原油的有水热解产生低分子量有机酸的研究

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。     

泥岩有水热解产生低分子量有机酸实验研究

直接采用泥岩岩屑进行有水热解,测定实验后水溶液中几种常见低分子量有机酸.结果表明,在实验的水溶液中检测到了丰富的低分子量有机酸,组成上主要为一元羧酸,其中又以乙酸占优势.讨论了不同热解条件对有机酸产率以及组成的影响.实验结果表明,有机酸总量随加热温度和时间增加而增加,并且溶液中不同有机酸相对组成也发生变化.当温度高于1...     

浅部流体对花岗岩储集空间改造作用实验研究

以渤海中生界花岗岩为研究对象,利用高压釜设备开展大气水、有机酸(地层水)、大气水+有机酸(地层水)3种不同流体与花岗岩进行相互作用实验。实验前后样品分析表明:3种流体在不同温度下与组成花岗岩的主要矿物碱性长石、斜长石发生相互作用,碱性长石、斜长石发生不同程度的溶蚀、溶解、次生作用,并形成次生孔隙和高岭石等次生矿物,提高了样品面孔率和喉道平均值;实验样品的重量在反应前后存在差异,具有温度越高样品重量损失越多的趋势。通过实验对比分析3种流体对花岗岩样品的改造结果可知,有机酸(地层水)溶液对花岗岩样品在提高储层物性上较其他2种溶液效果明显。     

有机酸与矿物间界面作用研究评述

介绍了近年来有机酸与矿物之间相互作用的研究进展，重点探讨有机还可能与矿物间相互作用的环境意义、作用模式以及低分子量有机酸和高分子量腐殖酸在与矿物作用时各自的特点和彼此间的差异。有机酸-矿物界面作用控制着金属、有机污染物的迁移、转化与归宿以及生物可给性。有机酸-矿物界面作用存在多种模式，主要受有机酸和矿物的活性基团类型、含量分布以及有机酸分子量大小和疏水性等因素的影响。     

不同有机酸对矿物溶解的动力学实验研究

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SiO2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Ca2＋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SiO2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     

有机酸盐影响下土壤中1.4 nm过渡矿物的转化特点

以我国中南地区黄棕壤和黄褐土的胶膜所对应的基质土壤为研究对象，用不同浓度的柠檬酸钠和乙酸钠溶液对土壤进行不同时间的培养试验，探讨1．4越过渡矿物．蛭石之间的转化特点。结果表明：基质土样中的部分1．4越过渡矿物已逐渐向蛭石转化；与其它处理相比，用O．5mol／L的柠檬酸钠和盐溶液培养基质土壤7个月后，其1．4啦过渡矿物向蛭石转化最为明显；培养前后用DCB脱铁与不脱铁的处理对样品中矿物转化的影响不显著。土壤经有机酸盐溶液培养后，其部分1．4越过渡矿物的层间羟基铝被柠檬酸钠或乙酸钠络合出层间，随后钾、钙、镁等的水合阳离子进入，使之转化为蛭石；有机酸盐的种类、浓度和培养时间的长短，对转化的进程起着重要的作用。     

在线PYGC分析技术在气源岩评价中的应用

为了研究高演化地区气源的生成特征与生气潜力，分别采用热解温度为560℃不加内标、CDS2000热解系统，700℃加内标（聚苯乙烯）、由实验室自制热解系统的在线热解气相色谱分析技术，对不同气源岩（代表性的煤、固体沥青及四川地区以下古生界碎屑岩为主的全岩）进行5s的快速热解分析。在对实验系统加内标定量的可行性进行了认真研究后，提出了产烃定量公式。560℃的热解谱图可清楚地将烃源岩分为生油、生气和生凝析油三种类型，并可根据谱图计算出油气比（GOGI）。根据700℃加内标的热解测试结果，计算了气源岩的热解烃总量和C1－5－C5－C15组分的相对含量。热解烃总量随热演变程度增高而递减，其中以碎屑岩的热解烃量减低最快。相同样品的热解烃量与TOC和Rock-Eval测定结果具有很好的可比性。对比不同演化阶段热解产物的相对组成，显示低演化阶段的烃源岩热解产物以C1－5组分为主。由此表明，在高演化阶段，好的油源岩就是好的气源岩。较高演化阶段（测试前R^0为2．5％－4．2％）烃源岩的热解烃中C5－15含量呈增加趋势，这一结果与前人资料吻合，它除了表明C5-15 分的含量可能与烃存在的载体，如无机矿物或固体有机质对早期轻烃的包裹与吸附有关外，可能还揭示了有机质在石墨化过程中高演化阶段有着与低演化阶段不同的特性。固体沥青广泛分布在四川地区下古生界地层中，PY－GC测试结果也表明，固体沥青比相同演化阶段的碎屑岩热解产物多数倍到一个数量级，因此，在高演化地区固体沥青是不可忽视的气源岩。     

