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℃.     

EFFECTS OF HEATING RATE AND PARTICLE SIZE ON THE PRODUCTS YIELDS FROM RAPID PYROLYSIS OF BEECH-WOOD

ABSTRACT

Effects of pyrolysis temperature (300–1000 ^°C), heating rates (100, 500, 1000, and 10,000 ^°C/s), and particle sizes (53–63,104–120,177–270, and 270–500 urn) on the yields and formation rates of tar, light oils, total gases, and char from pyrolysis of beech-wood under 1 atm helium pressure were studied. Wood particles were pyrolyzed in strips of stainless steel wire mesh in a captive sample apparatus; and yields of products were measured in weight percent of original wood as a function of temperature for different heating rates and particle sizes. The overall weight loss achieved from pyrolysis of this wood was about 90%. The total yields of tar and light oils from pyrolysis of this wood accounted for up to 80% of the original wood above 400 ^°C. Due to the post-pyrolysis reactions of tar and light oils, the tar and light oils yields go through a maximum with pyrolysis temperature for all particle sizes and most heating rates studied here. As particle size increases from 53–63 μm to 270–500 μm the maximum tar yield decreases from 53% to about 38%. The maximum tar yield also decreases with increasing the heating rate from 70% at 100 ^°C/s to 48% at 10,000 ^°C/s heating rate. Theses results indicate that as the intra-panicle post-pyrolysis cracking reactions of tar increases at higher heating rates and with larger particles the tar yield decreases. Tar was also analyzed with GPC for the effects of above pyrolysis parameters on the tar molecular weight. The tar average molecular weight. remains relatively constant (M_w = 300 amu, M_n = 155 amu, and M_z = 483 amu) under helium atmosphere with pyrolysis temperature at 1000 ^°C/s heating rate and with 53/63 u m particle size. The average molecular weight of tar does not significantly varies with heaung rate, but it decreases as the particle size increases.     

Structural characterization of oil shale occurring in Mengen,Turkey

This study deals with structural characterization of oil shale obtained from the township of Mengen in Bolu, Turkey by means of proximate analysis, ultimate analysis, FTIR spectrometry, XRF spectrometry and thermogravimetric analysis. Thermogravimetric analysis was employed to investigate pyrolysis of the oil shale samples at the heating rates of 5, 20, 40°C/min and the Coats and Redfern kinetic model to investigate their pyrolysis kinetics.     

油页岩有机碳的演化模式与评价方法

从干酪根的结构特性和有机碳的化学构成出发,来研究干酪根的演化与评价,能够深入地揭示油气生成过程的本质,可靠地进行生油岩油气生成量的估测。基于这一考虑,人们提出了“有效碳”、“有潜力碳”等概念。七十年代后期发展起来的固体样品 C-13核磁共振波谱分析新技术——交叉极化与幻角自旋(cross polarization and magic angle spinning,CP/MAS),可以直接测定固体试样中芳构碳与脂构碳的含量,从而为研究干酪根有机碳的构成及其演化提供了新的有效手段。     

PRODUCTS FROM FLASH PYROLYSIS OF A TURKISH LIGNITE IN A FREE-FALL REACTOR UNDER VACUUM

ABSTRACT

Flash pyrolysis of a Turkish lignite under vacuum in a free-fall reactor was examined at a temperature range of 400 - 800 °C. Gaseous products were analysed with an on-line GC equipped with a manuel injection valve. Solvent fractionation was applied to the liquid product to separate preasphaltenes, asphaltenes and oils fractions. Two particle distributions of the lignite were used: ?0.315+0.2 mm and ?0.1 mm. The liquid yield increased with temperature up to 650 °C and, thereafter decreased for the larger particles. The maximum liquid yield, excluding pyroltic water, was found to be 8 % wt (dal) at 650 °C. In the case of the smaller particles the liquid yield increased steadily with temperature and the yield of liquid, excluding pyrolytic water, was 5.9 % wt (da) at 850 °C. The gaseous product yield also increased with temperature for both size fractions, and CO and CO₂ in the gaseous products were present in large amounts.     

