CHARACTERISTICS OF PYROBITUMEN AND OIL OBTAINED FROM GREEN RIVER OIL SHALE PYROLYSIS

Pyrobitumens and oils generated from the isothermal pyrolysis of Green River oil shale at 400° 425°, and 440° C for different times were characterized. Elemental contents, average molecular weights, and hydrocarbon contents were determined for the pyrobitumens and oils. The pyrobitumens, a major initial pyrolysis product, had an average molecular weight exceeding 1200 and contained about 85% polars. The atomic hydrogen-to-carbon ratio, nitrogen content, and average molecular weight of the pyrobitumens changed with pyrolysis temperatures and times. The variable composition of the pyrobitumens suggests that pyrobitumen should not be considered as a single intermediate for kerogen decomposition. In contrast, oils contained 60% hydrocarbons and had a constant atomic hydrogen-to-carbon ratio and average molecular weight of about 250. However, the nitrogen content of the oils increased with increasing reaction time. The ratios of normal heptadecane/ pristane and normal octadecane/phytane, and odd-even predominance of oils were sensitive to pyrolysis temperatures and times. The rate constants, frequency factors, and activation center, for funding this work under cooperative Agreement Number DE-FE21-86MC11076.     

METALLOPETROPORPHYRINS AS PROCESS INDICATORS: SEPARATION OF PETROPORPHYRINS IN GREEN RIVER OIL SHALE PYROLYSIS PRODUCTS

Product oils from the LLNL Hot-Recycled-Solids (HRS) retorting process were separated to isolate and concentrate the metallopetropor-phyrins. A modified column chromatography procedure developed previously for heavy crude oils and tar sand bitumens was used. The fractions were then examined by UV-vis spectroscopy to determine categories of porphyrins and other related metal-containing species.

No porphyrins were found in the hexane fraction (least polar fraction); Ni porphyrins were found in the methylene chloride fraction (moderate polar fraction); and a free-base porphyrin-like species was found in the methanol fraction (the most polar fraction) of some of the oils. The CH₂Cl₂ fractions were further examined to quantify the amount of porphyrins detected. In the whole oil samples examined, ∼ 40 wt % of the Ni was found as Ni petroporphyrins. The vacuum residua of two product oils had ∼ 20 wt % of the Ni bound as Ni por-phyrins indicating that the vacuum distillation process destroys porphyrins.     

油页岩干酪根热解产物特性研究

采用裂解色谱(PY-GC-MS)、电子顺磁共振波谱(EPR)和红外光谱(FTIR)等技术手段,分析了Estonia油页岩中干酪根及其热解产物的结构特性,研究了不同温度下中间产物与最终产物的关联性.结果显示:油页岩热解符合干酪根热解为中间产物热沥青,热沥青再热解为页岩油、干馏气和半焦等产物反应路径,中间产物热沥青的生成趋...     

AROMATIC HYDROCARBONS OBTAINED BY THERMAL CONVERSION OF GREEN RIVER OIL SHALE KEROGEN USING CO AND H2O AT ELEVATED PRESSURE

Aromatic hydrocarbons produced from the reaction of Green River oil shale with carbon monoxide and water at elevated pressure and at temperatures from 300 to 450°C were investigated. The isolation of these aromatic hydrocarbons involved ion exchange, complexation, silica gel, and alumina chromatographic techniques. Compound types present in these aromatic hydrocarbons were studied by high resolution mass spectrometry and combined gas chromatography-mass spectrometry. Compound types were mostly phenylcyclohexylal- kanes, dinaphthenobenzenes, trinaphthenobenzenes, naphthenonaphthalenes, and carotenoid types at 300°C; but at 450°C compound types were mostly alkyl-benzenes, alkylbiphenyls, and alkylnaphthalenes. The composition of aromatic hydrocarbons from the benzene-extracted bitumen of Green River oil shale was found to be similar to that in the 300°C product from the CO-H₂O reaction.     

