桦甸油页岩有机岩相特征及其富集特性

为了研究油页岩中有机组分结合特性对有机质分离富集的影响,利用薄片透射光、反射单偏光、反射荧光等煤岩学研究手段研究桦甸油页岩中有机组分的种类、含量及赋存状态,并利用两种密度分离手段研究油页岩中有机质的解离特性.结果表明,桦甸油页岩有机质的变质程度较低,有机显微组分以沥青质体为主,占85.8%,镜质组和惰质组含量较低;有机质与矿物结合紧密,形成有机-矿物复合体,密度分离方法对有机质与矿物质分离效果有限;浮沉实验小于1.40g/cm³密度级样品的热解失重量及失重速率均低于较高密度级产物,这与颗粒状镜质组、惰质组与矿物质结合程度相对较差,在较低密度级产物中富集有关.     

桦甸油页岩热解特性的研究

在热分析仪上进行了桦甸油页岩的热解特性研究,升温速率分别为10℃/min、20℃/min、30℃/min和40℃/min,终温为900℃。实验表明油页岩的热解是分两步进行的。在低温段主要是油页岩中可挥发性的气体溢出引起热解失重;高温段则主要是一些有机质、固定碳的热解过程。低温段的热解是主要的,它基本上热解掉了油页岩重量的15％－27％左右,油页岩挥发分含量很高且具有集中析出的特性,在400℃－530℃区间内可挥发物质迅速热解守比,其在高温段的热解产率很小,只有总重量的10％左右。随着升温速率的增加低温段的高温段热解的区分更加明显,且使油页岩的热解产率提高。文中给出了不同升温速率下的桦甸油页岩热解特性数据和化学反应动力学参数。     

矿物质对桦甸油页岩热解产物影响特性

对桦甸油页岩进行逐级酸洗并对原样及各级酸洗样品的热解产物进行了碳平衡计算以及气相色谱和傅里叶红外光谱实验,得到了矿物质对油页岩热解不凝性气体、半焦以及页岩油的影响特性。结果表明,碳酸盐可以促进有机碳和氢向页岩油中转化,而硅酸盐对有机碳和氢向页岩油中转化具有抑制作用,碳酸盐和硅酸盐均可以使得页岩油中氢碳原子比降低。碳酸盐促进了油页岩热解产油并抑制了干酪根向不凝气分解转化,而硅酸盐抑制了油页岩热解产油但对干酪根向不凝气的分解转化具有促进作用。碳酸盐和硅酸盐均可以促进热解不凝气中CO_2和H_2的生成,而对CO的生成具有抑制作用,碳酸盐可以抑制热解不凝气中碳氢化合物的生成,而硅酸盐对其生成具有促进作用。碳酸盐和硅酸盐均可以使得页岩油中脂肪链长度变短及异构化程度变大,并能够提高干酪根热解产物的芳构化程度。     

油页岩与煤的混烧特性研究

使用STA409型热综合分析仪进行了桦甸油页岩与高硫合山煤的混烧特性实验研究，得到了油页岩和高硫煤混烧的TG和DTG曲线，分析了不同Ca/S对油页岩和高硫煤混烧特性的影响规律，同时运用Freeman-Carroll法计算得到了不同Ca/S下的油页岩燃烧特性化学反应动力学参数。研究表明，在高硫煤中加入少量的油页岩，高硫煤的燃烧特性有所改善，燃烧特性趋好；油页岩的加入使得高硫煤低温段的燃烧产物初析温度降低，着火温度提前；在高硫煤中加入20%左右的油页岩作为可燃脱硫剂从燃烧角度讲是切实可行的。     

油页岩裂解色谱质谱分析

油页岩是一种含油有机质的沉积岩,从油页岩提炼可得到页岩油,是石油的部分替代能源.随着原油储量的日趋减少,油页岩的研究及利用将会受到更多的重视.油页岩热加工得到的页岩油类似天然石油,但与石油相比,其不饱和烃和杂原子化合物含量较高,定性极差,但这些非烃化合物是宝贵的化工原料.对页岩油的烃类、非烃类杂原子化合物进行深入的研究,对页岩油的进一步加工以及非烃化合物的综合利用,都是非常必要的.     

