高演化沉积有机质中共价键结合的生物标志物的提取及分析

采用催化加氢热解技术提取了高演化沉积有机质中共价键结合生物标志物，探讨了干酪根催化加氢热解反应机理，考察了产物分布和影响反应的关键变量。在升温速率5℃／min、氢压10～15MPa、氢气流量1．01／min和ω（Mo）：1％的MoS2分散型催化剂的反应条件下，对烃源岩和煤样进行了催化加氢热解反应。所得产物经GC—MS分析，结果表明，催化加氢热解产物收率约为DCM索氏抽提方法的10倍以上，产物的饱和烃的GC—MS分析总离子流图与对应的索式抽提产物基本一致。催化加氢热解是一种提取高演化固体沉积有机质中生物标志化合物的有效分析手段，具有提取的生物标志物收率高，碳骨架结构、立体化学构型保持完整和重排作用小等优点。     

粘土矿物对生物-热催化过渡带有机质热解影响的研究

作者通过对低演化烃源岩中抽提物干酪根、干酪根+粘土基质在具有高灵敏度、大跨度温度范围的差热-色谱联用仪上,由低温（150℃）到高温（650℃）进行了热解成份分析。试验结果表明:,1,Ⅱ型干酪根比Ⅲ型干酪根对形成生物-热催化过渡带气具有更大的潜力。,2,蒙脱石在低温阶段（<350℃）对有机质成烃起着主要的催化作用,它能使C10和C1-4的产量提高到2-3倍。,3,伊利石在低温阶段催化作用不大而在高温阶段（>350℃）影响较为明显,使C10和C1-4的量提高2倍之多。4,高岭石对有机质成烃有一定的催化作用,但不明显。     

川东北地区过成熟烃源岩催化加氢热解研究

针对川东北地区过成熟干酪根样品,采用固定床反应器进行催化加氢热解,利用GC-MS技术对产物进行检测并与源岩抽提产物进行对比,考察了饱和烃中甾烷、萜烷,芳烃中硫芴类和三芴类生物标志物的分布特征及地球化学信息,根据藿烷指数、姥鲛烷/植烷之比、伽马蜡烷指数、规则甾烷/17α(H)-藿烷、C₂₇-C₂₈-C₂₉甾烷、重排甾烷/规则甾烷、硫芴系列化合物、三芴化合物等参数的结果,研究表明川东北烃源岩沉积的环境为缺氧的亚氧化、非超盐度、贫粘土的海相碳酸盐岩,沉积有机质来源于浮游生物。     

加氢催化裂解技术用于高演化源岩有机质表征研究

加氢催化裂解技术作为近年来新发展起来的有机质大分子裂解技术,专门应用于大分子中共价键结合小分子的释放.本研究探索该技术应用于含油气沉积盆地高演化油气源岩原生有机质提取的可能性.以塔里木盆地下古生界油气源岩为例,选取了障壁泻湖相、欠补偿盆地相、闭塞欠补偿陆源海湾相、灰泥丘相等四类典型潜在源岩进行了加氢催化裂解实验,结果表明,加氢催化裂解产物中正构烷烃与甾烷的分布特征与上述源岩相完全吻合,证明加氢催化裂解实验可以有效地提取高演化油气源岩的原生有机质,为下一步实现该技术应用于油气源的对比奠定了基础.     

精细化工中催化加氢技术的运用

在我国社会快速发展的今天,越来越多先进的技术不断涌现出来,对我国各个方面的发展起到一定的促进作用.就从目前情况看来,精细化工生产在我国占据着非常重要的地位,实际生产效果与经济水平之间有着紧密的联系,不过部分单位在实际的生产过程中还在沿用传统的方法和理念,这样就会导致整体的生产效率和质量比较低.为此,相关化工单位在精细化...     

利用热解参数分析切11井E_3~2地层烃源岩有机质特征

通过岩石热解分析方法,对青海柴达木盆地昆北地区切十二号构造切11井下干柴沟组上段(E_3~2)12块烃源岩进行分析研究。结果显示,12块样品为差-中烃源岩,干酪根类型以Ⅲ为主,Ⅱ型次之,热演化程度随着埋藏深度的增加而变高,大多数烃源岩还没有进入生油门限。     

新疆北部石炭系高演化烃源岩加氢催化裂解实验

针对新疆北部石炭系高演化烃源岩常规索氏抽提物含量低的特点,开展加氢催化裂解实验,对比分析两者的生物标志化合物特征,提高烃源岩的沉积背景及母源特征研究的可靠度。结果显示应用氢解产物的正构烷烃和甾烷化合物指示母质来源效果更好。浅部泥岩的正构烷烃呈nC₁₈和nC_22-24的双峰型分布,表明远洋水生浮游动物的贡献大,而深部泥岩呈主峰碳为nC₁₈-nC₂₄的单峰型分布,指示以低等菌藻类水生生物贡献为主;抽提物中C₂₇和C₂₉规则甾烷含量相当,指示混合母质来源,而氢解产物中规则甾烷以C₂₉为主,明确指示单一的母质来源。此外,氢解产物中含有更加丰富的βα-莫烷及ββ-升藿烷系列化合物,丰富了烃源岩的母质信息。研究明确石炭系烃源岩发育于较还原的沉积环境,优质烃源岩主要分布在下段,以菌藻类等单一的水生生物为有机母质来源,具备良好的生烃的背景及物质基础。实验也进一步证实氢解实验能够获取更多的生物标志物信息,对常规抽提方法是一种有益的补充。     