RECOVERY OF ORGANIC MATTER FROM GREEN RIVER OIL SHALE AT TEMPERATURES OF 400°C AND BELOW

Experiments to recover organic matter from Green River oil shale in high yields at temperatures of 400^°C and below are described. Three different recovery procedures are discussed: 1) experiments wherein liquid organic materials were extracted at atmospheric pressure and temperatures below 75^°C by solvents of different strengths, 2) autoclave experiments where liquid organics were recovered by heating the shale with a variety of solvents at temperatures between 300 and 400^°C and pressures between 5 and 32 MPa, and 3) an autoclave experiment where liquid organics were recovered by heating shale in an argon atmosphere for 1 hour at 400^°C. The liquid organic materials recovered in these experiments represent from four to 90 weight percent of the total organic material in the shale. The liquid organic materials have an average molecular weight of between 500 and 600 amu as compared to a typical shale oil that has an average molecular weight of 300 to 350 amu. Elemental analyses show that the liquid organic materials contain high percentages of hydrogen and nitrogen, as does shale oil. Moreover, the liquid organic materials also contain much larger concentrations of oxygen-containing compounds than shale oil. The experimental results suggest the possibility of developing a new process for recovering both organic and inorganic material from Green River shale.     

AROMATIC HYDROCARBONS OBTAINED BY THERMAL CONVERSION OF GREEN RIVER OIL SHALE KEROGEN USING CO AND H2O AT ELEVATED PRESSURE

ABSTRACT

Aromatic hydrocarbons produced from the reaction of Green River oil shale with carbon monoxide and water at elevated pressure and at temperatures from 300 to 450°C were investigated. The isolation of these aromatic hydrocarbons involved ion exchange, complexation, silica gel, and alumina chromatographic techniques. Compound types present in these aromatic hydrocarbons were studied by high resolution mass spectrometry and combined gas chromatography-mass spectrometry. Compound types were mostly phenylcyclohexylal- kanes, dinaphthenobenzenes, trinaphthenobenzenes, naphthenonaphthalenes, and carotenoid types at 300°C; but at 450°C compound types were mostly alkyl-benzenes, alkylbiphenyls, and alkylnaphthalenes. The composition of aromatic hydrocarbons from the benzene-extracted bitumen of Green River oil shale was found to be similar to that in the 300°C product from the CO-H₂O reaction.     

INTERACTION OF SUPERCRITICAL METHANOL AND WATER WITH ORGANIC MATERIAL IN GREEN RIVER OIL SHALE

A series of experiments to study the interaction of supercritical methanol and water with Green River oil shale was performed. The volume percentage of methanol (CH₃0H) in water was varied. The temperature was held constant at 400°C. The products were fractionated and characterized with infrared spectroscopy and elemental analyses. A ¹³CH₃0H experiment was carried out and 13C nuclear magnetic resonance (NMR) analysis was used to prove the incorporation of methanol into the products. The methyl esters resulting from the incorporation were isolated and characterized by high resolution mass spectrometry. The experiments on a model compound and gas chromatographic/mass spectral (GC/MS) analysis of the product showed that methanol can react with carboxylic acids found in Green River oil shale to form methyl esters. However, this incorporation of methanol into the product oil from supercritical fluid extraction was found to be not sufficient to account for the increased oil yields, The role of methanol in these experiments on Green River oil shale is discussed.     

CHARACTERIZATION OF ORGANIC MATTER RECOVERED FROM GREEN RIVER OIL SHALE AT TEMPERATURES OF 400°C AND BELOW

Organic matter extracted from Green River oil shale by supercritical extraction experiments was characterized by elemental analysis, number average molecular weight determination and field ionization mass spectrometry. The organic matter was also separated into fractions of organic acids, bases, and hydrocarbons. Characterization data demonstrate that the organic matter recovered in high yield from autoclave experiments is similar in composition to organic matter extracted in low yield at solvent reflux temperatures. The composition of organic matter extracted from Green River shale by supercritical techniques is compared with the composition of Green River shale oil produced by several pilot-scale retorting processes.     

INTERACTION OF SUPERCRITICAL METHANOL AND WATER WITH ORGANIC MATERIAL IN GREEN RIVER OIL SHALE

ABSTRACT

A series of experiments to study the interaction of supercritical methanol and water with Green River oil shale was performed. The volume percentage of methanol (CH₃0H) in water was varied. The temperature was held constant at 400°C. The products were fractionated and characterized with infrared spectroscopy and elemental analyses. A ¹³CH₃0H experiment was carried out and 13C nuclear magnetic resonance (NMR) analysis was used to prove the incorporation of methanol into the products. The methyl esters resulting from the incorporation were isolated and characterized by high resolution mass spectrometry. The experiments on a model compound and gas chromatographic/mass spectral (GC/MS) analysis of the product showed that methanol can react with carboxylic acids found in Green River oil shale to form methyl esters. However, this incorporation of methanol into the product oil from supercritical fluid extraction was found to be not sufficient to account for the increased oil yields, The role of methanol in these experiments on Green River oil shale is discussed.     