高丰度低演化程度湖相页岩储层特征——以柴达木盆地北缘中侏罗统为例

页岩储层特征对于页岩气的赋存状态、含气量和后期开发均具有重要意义。湖相页岩多处于生油窗阶段,其储层特征与海相页岩区别较大。以柴达木盆地北缘中侏罗统页岩为研究对象,利用岩芯观察、有机地球化学分析、XRD矿物成分分析、低温氮气吸附、FE-SEM以及甲烷等温吸附等手段分析页岩储层的岩石类型、地化、矿物组成、孔隙结构和含气性特征。结果表明,与海相页岩相比,柴达木盆地北缘中侏罗统页岩具有"两高两低两种类型"的特点,即有机碳含量高、黏土矿物含量高,热演化程度低、脆性矿物含量低,有机质类型以Ⅱ、Ⅲ型为主。较低的热演化程度导致样品有机质孔隙发育较少;有机酸的溶蚀作用及矿物的转化作用是次生孔隙形成的主要因素。与海相页岩不同的是,高丰度低演化程度导致该演化阶段以产液态烃为主,且样品中可溶有机质含量较高,它对于样品的孔隙结构和甲烷赋存状态都有影响,表现为随比表面积增大,样品等温吸附实验结果呈现下降的趋势。对于高丰度低演化程度湖相页岩储层特征的研究,不仅为柴达木盆地北缘中侏罗统页岩气的勘探开发提供地质依据,同时也完善了页岩气地质理论。     

浙江土壤矿物组成特征

对浙江省29种母质和16种土类或亚类构成的69个母质一土类单元共194个土壤样品中的矿物成分进行测定，分析得出矿物种类及矿物百分含量。在此基础上分析了浙江省土壤矿物组成特征。不同土类或亚类土壤中矿物组成存在明显差异，矿物种数和含量变化较大。突出的特征是，相同母质类型土壤含有相似的矿物种类，而且相同母质不同样品中同一矿物含量变化也较小，表现出同母质土壤矿物组成与含量具有相似性。在69个土壤剖面中，由A层到C层矿物种类和含量变化较小，土壤矿物组成明显受基岩影响和控制。宜把地质背景相同、矿物组成相近、土壤环境相似的成土母质作为划分土壤重金属污染评价单元，土壤类型只能作为评价单元的辅助划分依据。     

黄土高原黄土-古土壤的矿物组成及其环境意义

采自洛川和西峰剖面的34个黄土-古土壤样品分为砂、粉砂、粘土三个粒级进行了矿物成分分析。结果表明．黄土高原黄土和古土壤的矿物组成基本一致．除了方解石和褐铁矿、磁铁矿因在样品处理时已被剔除未予计算外，其主要矿物是石英、云母、长石和绿泥石。这4种矿物占总量的88％-91%，其他矿物有高岭石、蒙脱石、蛭石和少量重矿物。不同地质剖面和不同地层层位的矿物差异主要表现为组成矿物在含量和粒度上的变化。洛川与西峰剖面、古土壤与黄土以及相同古土壤层的上部与下部相比，它们的矿物组成主要表现为前者古有较少长石和较多云母和蛭石，而且颗粒较细，表明在土壤发育过程中使矿物转变的生物化学风化过程和使矿物颗粒由粗变细的物理风化过程并存。这一结果有利于这样一种土壤发育机制解释，即古土壤发育与黄土堆积过程同时进行，只是在古土壤发育时期黄土的堆积过程缓慢，成土作用大于黄土堆积作用而发育土壤。     

Compositional and source characterization of base progressively extracted humic acids using pyrolytic gas chromatography mass spectrometry

