天然矿物低温催化脂肪酸酯生烃反应动力学研究

选择十八烷酸甲酯为模型化合物,以 10种天然矿物为载体,通过动力学方法考察了天然矿物对脂肪酸酯生烃反应的催化作用.结果表明,地质低温条件下天然矿物对脂肪酸酯生烃反应具有催化作用.矿物的催化作用主要体现在对反应活化能和指前因子的影响上.粘土、碳酸盐和金属元素对于脂肪酸酯生烃反应具有不同的催化作用,碳酸盐矿物相对于粘土矿物使生烃反应的活化能降低,过渡金属化合物矿物存在时,催化反应活化能介于碳酸盐和粘土矿物之间.天然矿物的存在能够升高或降低反应指前因子.     

烃源岩催化酯生烃动力学研究——以东营凹陷沙河街组三、四段烃源岩为例

烃源岩生烃动力学广泛应用于含油气盆地烃源岩评价与勘探中。为模拟低成熟烃源岩的实际沉积环境,实验选取了抽提有机质后的东营凹陷下第三系沙河街组三、四段烃源岩为矿物催化剂,以十八烷酸甲酯为模型化合物,在高压下做矿物低温催化脂肪酸酯脱羧生烃动力学实验。求取了化学反应的动力学参数,并分析了烃源岩层段的pH值与Eh值。结果表明,矿物对脂肪酸酯的脱羧生烃具有明显的催化作用,用连串反应模型处理脂肪酸酯的水解反应基本上为一级反应,而生烃反应则基本上为零级反应。认为对于同一类型的烃源岩,其所处的氧化还原环境对有机质的生烃有较大的影响;而对于不同的烃源岩,矿物的组成则起着非常重要的作用。     

压力对未熟烃源岩低温催化脂肪酸酯水解的影响

选择十八烷酸甲酯为模型化合物,以 7种抽提有机质的未熟烃源岩为载体考察了压力对未熟烃源岩矿物催化脂肪酸酯水解反应的影响。结果表明,在未熟烃源岩低温催化脂肪酸酯的水解反应中,压力是重要的影响因素,压力效应不可忽视。7种未熟烃源岩产生了不同的压力效应,并因此引起了水解率的升高或降低。文中对压力效应产生的原因进行了探讨,认为观测到的压力效应是压力对反应促进和抑制作用共同作用的结果。     

未熟烃源岩中矿物低温催化脂肪酸脱羧生烃动力学模拟实验研究

在150～160 ℃和未熟烃源岩矿物的催化下,使十八烷酸脱羧生烃,用测定反应放出的CO2量随时间的变化关系直接研究了我国7个油田未熟烃源岩对脂肪酸催化脱羧生烃的动力学.由所得到的动力学参数与未熟烃源岩中碳酸盐含量的关联中发现,在低温、常压、无水条件下或低温、高压、碱性盐水条件下未熟烃源岩对脂肪酸催化脱羧生烃的动力学参数与其碳酸盐的含量有关,一般碳酸盐含量高反应速率常数大,而反应活化能低.     

未熟烃源岩中矿物低温催化脂肪酸脱羟生烃动力学模拟实验研究

在１５０～１６０℃和未熟烃源岩矿物的催化下,使十八烷酸脱羟生烃,用测定反应放出的ＣＯ２量随时间的变化关系直接研究了我国７个油田未熟烃源岩对脂肪酸催化脱羟生烃的动力学。由所得到的动力学参数与未熟烃源岩中碳酸盐含量的关联中发现,在低温、常压、无水条件下或低温、高压、碱性盐水条件下未熟烃源岩对脂肪酸催化脱羟生烃的动力学参数与其碳酸盐的含量有关,一般碳酸盐含量反应速率常数大,而反应活化能低。     

无机盐类对干酪根生烃过程的影响

利用岩石热解评价仪（Rock-Eval）和热解气相色谱仪（Py-GC)，对采自东营凹陷和松辽盆地的烃源岩干酪根进行了热模拟实验，探讨了地层水中所存在的无机盐类对生烃过程的影响，求得了不同盐类作用下的反应动力学参数。结果表明，无机盐类对干酪根的热解生烃过程具有不同的影响。其中，氯化盐类具有一定程度的反催化作用，其他盐类表现出正的催化作用。这种催化作用是通过降低热解反应的表观活化能或提高反应的频率因子而表现出来的。最后，对无机盐类的催化作用机制进行了初步探讨，认为电子诱导效应理论可以初步解释无机盐类的催化作用。     