EFFECT OF TIME AND PRESSURE ON RECOVERY OF OIL FROM GREEN RIVER OIL SHALE IN EXTRACTION EXPERIMENTS CONDUCTED AT 400°C

The paper describes the effect of time and pressure on liquid product yields when Green River shale was exposed to supercritical methanol-water at 400^°C and then extracted with benzene-methanol. Reaction times between 1 second and 34 minutes were studied as were pressures between 1800 and 5200 psi. Maximum yields of liquid product were obtained after a methanol-water treatment time of about 34 minutes. Presssure did not have a significant effect on product yields. Chemical characterization of Selected liquid products is reported and shows that the product composition varies with time. Exfoliation of shale also increases with treatment time. This phenomenon is discussed and illustrated.     

页岩油及其特征

通过与“油页岩”、“致密油”和“泥岩裂缝性油藏”等资源的对比分析,将石油勘探界的页岩油定义为以页岩为主的页岩层系中所包含的石油资源.通过分析页岩油地质特点,认为页岩油与常规石油资源有较大区别,但与页岩气在地质特征和开发方式方面有很多相似性.页岩油的“甜点”与裂缝发育程度、基质孔隙大小和地层异常压力情况关系密切.在分析鄂尔多斯盆地延长组页岩层系地质特征后认为,该区页岩油与页岩气可能存在共生现象,页岩油资源潜力巨大;中国在页岩油理论研究和勘探实践过程中应借鉴美国成功的理论模型和勘探开发经验,同时根据中美地质条件的差异性探索适合中国地质条件和经济技术水平的页岩油之路.     

NON-ISOTHERMAL PYROLYSIS OF TWO KINDS OF CHINESE OIL SHALE

Abstract

Non-isothermal pyrolysis of two kinds of Fushun oil shale with particle sizes, <0·075 mm, 0·3 - 0·5 mm, 0·75 - 1·0 mm and 1·5 - 2·0 mm, has been investigated in stream (nitrogen) at the flow rate of 100 ml/min by thermo-gravimetric analyzer with a linear heating rate 6·8K/min. It has been found that the temperaturee intervals of oil-generation from rich grade shale ( 9·8 % Fisher Assay oil yield ) and poor grade shale ( 3·9% Fisher Assay oil yield ) with particle size less than 2·0 mm are 400 - 500 °C and 400 - 520° C respectively. The kinetic treatment of the thermo gravimetric data reveals that pyrolytic reactions of the two kinds of Fushun oil shale are both of the first order, but with different activation energy E and pre-exponential factor A in different temperaturee regions during pyrolysis. This is different from what was described in general terms as global first order reaction for oil shale pyrolysis by other anthers. The kinetic parameters for pyrolysis of the two kinds of Fushun oil shale with different particle sizes were calculated by means of least square curve fitting, and the influence of particle size on pyrolysis was also discussed.     

石油焦与油页岩混合燃烧特性及其燃烧动力学

采用ZRY-2P综合热分析仪对不同质量比的石油焦/油页岩的混合燃料进行了热重分析,得到了它们的热重(Thermogravimetric, TG)及微商热重(Differential thermogravimetric,DTG)曲线和混合燃烧特性,并计算出燃烧动力学参数。结果表明,随着石油焦/油页岩的质量比逐渐降低,石油焦/油页岩混合燃料的TG曲线变化逐渐缓慢,DTG曲线逐渐呈现3个峰,其中有2个峰明显;当石油焦/油页岩的质量比为3/2时,综合燃烧性能最好,体现出混合燃烧所具有的优势。除石油焦/油页岩质量比为4/1的样品外的其他混合样品,在低温段和高温段活化能按大小排列的顺序与频率因子大小排列的顺序均相同,这体现了活化能和频率因子变化的一致性.石油焦与油页岩混合燃料在低温段的燃烧反应级数为1.30左右,所需活化能较低;在高温段的燃烧反应级数为1.00左右,所需活化能较高。石油焦与油页岩的混合燃料具有很大的实际工程应用价值。     

抚顺油页岩热分解过程的热重法研究

采用线性升温速率6.8k/min的热重装置,在惰性气(氮)流量100ml/min的条件下,考察了粒度<0.075mm,0.3～0.5mm,0.75～1.0mm及1.5～2.0mm的两种抚顺页岩的非等温热分解过程.根据试验得出的热重曲线,失重速率-温度曲线及转化率-温度曲线,获得了抚顺页岩的初始分解温度及失重速率峰值温度等动力学特征值,并确定,粒度小于2.0mm的抚顺富矿页岩(铝甑产油率9.8%)及贫矿页岩(铝甑产油率3.9%)的主要热解生油阶段分别为400～500℃及400～520℃.     

