正相关的关系。而无论碳酸盐含量高低,Si在溶液中的含量都会随着温度的升高而增大。酸性溶液对烃源岩的溶解能力最强,无论原始反应溶液的酸碱性,反应结果都最终趋于弱碱性。流体的含盐量对烃源岩中Mg的溶解影响差异较大,低盐度的流体有利于Mg溶解。 相似文献
11.
Hydrous pyrolysis, commonly used for the simulation of liquid hydrocarbon generation, is a potentially useful technique for the study of dissolved organic acid synthesis if modifications to conventional methods are made. Simple experiments demonstrate the thermal origin of formic, acetic, proprionic, and butyric acids. The use of stainless steel reactors at high temperatures ( ca. 300°C), however, results in short chain aliphatic acid yields and distributions that are a function of experimental conditions. Once generated, propionate is destroyed more rapidly than acetate during the experiments. Experimental artifacts can be reduced by using lower temperatures and less catalytically active reactor materials.With present methodology, hydrous pyrolysis provides a useful semi-quantitative method for assessing the organic acid generating capacities of different rocks and organic matter types. As much as 1.2 wt% of the organic C in low thermal rank kerogen can be converted to short chain aliphatic acids. However, carbon dioxide is the dominant oxygen-containing product, exceeding organic acid yields by roughly 10 times. Relative organic acid generating capacities can vary by a factor of two or more in narrow stratigraphic intervals (<3 m). Bulk geochemical parameters, like oxygen indices, and gross organic petrography (organic matter type) only partly explain the observed variations in organic acid yields between samples. 相似文献
12.
深层、超深层中有机酸的分布特征及其热稳定性对储层物性有着重要影响。采用高温高压水—岩模拟装置对储层中典型一元和二元有机酸（乙酸和乙二酸）的分解反应进行了模拟,对动力学参数进行了计算,并分析其影响因素。结果显示:乙二酸比乙酸更容易分解,且分解反应的速率更高;乙酸和乙二酸分解反应的起始温度分别为230 ℃和180 ℃,其反应速率随着温度的升高而急剧增加。反应体系中高pH值和钾长石的存在明显提高了乙酸和乙二酸分解反应的反应速率,但对起始温度影响较小。高流体压力和静岩压力均会抑制乙酸和乙二酸的分解,在提高有机酸分解反应起始温度的同时降低分解反应速率。从地质意义上来讲,相对高压、低地温的地层环境更有利于有机酸的保存,因此具有低地温梯度的沉积盆地形成深层—超深层优质储层的可能性更高。 相似文献
13.
In general, aragonite exists as a metastable carbonate mineral under near-surface conditions, and is commonly transformed into calcite under the subsurface and during diagenesis. It is thus seldom found in sedimentary rocks, but aragonite is common in the Paleogene lacustrine shales in the Jiyang Depression in eastern China. Dissolution experiments were conducted on the Paleogene aragonite-enriched and calcite-enriched shales at different temperatures, pressures and acetic acid concentrations, and in different types of solution. The results show that aragonite is insoluble in the in situ formation water but dissolved more readily under acetic acid conditions than calcite with the degree of dissolution increasing with increasing temperature, pressure and acetic acid concentrations. During the shallow burial diagenesis of the Paleogene sediment sequence in the Jiyang Depression, aragonite was relatively stable and was not dissolved by the connate pore water in the shales. Increasing burial (temperature) and maturity of the organic matter produced large amounts of organic acids that accelerated the dissolution of aragonite. In the late stage, as the organic matter became over-matured, the pore water changed from acidic to alkaline, and calcite precipitated from the carbonate-rich solution. Therefore, the conditions provided by organic acids enabled the conversion of aragonite to calcite during sedimentary diagenesis in the Paleogene lacustrine shales in the Jiyang Depression. This transformation corresponded to the thermal evolution of the organic matter within the shale sequence. 相似文献
14.
探讨氯化锌活化黄姜皂素纤维渣的机理, 应用TG-FTIR联用技术考察了黄姜皂素纤维渣的氯化锌热解特性.不同的配比、氛围及升温速率对热解均有影响.低温氧化有利于活性炭的形成, 但高温氧气的存在对炭体烧失较大; 氯化锌与原料的配比越高, 对原料的侵蚀性越强, 采取相应的活化温度较低; 升温速率越低越有利于原料中有机质蓄积热量热解, 相应的活化温度也越低; 红外光谱图也表示挥发分产物的出现与热重分析相符, 没有时间滞后现象.因此, 确定制备活性炭的初步工艺为先在300℃左右低温炭化, 再在保护气氛中(如N2) 500℃左右活化, 升温速率10K/min左右.工业生产条件下, 活化温度最高不宜超过650℃. 相似文献
15.