Cyclic base extraction is a commonly used method for the isolation of humic acids from soils and sediments. However, every extract may differ in chemical composition due to the complex nature of humic acids. To better understand the chemical composition of each extract, the heterogeneous property of humic acids and their speciation in environmental samples, eight fractions of humic acids were obtained in the present work by progressive base-extraction of Pahokee peat, and their chemical composition was characterized using two complementary pyrolytic techniques, namely conventional pyrolysis and methylation pyrolysis (TMAH) GC/MS. These quick and effective procedures provide an insight into the structure of macromolecules. The work shows that the lignin-derived aromatic compounds are major components of pyrolysates in both pyrolytic techniques, while aliphatic compounds originating from microorganisms and plants are minor components. Other compounds derived from proteins and carbohydrates at lower concentrations were also detected. Fatty acids were found in the pyrolysis without methylation, indicating their association with humic acid in a free state. These compounds are different from those formed during pyrolysis with in situ methylation, where fatty acids are generally believed to be the cleavage products of carboxylic groups bound to humic acids. A relative decreasing abundance of aromatic components and increasing abundance of aliphatic components in the pyrolysates as the peat was progressively extracted was also observed in this work, suggesting that the extraction of more hydrophobic aliphatics may be delayed in comparison to the aromatic components. Speciation and origin differences may also be important particularly considering that the contribution from lignin organic matter decreased with extraction number, as the contribution of microbial organic matter increased. The observed change in chemical composition with the extracted fractions indicates again that the humic acid distribution and their speciation are complex, and complete extractions are necessary to obtain a representative humic acid sample.     

铀有机地球化学研究进展

与铀矿有密切关系的有机质主要是腐殖酸(HAs)、富里酸(FAs)、微生物及细菌.腐殖酸与铀酰存在着强烈的吸附、络合及还原作用关系.微生物和细菌在铀矿形成过程中也起到很微妙的作用.在研究手段上包括试验、计算、热解分析、X射线分析、裂变径迹分析、电子探针、红外光谱、紫外光谱、荧光光谱、顺磁共振、色谱质谱联用等方法.     

Organic acids from source rock maturation: generation potentials,transport mechanisms and relevance for mineral diagenesis

Hydrous pyrolysis has been used to simulate maturation of source rocks with respect to the generation of organic acids and CO₂. The results from pyrolysis experiments on eight different source rocks at this laboratory are given and compared with published data. The investigation show levels of generation for acetic acid equivalent to 0.2–1.2% of the TOC of the source rock and total acids at a level of 1–2% of the TOC. The generated CO₂ is equivalent to 1–10% of the TOC. The relative amounts of CO₂ and organic acids and the maturity dependence of the yield are a function of the source rock type.The amounts of acids generated are sufficient to give significant concentrations in the fluid phases of the source rock and, after migration, in adjacent rocks. Reaction and equilibration with minerals will occur at the first contact, which in most cases will be in or close to the source rock. The organic acids may initially be dissolved in the oil phase, but their high aqueous solubilities will make them diffuse rapidly out of the oil phase and into the surrounding water phase as soon as the oil has migrated into porous carrier beds. The migration of the petroleum phase is driven by buoyancy and there is no equivalent drive for water flow from source rock to reservoir. If the distance between source and reservoir s large, the organic acids found in the reservoir formation waters must therefore have been transported in the oil phase or generated in situ from emplaced oil or disseminated kerogen. The high water solubility of the acids will, however, limit the distances they can be transported in the oil phase. In situ generation in the reservoir must therefore be seriously considered.     

Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: When clay minerals lead to identical molecular signature

Different studies have already pointed out the influence of clays during the analysis of pure organic compounds (especially alkanols, alkanoic acids) as well as macromolecules (humic acids) by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS). Especially, the occurrence of clay minerals favors the generation of aromatic units such as alkylbenzenes and polycyclic aromatic hydrocarbons. So as to better identify the nature of the organic compounds which are sensitive to the presence of clays during flash pyrolysis, a humic acid mixed in variable proportions of a Na-homoionic clay was tested. The smectite/humic acid mixtures containing from 10% to 100% humic acid allowed us to identify the progressive disappearance or appearance of specific compounds after PyGC–MS.n-Alk-1-enes disappear when the clay proportion is higher than 67%. For higher contents of Na-smectite, n-alkanes become less and less abundant with a preferential consumption of high molecular weight n-alkanes, whereas the aromatic hydrocarbon proportion increases. Moreover, the distribution of each aromatic hydrocarbon family (alkylbenzenes and alkylnaphthalenes) has been investigated. The pyrogram of pure humic acid exhibits a specific distribution of alkylbenzenes and alkylnaphthalenes reflecting the structure of the organic macromolecule. With the increase in clay proportion, these distributions are modified and lead to other distributions with a preferential predominance of thermally stable isomers.Pyrograms of humic acid and undecanoic acid in the presence of 90% of Na-smectite are similar, especially concerning alkylbenzene and alkylnaphthalene distributions. Therefore, clays (Na-smectite in our experiments) in high proportion modify initial organic products by recombination reactions and lead to the generation of new compounds of very similar distribution, whatever the nature of the initial organic matter. Such results underline the very important catalytic properties of clay minerals on functionalized organic matter during flash pyrolysis.     