造山的高原——青藏高原巨型造山拼贴体和造山类型

有机质丰度是传统评价烃源岩方法的重要指标,笔者认为有机粘土复合体是烃源岩有机质的主要赋存形式。有机质生烃反应是一种有机粘土化学反应,有机质脱羧基反应是有机粘土的氧化-还原反应,有机质的热解反应是一个加氢裂解过程,含有剩余C0是烃源岩的基本特征,它说明在烃源岩生烃反应中C0始终是有剩余的,不会因为C0的不足而影响烃源岩的生烃能力。笔者认为制约烃源岩生烃能力大小的不是烃源岩C0的丰度,而是氢的来源和丰度,烃源岩粘土通过吸附水分子为生烃反应提供H+能力(Br nsted酸性)的大小和时间是决定生烃潜力大小的关键。烃源岩粘土的不同催化特性是影响油气组成的重要因素,蒙皂石对甾烷的异构化有明显促进作用。     

山西沁水盆地石炭-二叠系煤层生排烃史分析

通过对沁水盆地石炭-二叠系煤层夹矸及煤层顶板砂岩石样品中的包裹体类型、与矿物的共生关系以及包裹体均一化温度研究,结合山西南部上古生界煤层埋藏史及热史演化分析,讨论了太原组和山西组煤层的排烃历史。结果表明,太原组和山西组煤层排烃主要发生在晚三叠世末期煤层抬升释压以来,大体可以分为中侏罗世、早白垩世早期和晚白垩世一直到古新世三期。早期有过煤成油的阶段,并且有一定规模的排油过程;主要的排气阶段正好与热催化生油气阶段和热裂解生凝析气阶段相对应,那么可以认为热解气和热裂解气是煤层气的主要组成部分。煤储层中液态烃与煤层夹矸及顶板岩石中液态烃组成特征存在着明显差别,可能是由排烃过程吸附分馏作用和不同成熟度液态烃的混合作用不同所致。甾烷和藿烷总体组成特征相似,说明煤层、煤层夹矸及顶板砂岩中油气来源于煤层。     

生油岩矿物低温催化脂肪酸脱羧生烃的活性评价

在地质低温条件下,未熟生油岩矿物催化脂肪酸脱羧生烃反应生成的ＣＯ２含量很低,因此,通过金属镍催化剂将ＣＯ２转化为ＣＨ４后再用氢离子火焰检测器检测其含量,以提高检测的灵敏度。运用该方法评价了我国七个油田未熟生油岩矿物催化脂肪酸脱羧生烃活性实验结果表明,脂肪酸在未熟生油岩矿物低温催估作用下,其脱羧率与未熟生油岩矿物中的碳酸盐及过渡金属Ｆｅ元素的含量有关。     

粘土矿物对有机质生烃的催化作用

烃源岩的有机质主要以有机粘土复合体的形式存在。有机质生烃是一种有机粘土化学反应。反应过程中,有机质与粘土之间存在质子和电子迁移,粘土通过对水分子的吸附和离解为有机质加氢裂解提供H+,而有机质生成的有机酸激活了粘土的催化活性,也为蒙皂石伊利石化反应创造了条件。烃源岩不同粘土矿物的选择性催化特征是影响油气组成的最重要因素。粘土的催化活性大小和发育时间是决定烃源岩生烃潜力大小的因素。由于烃源岩在蒙皂石伊利石化阶段具有最大的催化活性,而且与有机质生烃反应同步,因此富含伊$蒙混合层的烃源岩是世界含油气盆地的最有利烃源岩。不同地质时期的烃类地质储量与烃源岩膨胀性粘土的丰度有密切关系。     

烃源岩催化生烃机制研究进展

本文扼要综述了国内外在热模拟催化生烃领域的研究进展,并针对其存在问题或不足之处,提出了新的研究思路,设计了新的实验方案,对烃源岩催化生烃机理和过程进行定量的研究,建立定量的催化反应速率数学模型和催化生烃产离数学模型,并制作成可操作的计算软件,划分出起正催化作用和反催化作用的催化剂。在研究过程中,全面考虑某生油岩中的所有粘土矿物和地下水中的无机盐类对生烃的催化作用,即系统地分别考虑生油岩中存在的各单     

Diversified roles of mineral transformation in controlling hydrocarbon generation process,mechanism,and pattern

