生物质与油页岩混合热解特性研究

为了充分利用油页岩和生物质,以生物质和油页岩按照不同质量比的混合试样作为研究对象,采用TG-DSC联用技术进行了热重实验,分析了热解过程特性曲线并计算热解特性参数,采用差减微分法计算了热解动力学参数。结果表明:混合试样DTG曲线分别在低温段及高温段出现2个峰,前者主要是生物质的纤维素及半纤维素挥发分的热解析出,后者主要为油页岩热解析出挥发分;随混合试样中油页岩含量逐渐增多,热解后期逐渐出现因油页岩无机盐热分解吸热过多而出现DSC曲线吸热峰;混合试样低温段挥发分析出量及挥发分综合释放特性指数均大于高温段的值;生物质含量最高的混合试样(生物质与油页岩的质量比为4∶1)的挥发分初始析出温度最低,其挥发分最大释放速度的峰值及挥发分综合释放特性指数均最大;生物质含量较多的混合试样低温段活化能大于高温段活化能的值,油页岩含量较多的混合试样低温段活化能低于高温段的值。     

页岩灰对油页岩热解特性的影响

以吉林桦甸-公郎头四层油页岩为原料,以掺混SiO2的油页岩为对比样品,利用热重-红外联用仪考察了页岩灰对油页岩热解特性的影响,通过分析热解固相产物组成变化对热解失重及产物析出规律进行了研究. 结果表明,页岩灰对油页岩中的有机质和矿物质失重过程均有促进作用,当页岩灰或SiO2含量为83%时,在300~600, 600~750, 750~900℃三个加热温度区间内,掺混页岩灰样品比掺混SiO2样品的失重率分别提高1.92%, 3.39%和18.99%. 低温段有机质热解过程中CO2先于脂肪烃热解析出,且750℃后CO2析出峰仅出现在掺混页岩灰的样品中,应为油页岩中难分解的碳酸盐在页岩灰作用下加速分解及页岩灰中CaSO4与残炭反应共同作用所致.     

油页岩半焦热解特性

利用热重分析仪对油页岩半焦热解特性进行了研究.综合考虑制取半焦所获得的页岩油品质、半焦成分、发热量和循环流化床设计,认为干馏温度介于500～600℃为宜;干馏度对半焦热解初析温度和低温段热解过程有影响,但对高温段热解影响不明显,高温干馏所制取的半焦其热解过程包含于低温所制取的半焦热解过程中;随升温速率的提高,相同温度下的半焦热解度降低,当升温速率超过40℃•min^-1后,升温速率对半焦热解过程影响不大;最后采用Coasts法计算了油页岩半焦热解动力学参数,计算结果可供数值仿真和工程设计参考.     

蒙脱石对油页岩干酪根热解特性的影响

选取中国桦甸、抚顺、窑街3个地区油页岩,酸洗得到各干酪根样品。应用TG-FTIR技术对不同升温速率下各干酪根与蒙脱石共热解行为进行了研究,并利用Coats-Redfem积分法对升温速率为10℃/min下的干酪根掺混样品进行热解反应动力学分析,获得了蒙脱石对干酪根热解产物析出规律的影响及热解过程的活化能(E)和指前因子(A).结果表明,随着蒙脱石掺混比例增大,桦甸和抚顺干酪根热解失重率先升高后降低;在热解过程中,440℃前干酪根与蒙脱石掺混样品的热解失重率较干酪根单独热解低,而440℃后其热解失重率较干酪根热解有所提高;蒙脱石掺混比例增大使得各干酪根热解产物中CH₃/CH₂值有所增加;有蒙脱石掺混的干酪根热解活化能相比干酪根热解活化能有所降低。表明蒙脱石对油页岩干酪根热解具有物理吸附和裂解催化两种作用,且随着热解过程的加深和蒙脱石配比的改变而不同。最后,对升温速率为10℃/min的样品进行了热解反应动力学分析,进一步探讨了蒙脱石对干酪根的热解影响机理。     