汪清油页岩干馏过程中稀土元素迁移特性

利用逐级化学提取实验和电感耦合等离子质谱(ICP-MS)相结合的方法,以吉林汪清罗子沟油页岩为研究对象,对油页岩原样及半焦中的稀土元素含量、地球化学特性、分布模式及其赋存状态进行研究。结果表明,与中国煤相比,汪清油页岩中稀土元素含量明显富集,且轻稀土元素富集程度高于重稀土元素,轻重稀土元素分馏明显。δCe_N为1.46,表现为明显正异常,表明其成岩环境不受海水影响,稀土元素与陆源岩关系密切且来源一致。汪清油页岩中稀土元素主要赋存在无机矿物质中,有机质中含量极少,硅铝化合物结合态占大部分,不同提取态对油页岩中稀土元素的分馏效应影响不同。经过干馏过程,油页岩半焦中稀土元素含量变化不大,稀土元素有明显富集趋势。稀土元素在干馏过程中的迁移主要是由于稳定态、硫化物结合态减少,碳酸盐结合态增多,其中铁锰氧化物结合态变化不明显。     

油页岩固定床热解反应器中内构件强化作用

在内构件(传热板和中心集气管)外热式固定床反应器中研究了油页岩热解产物生成特性,并与无内构件的相同常规固定床反应器内的油页岩热解行为对比,考察了两反应器中油页岩升温特性、热解产物分布、页岩油品质以及气体产物组成的变化规律.结果表明,内置传热板和中心集气管显著强化了反应器内的传热,相对于无内构件常规固定床反应器,料层升温速率提高了约2倍.对于依兰油页岩,其热解页岩油产率明显提高,最高达11.1 wt%(干燥基),明显高于无构件常规固定床反应器获得的页岩油产率.随着外加热炉温度的升高,内构件固定床反应器的页岩油产率逐渐增加,而无内构件常规固定床反应器的页岩油产率则明显降低.当外加热炉温度为1000℃时,前者页岩油产率是后者的2.3倍,并且内构件固定床反应器的热解水产率较低.两反应器中热解气产物组成相近,其H2与CH4之和占气体总量的70 vol%左右,热值为4406~5400 kcal/Nm3.     

颗粒粒径对油页岩热解产油率的影响

以桦甸油页岩为原料研究了颗粒粒径对油页岩热解产油率的影响。将油页岩破碎、筛分得到<0.074、0.074~0.125、0.125~0.25、0.25~0.5、0.5~1和1~3 mm不同粒级样品,再将0.25~0.5、0.5~1和1~3 mm大粒级样品粉碎制得对应的细粉样品,采用低温干馏法和热重分析分别测定表征样品的油产率和有机质含量。结果表明,油产率随着粒径减小逐渐降低,从1~3 mm下的11.92%降到<0.074 mm下的6.14%。热重分析表明,有机质含量随着粒径降低而降低,且油产率与有机质含量有明显的线性关系。0.25~0.5、0.5~1和1~3 mm样品经粉碎后油产率降低、气产率升高,但变化值均小于1%。在破碎过程中有机质选择性地富集在大粒级样品中,且页岩油二次反应程度随着粒径的减小而增大,使得页岩油产率随着粒径的降低而降低,且有机质选择性富集是主导因素。     

油页岩热解挥发分中轻油吸附回收工艺初探

将活性炭纤维吸附回收工艺应用于油页岩热解气轻质油品回收,自行建立了移动床油页岩连续热解实验装置及相应的油品回收系统。实验结果表明,冷凝冷却至室温的桦甸油页岩热解气中轻质油品含量可达20 g/m³以上。通过活性炭纤维吸附,可将煤气中的轻质油品完全回收。竞争吸附实验表明,"轻油"中的BTX、乙苯、C_10~13的烷烃、烯烃等更容易吸附,碳数相对较低的烯烃、烷烃、环烷烃吸附能力相对较弱。这将为油页岩热解气轻油高效回收工艺开发提供基础数据。     

世界油页岩科技进展

本文概述了油页岩日趋重要的作用和用途,展望了八十年代油页岩工业的发展前景,重点评述了世界上油页岩炼油的一些工业试验炉型,包括用于块状页岩干馏的气体内热式炉型及用于颗粒页岩干馏的固体热载体干馏炉型,并涉及到某些新干馏工艺。本文还介绍了近年来油页岩的实验室试验和基础性研究工作,包括油页岩的生成,油母的组成、结构及性质、页岩油的组成和加工研究、油页岩热加工产物的组成及其综合利用等。     