生物油模型化合物催化裂解精制机理

采用糠醛作为生物油的模型化合物,以HZSM-5分子筛为催化剂,在500℃、重时空速5.0 h-1的条件下,研究了不同水含量下糠醛的催化裂解反应,并采用GC-MS分析了产物的组成。实验结果表明,糠醛催化裂解后生成了醛类、酮类、呋喃类、茚类、苯类、萘类及其衍生物;随原料中水含量的增加,糠醛容易发生环化反应,茚类、苯类和萘类的含量增加,醛类、酮类和呋喃类的含量降低。根据糠醛催化裂解产物分布推测了糠醛催化裂解反应机理,生物油中糠醛类化合物在催化裂解过程中主要发生脱羰基、脱羧基和环化反应。     

催化加氢—蒸馏技术在加氢脱硫中的应用与对比

文中介绍了目前加氢脱硫应用中成本低、转化率高、进料位置灵活、选择性好、节能等优势的催化加氢—蒸馏技术,同时对加氢脱硫技术中的其它3类具有代表性的技术进行了阐述。通过技术对比得出催化加氢—蒸馏技术有较大工艺优点,但结合国内汽油质量发展以及催化裂化（FCC）汽油特点,发现固定床加氢脱硫技术在国内应用市场优势更大。     

催化加氢还原芳香硝基化合物制备芳胺的技术进展

综述了催化加氢还原芳香硝基化合物制备芳胺及其衍生物的近况,讨论了影响催化加氢反应的主要因素和工艺条件,并展望了催化加氢法制备芳胺工艺的应用前景和发展方向。     

Mechanism of catalytic hydropyrolysis of sedimentary organic matter with MoS2

MoS2 was used as an efficient catalyst for hydropyrolysis(Hypy) of three samples of sedimentary organic matter with different maturities.Through comparison with Soxhlet extraction(SE),it was found that MoS2 catalytic Hypy can remarkably promote the yields of total chloroform extracts,saturates,aromatics,hopanes and steranes.In addition,the difference of biomarker parameters indicated that isomerization of covalently-bound biomarkers is much more difficult than their free counterparts.Meanwhile,the high conversion of total organic carbon(TOC) in MoS2 catalytic Hypy of organic matter proved that the presence of dispersed molybdenum sulfide accelerated the breaking of C-C bonds and the release of hydrocarbons.To address the catalytic mechanism,a series of control experiments based on free Hypy and catalytic Hypy were conducted.The results showed that the calculated atomic ratio of carbon conversion/hydrogen conversion for catalytic Hypy was much larger than the presumed value of 1/2,indicating that intensive hydrogenation took place and significantly influenced the distribution of liquid products.Analysis of stable hydrogen isotope data,infrared spectra and m/z 83 ion chromatograph of the saturate fraction further confirmed this hypothesis.The difference of S content changing(ΔS) between catalyst-free Hypy and catalytic Hypy,and the thermal characteristics of the catalyst,indicated that active H2S was def initely generated and it probably initiated free radical reactions in the early stage of hydropyrolysis of organic matter.     

The composition of organic matter of Domanic deposit of the Bavly field

Core material taken from Zavolzhsky and Dankovo-Lebedyan horizons of the Bavly oil field attributed to the Domanic deposit is studied by thermal analysis methods. The content of total organic matter, the share of bitumoid and kerogen in it and their fractional composition are estimated. The features of fractional and hydrocarbon compositions of the bitumoids are revealed by thermal analysis, gas chromatography and IR spectroscopy methods. It is shown that, in some cases, the domanic deposit contains light hydrocarbons that can be extracted from the rock using solvents. An estimation of the oil-generating potential of the organic matter of the Zavolzhsky and Dankovo-Lebedyansky horizons is made.     

有机质"多代链式反应"成烃机理的研究与探讨--有机质成烃的微观物理解释

应用“活力论”原理研究“活性分子”在有机质成烃过程中的作用.首先阐明了烃源岩的粘土矿物晶格水和粘土矿物集合体间的层间水的水分子性质及其演变过程,然后叙述了水“活性分子”形成质子酸束(H^ )的原理和机制及其在可溶性有机质成烃过程中的加氢脱水作用和加氢脱羧酸成烃作用;探讨了水“活性分子”的质子酸束对大分子干酪根轰击的“多代链式反应”的裂解成烃过程及其烃类产物的性质与组成;最后解释了生物标志化合物胆甾烷的立体同分异构体不同深度丰度变化的原因。     

Characterization of hydrocarbon/pores generation and methane adsorption in shale organic matter