试论有机质在华南花岗岩风化壳REE溶出、迁移和富集中的作用

通过实验研究，论证了花岗岩风化壳中存在有机质，含有丰富的一元脂肪酸和二元脂肪酸，腐殖酸及多糖化合物。ＲＥＥ能以ＲＥ（Ｈ２Ｏ）配位离子从原岩溶出，一些有机介质和无机介质有助于ＲＥＥ从原岩溶出、迁移，其中以脂肪酸溶出量最高。溶出过程配位反应与水解反应同时出现，溶出和在风化壳中保留同时进行，反应受ｐＨ控制。风化壳中ＲＥＥ存在有机结合形态，可能与长链酸或腐殖酸关系比较密切。活性态ＲＥＥ除了与粘土矿物关系密切外，可能与多羟基化合物或多糖有关。     

北京西山地区下苇甸剖面寒武系张夏组鲕粒硅化成因探讨

鲕粒作为碳酸盐岩中非常重要的指相颗粒,其研究主要集中在成因上面,而成岩作用研究较少。北京西山地区下苇甸剖面寒武系张夏组发育大套鲕粒灰岩,通过对该剖面野外实测、薄片观察、XRD测试等手段,结合有机碳、热解等地化参数,对鲕粒的硅化机制及其硅质来源做了系统的研究。结果表明,鲕粒溶蚀再沉淀或者新生变形作用造成鲕粒边缘有机质富集,有机质演化释放的有机酸是硅质沉淀的主要因素,硅质来源主要为陆源输入和黏土矿物的转化。由于有机质主要富集在鲕粒边缘,形成有机质膜,从而造成硅质的沉淀主要沿鲕粒边缘发生,形成鲕粒边缘特有的硅化套,这种结果也从侧面反映了微生物在原始鲕粒形成中发挥了重要作用。     

泥页岩热模拟实验及成岩演化模式

随着泥页岩油气勘探开发的不断推进,对泥页岩的成岩作用研究越来越受到重视。通过对三种不同干酪根类型的泥页岩样品的热模拟实验发现,随着有机质成熟度的增加,干酪根热解生烃产生的有机质孔及不稳定矿物溶蚀孔增加,是泥页岩储集空间增加的主要原因;泥页岩成岩作用类型主要有黏土矿物转化、不稳定矿物溶蚀作用和重结晶作用;结合镜质体反射率,建立了基于热模拟实验的泥页岩综合成岩演化模式。研究表明:不同类型的干酪根在生烃过程中演化特征不同,Ⅰ型干酪根以"解聚型"的途径生烃,以产生有机质边缘孔为主;Ⅲ型干酪根以"平行脱官能团型"的途径生烃,以产生有机质内部孔为主;Ⅱ型干酪根介于两者之间,既可以产生有机质内部孔,也可以产生有机质边缘孔。     

Verwitterungsversuche mit organischen Säuren an einigen schwerlöslichen Fe-Pb-Zn und Cu Erzmineralen,angewendet auf die Genese des Kupferschiefers

The 1–2 mm fraction of FeS₂, Fe₃O₄, PbS, PbSO₄, ZnS, ZnCO₃, Cu₂S and Cu₂(OH)₂CO₃ was dissolved in water, dilute HCl and 0.01 m organic acids (tannin, salicylic acid and citric acid) at 1 atm and 20° C. Duplicate samples of one gram each were placed in 50 ml of solvent with shaking once each day for one month at pH's of 2, 4 and 6. The pH of all the solutions was maintained by periodic addition of either HCl or NaOH. Comparing the results at pH 6, a value observed under surface conditions, the organic acids had a higher metal ion concentration because of their complexing ability. Results at pH 6 in ppm of the metal ions are shown below: For example the Fe concentration dissolved from pyrite in water was 0.02 ppm but 2.3–4.3 in the organic acids. From malachite 0.2 ppm Cu were dissolved by water but 25–1550 ppm by the organic acids. In general Cu minerals seem to be more soluble in organic acids than the Pb, Zn and Fe minerals. The different solution power of the organic acids within the experiments seems not to be caused by the crystallography of the minerals tested. Further there apparently is no preferential complexing of an organic acid with respect to a distinct anion or cation of the minerals. The experiments therefore show, that it is difficult to predict exactly which organic acid is most effective in dissolving minerals. However the experiments should apply to natural weathering conditions of ore minerals and may aid in understanding metal ion transport. For example the origin of the high Cu concentration in the sedimentary “Kupferschiefer” are more easily explained by weathering and transport of Cu in the form of organo-metallic complexes than by reaction with only water. The Cu content in organic acids is much higher than in water and the Cu concentration in the solutions now is not so strongly controlled by the solubility of Cu-cabonates and phosphates.