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

ABSTRACT

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.     

EFFECTS OF HEATING RATE AND PARTICLE SIZE ON THE PRODUCTS YIELDS FROM RAPID PYROLYSIS OF BEECH-WOOD

Effects of pyrolysis temperature (300-1000 ^°C), heating rates (100, 500, 1000, and 10,000 ^°C/s), and particle sizes (53-63,104-120,177-270, and 270-500 urn) on the yields and formation rates of tar, light oils, total gases, and char from pyrolysis of beech-wood under 1 atm helium pressure were studied. Wood particles were pyrolyzed in strips of stainless steel wire mesh in a captive sample apparatus; and yields of products were measured in weight percent of original wood as a function of temperature for different heating rates and particle sizes. The overall weight loss achieved from pyrolysis of this wood was about 90%. The total yields of tar and light oils from pyrolysis of this wood accounted for up to 80% of the original wood above 400 ^°C. Due to the post-pyrolysis reactions of tar and light oils, the tar and light oils yields go through a maximum with pyrolysis temperature for all particle sizes and most heating rates studied here. As particle size increases from 53-63 μm to 270-500 μm the maximum tar yield decreases from 53% to about 38%. The maximum tar yield also decreases with increasing the heating rate from 70% at 100 ^°C/s to 48% at 10,000 ^°C/s heating rate. Theses results indicate that as the intra-panicle post-pyrolysis cracking reactions of tar increases at higher heating rates and with larger particles the tar yield decreases. Tar was also analyzed with GPC for the effects of above pyrolysis parameters on the tar molecular weight. The tar average molecular weight. remains relatively constant (M     

COMPARATIVE STUDY BETWEEN THE KINETICS OF RETORTING OF OHIO ANO COLORADO SHALE

ABSTRACT

A comparative study between the kinetics of oil generation from Ohio and Colorado shales has been done. To facilitate comparison and to eliminate systematic errors, the same retorting system was used to study the kinetics of both Ohio and Colorado shales. Temperatures ranging to 923° K and nitrogen and carbon dioxide as sweep gases were used for this study. Both the isothermal and non-isothermal retorting techniques were employed for the kinetic measurement and the results obtained compared favorably with each other. The pyrolysis of Ohio shale was also found to comply with first order kinetics within the limits of experimental error. The study gave an apparent activation energy of 149.1 ± 2.8 KJ/mol for Ohio shale (25 cm³/kg) and 182.5 ± 3.5 KJ/mol for Colorado shale (110 cm³/kg).     

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

ABSTRACT

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.     

EVALUATION OF OIL YIELD LOSSES DURING THE RETORTING OF OIL SHALE AT LOW VOID FRACTIONS. PART 1. THE EFFECTS OF PARTICLE SIZE AND RESOURCE GRADE

ABSTRACT

The economics of vertical modified in situ (VMIS) retorting of oil shale can be improved by decreasing the quantity of oil shale which is mined and transported to the surface. However, decreasing the quantity of oil shale removed from the retort also decreases the void fraction in the shale bed and this can affect the retorting process. The Western Research Institute has completed a series of experiments designed to investigate the effects of different experimental parameters on retorting oil shale at low void fractions. The effects of changes in the experimental parameters, oil shale particle size and resource grade, on oil yield losses have been evaluated using previously described oil yield loss diagnostic methods. These methods show that cracking–plus–combustion losses are the major and more variable source of chemically related oil yield losses. In experiments investigating changes in oil shale particle size, these losses correlate with the temperature differential between thermocouples in the rubble and in the interior of the oil shale particles. The data from the experiments investigating the effects of changes in resource grade on oil yield losses do not follow this correlation because of additional combustion of the produced oil during the lean resource grade experiment. Coking losses from experiments investigating both parameters were found to decrease with increased heating rate of the oil shale when significant differences in the heating rate were observed.     