The exploration and development of shale gas reservoirs has been of growing interest in the industry in recent years. It has been widely acknowledged that, during different thermal evolution stages, some characteristics including: the hydrocarbon-generation mechanism, development of organic matter pores, and methane storage/transport mechanism in organic matter/pores will affect shale gas desorption and production fundamentally. However, current research has failed to reveal them completely, which introduces large discrepancies between actual and predicted production in some shale gas reservoirs. In this paper, for the four thermal evolution stages of shale organic matter, i.e., the biochemical, thermo-catalytic, thermo-cracking and deep high temperature phases, respectively, characteristics of products generated from shale kerogen, including the form and quality of the solid frame, gas-oil ratios, and pore characteristics in organic matter (e.g., types of pores, pore wall materials) were first investigated. A new classification method for organic-matter pores was proposed. Additionally, methane absorption characteristics in shale organic matter and pores were demonstrated, the fact that water is involved during each thermal evolution phase was addressed, and current theories of solid-gas interface adsorption/desorption in the organic matter in shale were questioned. This work concluded that the system of solid-gas interface differs from actual shale reservoirs, so predicting production based on this understanding leads to significant inaccuracies. This work explained the possibility of solid-liquid interface effects in the organic matter of shale through analyzing product-generation and pore-formation mechanisms during the evolution of shale, which will directly affect potential reserves of shale. Therefore, this work should provide a basis for improving the accuracy of production predictions in actual reservoirs and should assist analysts in determining reasonable shale gas targets.     

Hydrothermal transformations of organic matter of low permeability rocks from domanic formation of the romashkino oil field

Abstract

The oil generating potential of Domanic rocks from Dankov–Lebedyan horizon of the Zelenogorsk area of Romashkino oil field was evaluated by Rock-Eval pyrolysis technique. The result of given method depends on the content, composition, and thermal stability of organic matter in rocks. During hydrothermal processes, the distinctive conversion behavior of organic matter at temperatures of 200°С, 250°С, 300°С, and 350°С in CO₂ environment was revealed. The yield of obtained aquathermolysis products and their quality were evaluated. The results of the studies suggest that low-permeability carbonate rocks of the Dankov–Lebedyan horizon contain productive beds with content of C_org 1.89–3.03%, which when developed using thermal methods, can become an additional source of liquid hydrocarbons.     

激光拉曼技术评价沉积有机质热成熟度

在澳大利亚联邦科学与工业研究组织能源组对激光拉曼技术评价有机质成熟度研究成果RaMM（1）和RaMM（2）的基础上,提出了可以评价沉积有机质热成熟度的激光拉曼技术新模型RaMM（P）,模型使用范围为0.4%r（镜质组随机反射率）<2.5% ,其具有样品量小、微区（约2 μm）无损分析、无需镜下区分不同显微组分（镜质组、惰质组）的特点。RaMM（P）模型在不同层系煤（二叠系、石炭系）、富氢煤与贫氢煤（镜质体反射率受到抑制和增强）以及海相泥岩分散有机质中的应用结果表明,该方法可以有效评价沉积有机质热成熟度,能反映镜质体反射率异常的问题;同时将RaMM（P）与RaMM（1）和RaMM（2）方法进行了对比讨论。该方法在沉积分散有机质热成熟度评价,尤其是镜质体缺少/缺失或镜质体反射率受到抑制或镜质体识别困难的沉积地层具有广阔的应用前景。     

催化蒸馏技术在汽油醚化装置的应用

介绍了催化蒸馏技术在40×104 t/a汽油醚化装置中的应用情况。结果表明,汽油醚化装置运行稳定,加氢后的催化汽油蒸汽压由68kPa降至56kPa,轻汽油研究法辛烷值提高约1.33个单位,轻汽油烯烃含量降低了15.71%(φ),效果比较显著,经济效益提升明显;C5叔碳烯烃平均转化率达到95.13%,C6叔碳烯烃平均转化率达到52.28%;醚化效果明显。催化剂在40℃就能够催化醚化反应,且具有较高的转化率;催化剂较高的低温活性,有利于催化剂寿命的延长。醚化轻汽油中甲醇含量控制在0.18%(w)左右,可以通过优化进一步提高醚化汽油中的甲醇含量,达到效益最大化。通过催化蒸馏技术,使醚化反应器出口转化率由69.39%提高到了93.71%;甲醇消耗为90.9kg甲醇/t轻汽油;装置能耗为833.5×104 kJ/t(19.94kgEo/t)轻汽油,远低于设计值;废水排放少,符合催化蒸馏技术的特点。     

海相碳酸盐岩的形成环境与有机质特征

海相碳酸盐岩形成于海水蒸发量大、生物繁盛、Eh和pH值容易改变的浅海陆棚相环境。海水的动荡性与高含氧量破坏了海洋中死亡生物的软体部分,造就了碳酸盐岩有机质的低丰度和低品位,TOC低于0.2%且干酪根为Ⅲ型或Ⅱ₂型的碳酸盐岩在世界范围内具普遍性。因此,纯净碳酸盐岩不能成为有效烃源岩。碳酸盐岩随含泥量增加TOC变大,但仅有少量TOC大于0.5%的泥灰岩有可能成为有效烃源岩。