Radiochemical neutron activation analysis of individual rare earth elements in monazites from different geological environments

Radiochemical neutron activation analysis /RNAA/ has been applied for the determination of individual rare earth elements /REE/, except Tm, in 8 Indian monazites and one each from Malaysia and Thailand. Because of the very low amounts of heavy rare earths /HREE/ compared to light rare earths /LREE/ in monazite, HREE from Ho onwards have been determined only after the separation of the heavy and light rare earth fractions in the irradiated monazite samples. The results indicate significant variations in REE contents from Eu to Lu among different monazite samples. The chondritic normalized REE patterns of all the samples show a prominent negative Eu anomaly with different slopes at the heavy rare earth end. All the individual REE, except Tm, have been reported for the first time in various Indian monazites.     

Rare earth element patterns in ultramafic rocks of the Schist Belt of Southwestern Nigeria by instrumental neutron activation analysis

24 Ultramafic rock samples from 3 different areas of the Schist Belt of Southwestern Nigeria were analyzed for 11 rare earth elements (REE) by instrumental neutron activation analysis (INAA). REE patterns of the ultramafic rocks are similar for the 3 different areas, and the REE abundances are smaller than for other types of rocks from the same areas. However, the moderate fractionation between LREE and HREE observed for these samples is unusual for ultramafic rocks. Some geochemical implications of the results are discussed.     

川西凹陷雷口坡组稀土元素特征及其意义

对川西凹陷丰卤1井雷口坡组岩屑样品进行了稀土元素(REE)的分析.结果表明,通过REE参数∑REE、LREE、HREE、w(LREE)/w(HREE)、w(LaN)/w(YbN)、δ Ce和δ Eu的比较,雷口坡组∑REE与LREE和HREE的变化呈正相关,LREE占∑REE的74%,对∑REE的变化起主要影响作用;R...     

河台金矿中稀土元素在韧性剪切过程中迁移行为的研究

通过对两类糜棱岩及其原岩的稀土元素含量的分析研究, 结果表明, 稀土元素在韧性剪切过程中发生有规律的成分变异. 在云母石英片岩及混合岩形成糜棱岩、超糜棱岩过程中, 即随着变形强度的增强, 单个稀土元素、轻稀土、重稀土和稀土总量均出现有规律的增加或减少, 而稀土元素配分模式不变. 通过对构造岩变形前后的等比分析, 认为两类不同的糜棱岩类中稀土元素的成分变异极小, 但存在少量稀土元素的迁入和迁出, 变化的原因是在岩石变形过程中发生了体积的改变和大量的流体作用影响, 并导致轻稀土相对富集、重稀土相对亏损的分异作用.     

镧系收缩效应对稀土-煤相互作用的影响及煤中有机态稀土的赋存形式研究

通过酸洗脱灰及腐殖酸提取等方法对伊敏褐煤进行处理,并应用ICP-MS对处理前后的样品进行了稀土元素测定。在对脱灰前后稀土元素与灰分和C、H、O等有机组成元素的相关性以及稀土元素在腐殖酸中的赋存特征分析的基础上,认为煤中稀土元素-有机质相互作用受煤化作用过程中的脱氧、脱氢和增碳作用控制。稀土与煤中各类官能团相互作用形成四类有机态稀土元素复合物,第一类是与被烷基侧链高度取代的芳香结构单元形成的复合物;第二类是与氢化芳香结构单元形成的复合物;第三类是与低取代度的芳香结构单元形成的复合物;第四类是与含氧官能团作用形成的复合物,后两类的稳定性差。这些有机态稀土元素复合物的稳定性在总体受镧系收缩效应控制的基础上,还受稀土元素化学价态的影响;重稀土与有机质形成的有机态稀土元素复合物的稳定性大于轻稀土。轻稀土在原煤中和腐殖酸的结合不稳定,且具有与镧系收缩相反的效应;轻稀土在脱灰煤中和腐殖酸的结合,与中稀土、重稀土在原煤和脱灰煤中腐殖酸结合规律相同,都体现了良好的镧系收缩效应。     

黔西南卡林型金矿床稀土元素地球化学特征

分析了黔西南地区板其、、丫他及戈塘等卡林型金矿床的(La/Yb)N、(La/Sm)N、∑REE及LREE/HREE等稀土元素的含量及参数特征.结果表明,该区金矿床相对富集LREE;该区戈塘金矿具有明显的MREE富集及正Eu异常的特点,表明成矿热液应该是一种还原性流体,来源于深部或至少经历过对富含斜长石源区的水-岩反应矿...     