Pyrolysis characteristics of a North Korean oil shale

Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 °C at a heating rate of 10, 15, 20 and 25 °C/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 oC. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are CH4(the most abundant), H2, CO2, H2 S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.     

A COMPARISON OF TRANSPORT PROCESSES ALLOWING ORGANIC MATTER TO BE RECOVERED FROM GREEN RIVER SHALE AT 400°C

One-inch blocks of oil shale were treated under three different reaction conditions at 400°C to determine the kinds and amounts of organic materials recoverable. Extractions with liquid and combined liquid-supercritical solvent were found to be effective methods of recovering organic material from shale. Supercritical fluid extraction with methanol-water was found to be more effective than distillation-liquid flow mechanisms; however, large amounts of oil remained in the shale. Low-molecular-weight non-polar compounds were found to be the materials most easily recovered from shale while high-molecular-weight polar compounds were found to be the most difficult materials to recover.     

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。     

小颗粒页岩流化干馏工艺及其影响因素

以桦甸小颗粒页岩尾矿为原料,在流化干馏装置上进行热解实验。结果表明,页岩尾矿最佳热解反应条件为:粒径5 mm左右,加热速率6～10℃/min,干馏终温500℃。在此条件下,油页岩热解收率可达90%。     

COMPARATIVE STUDY BETWEEN THE KINETICS OF RETORTING OF OHIO ANO COLORADO SHALE

A comparative study between the kinetics of oil generation from Ohio and Colorado shales has been done. To facilitate comparison and to eliminate systematic errors, the same retorting system was used to study the kinetics of both Ohio and Colorado shales. Temperatures ranging to 923° K and nitrogen and carbon dioxide as sweep gases were used for this study. Both the isothermal and non-isothermal retorting techniques were employed for the kinetic measurement and the results obtained compared favorably with each other. The pyrolysis of Ohio shale was also found to comply with first order kinetics within the limits of experimental error. The study gave an apparent activation energy of 149.1 ± 2.8 KJ/mol for Ohio shale (25 cm³/kg) and 182.5 ± 3.5 KJ/mol for Colorado shale (110  cm³/kg).     

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.     

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.     

Thermogravimetric analysis and kinetic study of heavy oil pyrolysis

Pyrolysis, so-called devolatilization, is one of the first steps of all thermochemical processes occurring in an inert atmosphere. The authors discuss the main kinetic features of heavy oil pyrolysis, on the basis of the data derived m from a TGA analysis and by using a kinetic model. The samples were heated over a range of temperature from 400 K to 430°C at various heating rates between 10 and 80°C/min. Experimental results showed that the effect of time is considerable in the case of tar conversion, compared to char and gases.     

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.     

全氢型工艺再生废润滑油技术的开发

介绍了中国石化抚顺石油化工研究院开发的废润滑油高压加氢处理与补充精制两段加氢组合工艺再生润滑油基础油技术。以废润滑油小于510℃馏分油为原料,在小型加氢反应装置上进行试验,在最大限度保留废润滑油中大部分优质基础油组分的同时脱除杂质和芳烃饱和。结果表明:在反应压力为(基准+5)MPa、加氢处理/补充精制反应温度为(基准+20)℃/(基准+10)℃、加氢处理/补充精制体积空速为基准/(基准+1.0)h~(-1)、氢油体积比为800的条件下,废润滑油可再生为润滑油基础油,生成油色度达到+30号,分馏得到大于400℃馏分的倾点为-18℃,100℃黏度为6.856mm~2/s,黏度指数为100,可生产HVIⅡ6号基础油产品;320~400℃馏分的倾点为-23℃,100℃黏度为3.218mm~2/s,可作为HVIⅡ3号基础油产品或3号工业白油;280~320℃馏分的40℃黏度为6.725mm~2/s,倾点为-45℃,可作为40号通用变压器油;大于320℃基础油的收率在80%以上,总液体收率大于98%。