A SINGLE PARTICLE MODEL FOR PYROLYSIS OF OIL SHALE

ABSTRACT

In many heterogeneous pyrolysis reactions the porous solid undergoes geometrical changes due to the consumption of solid reactant which decrease the compressive strength of the solid matrix. In this study a volume expansion model is proposed for pyrolysis of a single shale particle. This model not only takes into account the structural changes and the intraparticle gradients, but also the functional dependencies of various parameters on the variation of solid reactant conversion and internal temperature distribution.

Effects of various parameters which are expected to be encountered in an in-situ retorting process were investigated. Primary emphasis was placed on determining the manner in which transport processes affect the yield of pyrolysis product. The results indicate that Intraparticle heat transfer is a dominant factor in the pyrolysis of oil shale and that volume expansion favors the decomposition rate.     

A SINGLE PARTICLE MODEL FOR PYROLYSIS OF OIL SHALE

In many heterogeneous pyrolysis reactions the porous solid undergoes geometrical changes due to the consumption of solid reactant which decrease the compressive strength of the solid matrix. In this study a volume expansion model is proposed for pyrolysis of a single shale particle. This model not only takes into account the structural changes and the intraparticle gradients, but also the functional dependencies of various parameters on the variation of solid reactant conversion and internal temperature distribution.

Effects of various parameters which are expected to be encountered in an in-situ retorting process were investigated. Primary emphasis was placed on determining the manner in which transport processes affect the yield of pyrolysis product. The results indicate that Intraparticle heat transfer is a dominant factor in the pyrolysis of oil shale and that volume expansion favors the decomposition rate.     

废轮胎热解油的研究现状及应用方案分析

综述了国内外对废轮胎热解油的分析和利用现状,总结了热解油的特点。根据热解油的性质和化学组成的分析结果,提出了废轮胎热解油的应用方案:由轻质馏分提取苯、甲苯、二甲苯、柠檬烯等具有高经济价值的化学品或经加氢精制后用作车用汽油;中质馏分经加氢精制脱除S、N后作柴油调和组分;重质馏分可作燃料油或焦炭的生产原料。     

茂名油页岩裂解气轻烃组成和热演化特征

本文通过对茂名油页岩模拟实验裂解气轻烃的研究,发现裂解气中的轻烃和沉积物中的轻烃较为相似。随热演化程度的增加,C_1含量逐渐减少。相对于正构烷烃的含量,异构烷烃的含量逐渐减少。在较高的成熟度阶段,正构烷烃表现为nC_7>nC_6>nC_5≈nC_4。这代表了一种富氢母源形成轻烃的特征。此外,本文对iC_4/nC_4,iC_5/nC_5指标也进行了讨论。     

河南页岩油与常规原油和油母页岩油性质比较

对河南油田的页岩油及其馏分进行了详细的性质测定及分子组成表征,并与大庆原油及传统的油母页岩油进行了比较。结果表明,河南页岩油与油母页岩油性质差别较大,与大庆原油性质比较接近,可采用与常规原油相似的加工方式进行加工。     

不同介质条件下油页岩热解的初步研究

利用高压釜热解实验装置,对采自民和盆地的油页岩进行全岩、全岩加去离子水和全岩加碱性饱和KCl溶液等3个系列的热解实验研究,并对这3个系列生成的页岩气和页岩油进行对比分析。结果表明：介质的加入有利于液态物的产出,跟油页岩直接加热相比,去离子水的加入使得页岩油的平均产率从83.66 mg/g提高到210.15 mg/g,但是抑制页岩气的生成;而碱性饱和KCl溶液的加入对页岩油和页岩气都有贡献,使得页岩油平均产率从83.66 mg/g提高到186.16 mg/g,页岩气平均产率从7.56 mL/g增大到9.08 mL/g。