Rare earth element patterns in lake sediments as studied by neutron activation analysis

Using instrumental neutron activation analysis, the vertical distribution of La, Ce, Nd, Sm, Eu, Tb, Yb and Lu was determined in 3 well dated sedimentary cores collected from Laguna Mar Chiquita, Argentina. Validation of the methodology was done using the Soil 7 (IAEA) reference material. The REE contents vary according to core location and lithological units, depending on the proportion of fluvial terrigenous components in the lake sediments. Lithologies with higher proportion of terrigenous components show higher REE concentrations, suggesting that the dominant REE carrier phase might be a detrital mineral. There is a consistent value of about 1.2 for (La/Yb)_N and (LREE/HREE)_N ratios for all sediments at the three sites, indicating a slight LREE enrichment in relation to the average shale NASC. Ce/Ce* values are close to 1.0, meaning that Ce behaves similarly to other light REE's.     

Measurement of rare earths elements in Kakul phosphorite deposits of Pakistan using instrumental neutron activation analysis

The rare earth elements (REEs) content of Kakul phosphate rock (PR) from different localities of the main Hazara deposits of Pakistan were determined using instrumental neutron activation analysis (INAA). 25 phosphorite samples were collected from different phosphorite sites and 6 samples representing different batches from the crushing plant near Kakul Mine. Concentrations of seven REEs (Ce, Eu, La, Lu, Sm, Tb and Yb) were determined in the PR samples. The highest amounts of Heavy and light rare earth elements (HREE and LREE) were quantified in the PR samples collected at the Phosphate Rock Crushing Plant while the lowest amounts of these REEs were measured in the Lambidogi Phosphorite deposit samples. Comparison with global data showed the REEs content of the studied PRs show lower range for all REEs and mostly comparable to the data reported by Israel and Syria. Calculated chondrite ratio for these elements depicts enrichment of LREEs in all phosphorite deposits.     

Instrumental neutron activation analysis of carbonatites from Homa Mountain, Kenya

Twenty eight (major and trace) elements including eight rare earth elements (REEs) in African carbonatite samples were determined by instrumental neutron activation analysis. The geochemical behavior of trace elements was studied in relation to the order of carbonatite intrusion from C1 to C4 through C2 and C3 at Homa Mountain, Kenya. The enrichment of Mn, Fe, Sr, Ba, Th, U and REE is found in the sixteen carbonatites examined in this study. The general increase in the concentrations of Na, Sc, Mn, Sb, Ba, Th, U and REE occurs from C1 to C4 through C2 and C2c, but C3 carbonatite shows a different pattern. The C3 carbonatite is extraordinarily enriched in Mn, Fe and Ba and is highly enriched in Cr, As, Sb and Th. The chondrite-normalized REE distribution pattern of the C3 carbonatite is not rich in the light REE. Strong fractionation between light and heavy REEs is found in the carbonatites, and moderate fractionation in the two alkalic igneous rock samples. In order to evaluate partitioning of REEs into carbonate, oxide and other mineral fractions, a selective chemical leaching technique on carbonatites was applied and is discussed in this study. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of individual rare earth elements in Vietnamese monazite by radiochemical neutron activation analysis

Radiochemical neutron activation analysis (RNAA) has been applied for determination of rare earth elements (REE) in Vietnamese monazite. The chemical separation procedure used is based on the chromatographic elution of rare earth groups, after the separation of²³³Pa(Th) in irradiated monazite samples by coprecipitation with MnO₂, the rare earth elements were retained by Biorad AG1×8 resin column in 10% 15.4M HNO₃-90% methanol solution. The elution of heavy rare earth (HREE) and middle rare earth (MREE) groups was carried out with 10% 1M HNO₃-90% methanol and 10% 0.05M HNO₃-90% methanol solution, respectively; while the light rare earths (LREE) were eluted from the column by 0.1M HNO₃ solution. The accuracy of the method was checked by the analysis of granodiorite GSP-I and the rare earth values were in good agreement.