Organic matter(OM)is intimately associated with minerals in clay-rich mudstones,leading to widespread organic-mineral interaction during hydrocarbon generation in argillaceous source rocks.What we are concerned is the effects of the different mineral properties on hydrocarbon generation process and mechanism during mineral transformation.In this way,pyrolysis experiments with smectite-octadecanoic acid complexes(Sm-OA and Ex-Sm-OA)were conducted to analyze correlation of mineralogy and pyrolysis behaviors.Based on organicmineral interaction,hydrocarbon generation process was divided into three phases.At 200–300℃,collapse of smectite led to desorption of OM,resulting in high yield of resin and slight increase in saturates.Subsequently,enhanced smectite illitization at 350–450
℃was accompanied with large amounts of saturates and a mere gaseous hydrocarbon.Featured by neoformed plagioclase,ankerite,and illite,500
C saw plenty of asphaltene and methane-rich gaseous hydrocarbons,revealing cracking reactions of OM.Noteworthy is that saturated and gaseous hydrocarbons in Ex-Sm-OA were considerably more than that in Sm-OA during second and third phases.Quantitative calculation of hydrogen revealed organic hydrogen provided by cross-linking of OM could not balance hydrogen consumed by cracking reactions,but supply of inorganic hydrogen ensured cracking could readily occur and consequently greatly promoted hydrocarbon generation.Further investigating characteristics of mineralogy and pyrolytic products,as well as effects of solid acidity on hydrocarbon generation,we concluded desorption of OM and decarboxylation promoted by Lewis acid were dominated at 200–300
C,resulting in lowdegree hydrocarbon generation.While high yield of saturated and gaseous hydrocarbons in second and third phases,together with occurrence of ankerite,indicated predominance of decarboxylation and hydrogenation promoted by Lewis and Br?nsted acid,respectively.Variations in organic-mineral interactions indicated(1)the controls of mineral transformation on hydrocarbon generation process and mechanism include desorption,decarboxylation,and hydrogenation reactions;(2)clay minerals acted as reactants evolving together with OM rather than catalysts.These findings are profoundly significant for understanding the hydrocarbon generation mechanisms,organic-inorganic interactions,and carbon cycle.     

Geochemistry of Bizerte lagoon affluent water, Northern Tunisia: principal component analysis

The monthly geochemical study of Bizerte lagoon principal affluent water consists in characterizing the water geochemical facies and their inorganic pollution degree by nutrients. The major elements analysis shows calcium sulfate to chloride calcium balanced facies. The geochemical analysis of water nutritive salts shows generally a good to excellent quality. Wadi Guenniche is considered more polluted as we recorded the highest nutrients contents. The principal component analysis of the connections between the physicochemical and geochemical parameters of Bizerte lagoon affluent water show that the low salinities, the turbidity, and the low contents of major sodium, chloride ions, and nutritive elements are the major factors of the environment controlling the good quality of this fresh water.     

A Reconstruction and Discussion of the Effect of Diagenetic Environment on Hydrocarbon Generation Based on Diagenetic Mineral Assemblage in Mudstone

Inorganic minerals in mudstone are composed of clay minerals,carbonate and detrital minerals.Detrital minerals(such as quartz and feldspar)are mainly original deposit.However,clay minerals(kaolinite,illite,and chlorite)and carbonate(calcite and dolomite)are mostly diagenetic minerals.Furthermore,conversion of the four kinds of clay minerals are common.The formation of clay minerals and carbonate is controlled by temperature,pressure,p H,Eh and type of cations during diagenesis.Therefore mineral assemblage can indicate the characteristics and change of diagenetic environment.In addition to inorganic minerals,there are also organic matter of different sources and chemical properties in mudstone.Traditionally,it is considered that evolution of organic matter is controlled by thermal effect.Now studies show that inorganic and organic matter can interact with each other and form clay-organic complexes.This suggest that attention should be paid to the influence of diagenetic mineral assemblage and diagenetic environment on the evolution of organic matter* Samples of mudstone from 1500-4500m of the Palaeogene in the Dongying Depression,China,were collected to investigate the changes of mudstone diagenetic environment.XRD,thin section and SEM were used to detect diagenetic minerals and assemblage characteristics.Results showed that content of detrital minerals,which are floating in mud matrix or preserved as silt laminae,is basically unchanged from shallow to deep strata.Clay minerals which are gathered as argillaceous matrix or preserved as argillaceous laminae have growth and decline relation to carbonate which mainly appear as micropoikilitic ferriferous calcite and ferriferous dolomite.All these characteristics indicate that detrital minerals are exogenetic,whereas carbonate is diagenetic minerals.Based on the SEM analysis of the clay minerals,it was found that smectite present honeycomb and reticulate structure,while illite present filiform and schistose structure and there are growth and decline relationship between them.Nevertheless,hexagonal tabular and stratified kaolinite has the highest content from 2400m to3300m.Rosette and stratified chlorite shows increase trend when the burial depth is deeper than 3300m.These characteristics indicated that clay minerals are diagenetic minerals and there are conversions among the four types.Therefore form shallow to deep,three diagenetic mineral assemblage zones can be divided based on the characteristics of carbonate and clay minerals in mudstone.Namely,smectite+illite/smectite zone in the depth of 2000-2500m;kaolinite+illite/smectite zone in the depth of 2500-3300m and illite+chlorite+carbonate zone below 3300m.Previous studies showed that kaolinite is stable under acidic conditions,while other clay minerals and carbonate are stable under alkaline conditions.Hence according to mineral assemblages feature,it was inferred that diagenetic environment of mudstonehasundergonethechangeof alkaline-acid-alkaline.For the organic matter with different chemical properties in mudstone,the hydrocarbon generation will be different in the acidic and alkaline diagenetic environment even if the conditions of temperature and pressure are the same.Therefore,for hydrocarbon generation we should not only focus on thermal effect,but also pay more attention to the differences of diagenetic environment which have great significance for the understanding of hydrocarbon generation,hydrocarbon expulsion and reservoir formation in mudstone.     