煤与油页岩热预处理特性及对热解的影响

对比研究了神木煤和桦甸油页岩在150~400℃热预处理时的孔隙变化和挥发分析出规律以及热预处理对后续慢速升温热解反应产物的影响。结果表明,热预处理显著增加了油页岩的孔隙结构,其比表面积提高4倍、孔体积提高5倍以上,而神木煤的孔隙结构则减少了,特别是孔径大于1 nm的孔体积减少了近60%、比表面积减少了近80%,而其1 nm以下的孔则相对稳定,孔体积和比表面积分别只减少了10%左右。低于400℃时热预处理过程中除脱去吸附水外,其他挥发分也有一定析出,并以CO₂为主,另有少量CO,但挥发分总失重量不超过5%。固定床慢速升温热解研究表明,经热预处理后,油页岩的油产率最高提高了22.7%,而水和气的产率则相应降低,气体中CH₄增加而H₂降低。热预处理对煤的热解油产率影响不明显,但热解水产率降低而热解气产率增加且其中CH₄增多而H₂降少。     

AKTS模拟分析龙口油页岩与半焦混烧动力学特性

利用热重分析仪对龙口油页岩与其500℃半焦按照不同比例混合燃烧时着火温度和燃烧特性进行探究考察。基于3种升温速率下燃烧试验所对应的TG-DTG曲线,整个燃烧过程可分为3个阶段,分别为水析出阶段、燃烧低温段和燃烧高温段。不同比例样品的燃烧特性参数随掺入的页岩比例增大呈现出增大的趋势。利用AKTS-Thermokinetics软件对实验得到的DTG数据分析,对比实验曲线与模拟曲线,并进行反应动力学的计算。基于计算结果发现,随着样品中油页岩的比例增大,活化能呈现出先减小后增大的趋势。综合各样品燃烧特性参数,发现页岩与半焦比例2：1为当前燃烧试验最优混合比。     

汪清油页岩燃烧反应动力学研究

采用Pyris-1TGA热重分析仪测定汪清油页岩不同升温速率(20,50,80,100℃/min)下的一组燃烧TG曲线,根据Popescu提出的一种新的多重扫描法,将不同机理函数式进行线性回归。结果表明,该油页岩燃烧反应符合三维扩散机理,从而确定了该油页岩机理函数的积分式与微分式,获得了活化能与频率因子的值。取转化率为0.1,0.2,…,0.9,将冉全印-叶素温度积分近似式与所求机理函数结合,利用迭代法求出转化率-温度的理论值。结果发现,理论TG曲线与实验曲线吻合较好,表明了所求得的油页岩燃烧机理函数的合理性。     

抚顺油页岩/聚乙烯热解动力学机理研究

利用热重分析(TGA)技术研究了抚顺油页岩、聚乙烯(PE)及其混合的热解反应过程。结果表明:油页岩和PE混合物共热解过程中,共热解残渣量比油页岩单独热解减少了1.17%,对最大速率热解温度,共热解温度比油页岩单独热解温度低5℃。采用Coats-Redfern和Criado法对油页岩、PE及其混合物热解数据进行处理,从15种常用的固相反应机制函数中遴选出最优解,建立动力学模型。结果表明:油页岩的热解遵循表观一、二级化学反应模型(F1、F2);PE热解过程为扩散模型(D4);而其混合物的热解机理遵循动力学模型F1。混合物共热解活化能均远远小于油页岩或PE单独热解的活化能,共热解期间存在较大的协同效应。     

石长沟油页岩的热解特性及动力学

通过热重、元素和XRD分析,研究了新疆吉木萨尔县石长沟矿区油页岩在不同升温速率下的热解特性及热解机理. 结果表明,油页岩中有机质热解生成页岩油和热解煤气的反应主要集中在300~550℃;升温速率从3℃/min增至15℃/min,热解反应向高温区移动,有机质完全热解温度从530℃升至575℃. 油页岩有机质的热解动力学分析显示,升温速率从3℃/min增至15℃/min,直接Arrhenius法计算的有机质热解活化能从243.52 kJ/mol增至257.32 kJ/mol;反应转化率从0.02增至0.97,Friedman法计算的活化能从96.39 kJ/mol增至292.84 kJ/mol.     

粒径和升温速率对煤热分解影响的研究

使用美国 Perkin Elmer公司生产的 Pyris1 TGA热重分析仪 ,对不同粒径煤采用非等温热重法进行了实验研究 ,研究表明 :煤热解过程可分为四个阶段 ,升温速率和粒径对煤热解曲线都有显著影响 ,并用挥发分释放特性指数反映煤热解特性 ,最后用热解动力学方程研究煤的热解过程 ,计算结果表明 ,热解动力学参数能很好地反映煤的热解状况 .     