Hydrothermal pyrolysis of organic matter in Riphean mudstone 总被引：1，自引：0，他引：1
V. N. Melenevsky A. E. Kontorovich Wuu-Liang Huang A. I. Larichev T. A. Bul’bak 《Geochemistry International》2009,47(5):476-484
The catagenesis of organic matter (OM) was modeled by the hydrothermal pyrolysis of a source rock (Riphean mudstone from eastern Siberia). Isothermal experiments 72-h long were carried out in an aqueous environment in autoclaves at temperatures of 300, 310, 320,..., 370°. The pyrolysis products were analyzed for yield of extract, organic carbon, and parameters of Rock-Eval pyrolysis. The amount of the generated liquid hydrocarbon (HC) compounds increased to a temperature of 340°C and then decreased. The experimental trend of the hydrogen index (HI) dependence on the T Max temperature generally coincided with that for natural OM maturation. The carbon isotopic composition of the insoluble (in organic solvents) OM remained practically unchanged in the course of the experiments. The carbon structure of the solid remnants of the experimental samples was ordered (after the experiments) with the origin of turbostratic graphite with a spacing of d 002≈3.5 A°. We also conducted pyrolysis in a diamond anvil cell equipped with a digital camera in order to obtain additional qualitative and quantitative information on oil generation and emigration in the source rock and isolated kerogen. Chemical kinetic parameters of kerogen cracking were calculated for pyrolysis in an open system. The extrapolation of the high-temperature experimental results is discussed with reference to natural OM maturation. 相似文献
16.
Organic acids and acid anions occur in substantial concentrations in many aqueous geologic fluids and are thought to take part in a variety of geochemical processes ranging from the transport of metals in ore-forming fluids to the formation of natural gas to serving as a metabolic energy source for microbes in subsurface habitats. The widespread occurrence of organic acids and their potential role in diverse geologic processes has led to numerous experimental studies of their thermal stability, yet there remain substantial gaps in our knowledge of the factors that control the rates and reaction pathways for the decomposition of these compounds under geologic conditions. In order to address some of these uncertainties, a series of laboratory experiments were conducted to examine the behavior of organic acids and acid anions under hydrothermal conditions in the presence of minerals. Reported here are results of experiments where aqueous solutions of acetic acid, sodium acetate, or valeric acid (n-pentanoic acid) were heated at 325°C, 350 bars in the presence of the mineral assemblages hematite + magnetite + pyrite, pyrite + pyrrhotite + magnetite, and hematite + magnetite. The results indicate that aqueous acetic acid and acetate decompose by a combination of two reaction pathways: decarboxylation and oxidation. Both reactions are promoted by minerals, with hematite catalyzing the oxidation reaction while magnetite catalyzes decarboxylation. The oxidation reaction is much faster, so that oxidation dominates the decomposition of acetic acid and acetate when hematite is present. In contrast to previous reports that acetate decomposed more slowly than acetic acid, we found that acetate decomposed at slightly faster rates than the acid in the presence of minerals. Although longer-chain monocarboxylic acids are generally thought to decompose by decarboxylation, valeric acid appeared to decompose primarily by “deformylation” to 1-butene plus formic acid. Subsequent decomposition of 1-butene and formic acid generated a variety of short-chain (≤C4) hydrocarbons and moncarboxylic acids as well as CO2. Valeric acid decomposition proceeded more rapidly (by a factor of 2) in the presence of hematite-magnetite-pyrite than with the other mineral assemblages, with the greater reaction rate apparently attributable to the effects of fluid chemistry. Valeric acid was observed to decompose at a substantially faster rate than acetic acid under similar conditions. The results suggest that decomposition of aqueous monocarboxylic acids may make a significant contribution to the conversion of petroleum to light hydrocarbons in natural gas and thermal fluids. 相似文献
17.
对鄂尔多斯盆地奥陶系平凉组海相页岩进行了3种升温速率下的 Rock-Eval 热解模拟实验,研究了其干酪根在开放体系下的热解生烃演化特征.通过分析热解烃 S2的产率随温度的变化,结合 Kinetics 生烃动力学专用软件计算,获得了其开放体系下的生油动力学参数,活化能分布范围为(57~81)×4.185 kJ/mol.在此基础上进行的动力学模拟结果与实验数据非常吻合,可较好地将实验数据外推到地质实际过程.此外,发现热解残渣中的 H/C(原子比)值与热解温度、干酪根转化率有较好的相关关系,可建立 H/C 值与转化率或者等效镜质组反射率的可靠模板,表明 Rock-Eval 热解实验与 H/C 值结合,可快速评价下古生界源岩的成熟度、转化率和生烃量等指标,将其应用于资源量计算等方面 相似文献
18.
V. N. Melenevskii 《Geochemistry International》2012,50(5):425-436
The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations
of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis
in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models
for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The
maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated
hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry.
We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions
of regional catagenesis. 相似文献