Amorphous silica solubilities IV. Behavior in pure water and aqueous sodium chloride,sodium sulfate,magnesium chloride,and magnesium sulfate solutions up to 350°C

Solubilities of amorphous silica were determined in separate aqueous solutions of sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate at temperatures up to 350°C. These salts, of strong interest in hydrothermal oceanography and geothermal energy, generally ranged in concentration from zero to saturation. Solubilities in the sodium chloride solutions followed closely earlier observed decreases in sodium nitrate solutions at high temperatures.Amorphous silica solubilities were depressed most by magnesium chloride, followed by magnesium sulfate, and less by sodium chloride. As the temperature rose the relative decrease in solubility caused by added salt became smaller. Surprisingly, sodium sulfate solutions, showing little effect at 25°C, sharply raised the solubility as the temperature increased to 350°C. Plots of the logarithms of derived activity coefficients against molalities of added salt gave approximately straight lines. These plots allow simple predictions of amorphous silica solubility in single salt solutions.     

湖相页岩有机储集空间发育特点与成因机制

有机储集空间是页岩的重要储集类型, 但对处于生油窗内的湖相页岩是否发育有机储集空间却缺少研究.系统采集处于生油窗范围内不同演化程度的湖相页岩样品, 利用氩离子抛光样品制备技术, 分别使用Quanta200扫描电镜及EDAX能谱仪联机和JSM-6700f冷场发射扫描电子显微镜对湖相页岩进行微观特征观察和岩石组分分析, 背散射图像和二次电子图像均显示, 页岩内大量发育呈暗色条带状的有机质-粘土-碳酸盐和有机质-粘土-硫酸盐混合体.该混合体内极易发育孔隙, 从2 500~4 000 m, 该类孔隙连续分布, 当埋深小于3 600 m时, 这类孔隙的尺度一般为微米级, 但随着演化程度增高纳米孔隙增加, 并且呈密集分布.混合体内孔隙的发育分别与页岩含油饱和度迅速增高及游离有机酸含量的增加同步, 该类孔隙的发育不仅仅取决于生烃作用, 它的形成是生烃转化和有机酸溶蚀共同作用的结果.上述结果表明, 在生油窗范围内湖相页岩中, 有机质与无机矿物作为整体共同演化且相互作用, 在生烃与溶蚀叠合作用下形成了丰富的有机质-矿物混合体内储集空间, 该储集类型对陆相页岩油气赋存具有重要意义.      

铁细菌培养过程中低分子有机酸钠盐对含硫酸根铁矿物形成的影响

普遍存在环境中的低分子有机酸盐对氧化亚铁硫杆菌的矿化产物(施氏矿和黄钾铁矾等铁矿物)会产生影响,从而导致环境中有毒重金属迁移转化发生变化。本文探讨了低分子有机酸钠盐对铁细菌HX3成长过程中代谢产物铁矿物的影响,并利用XRD、FTIR、FESEM和EDS对形成的铁矿物进行了表征与分析。研究结果表明,低浓度低分子有机酸钠盐的加入对细菌氧化Fe~(2+)的影响不明显,但可加速黄钾铁矾的形成;苹果酸钠的加入较柠檬酸钠和草酸钠更利于施氏矿向黄钾铁矾转变。高浓度低分子有机酸钠盐(苹果酸钠、柠檬酸钠和草酸钠依次为20、40和40mmol/L)的加入对细菌培养过程中Fe~(2+)的氧化有抑制作用;抑制影响从大到小的顺序为:苹果酸钠柠檬酸钠草酸钠。该研究结果可为含氧化亚铁硫杆菌等铁细菌的酸性矿山废水中铁矿物的形成转化和生物矿化机理提供理论参考。