Effect of demineralization and heating rate on the pyrolysis kinetics of Jordanian oil shales

The effect of mineral matter content on the activation energy of oil shale pyrolysis has been studied. Kerogen was isolated from raw oil shale by sequential HCl and HCl/HF digestion. Oil shale and kerogen samples were pyrolyzed in a Thermogravimetric Analyzer at different heating rates (1, 3, 5, 10, 30, and 50 °C/min) up to a temperature of 1000 °C. Total mass loss of all oil shale samples remained almost constant irrespective of the heating rate employed, whereas it decreased with the increase of heating rate for kerogen (74.5 to 71.4%). From the pyrolysis profile activation energy (Ea) was found to vary between 70 and 83 kJ/mol for oil shale, while 82-112 kJ/mol has been determined for isolated kerogen. An increase of both Ea and pre-exponential factor was observed with an increasing heating rate. It is concluded that the mineral matter in oil shale enhances catalytic cracking as is evident from the reduced Ea values of oil shale compared with those for kerogen.     

Effect of lignite addition and steam on the pyrolysis of Turkish oil shales

Steam was found to be a more effective sweep gas than nitrogen at low velocities in fixed-bed pyrolysis of Goynuk oil shale but, at higher velocities and in fluidized-bed pyrolysis, the differences were considerably less marked. Relatively small but significant synergistic effects were observed between lignites and the two oil shales investigated — Goynuk and Seyitomer — under static retorting conditions. These effects were more pronounced with large concentrations of oil shales but disappeared in fluidized-bed pyrolysis, where conversions are considerably higher because mass transfer limitations largely disappear.     

Gas evolution during pyrolysis of various Colorado oil shales

Rates of evolution of C0₂, CO, H₂, CH₄ and the C₂ and C₃ hydrocarbons during the pyrolysis of seven Colorado oil shales have been measured. These shales, which are from various depths at two different sites, yield 34–255 ¦ of oil per tonne raw shale (9–61 US gal of oil per short ton raw shale) and linear heating at a rate of 2°C min⁻¹ was used for the retorting of all samples. The objective of the study is to monitor variations in gas evolution from shales of different organic content and from various stratigraphic and areal locations. Comparisons between shales from each site are made together with correlations with data from Fischer assays. A kerogen concentrate (mineral fraction removed by HCl-HF treatment) and retorted shale from a Fischer assay are also included. The ability of a kinetic model due to Campbell et al. to predict gas evolution is tested and it is found necessary to modify slightly some of the stoichiometric coefficients to obtain good agreement. The resultant kinetic model should adequately describe the gas and oil evolution behaviour of shale from the upper portion of the Green River formation.     

程序升温下页岩油泥热解机理

采用热重分析仪,进行了桦甸和汪清页岩油泥在不同升温速率（5 ℃/min,10 ℃/min,20 ℃/min,40 ℃/min）下热失重实验,并通过瓦斯气析出情况研究页岩油泥热解机理。结果表明,页岩油泥热解分为3个阶段：第一阶段（20～180 ℃）为水分和轻质组分析出;第二阶段（180～360 ℃）重质组分稳定析出,是动力学研究的重点;第三阶段（360～600 ℃）为半焦炭化及矿物质失重过程。研究发现,催化剂K2CO3能有效降低油泥热解温度及其残渣率,而Al2O3对油泥热解催化不明显甚至起抑制作用。在页岩油泥热解过程中,生成的有机大分子侧链发生C—C键断链,生成小分子的烷烃和不饱和烃,在低压高温条件下,其断链位置倾向于碳链端部,使得小分子烃含量较多。     

Processing oil shales with heavy oil recycle

Recycle of heavy oil (>340 °C) to the retort, in order to crack/coke the oil to lighter fractions, was investigated as a means of producing shale oil of more desirable product slates. Conversion of heavy oil to light oil (<340 °C) by thermal cracking and coking in the absence of and during oil shale retorting was studied using the CSIRO BIRCOS retort. As expected, the conversion by thermal cracking increased as temperature increased, with most of the net oil loss in the form of gas. By contrast, the conversion by coking alone decreased as temperature increased, with coke representing all the net oil loss. Thermal cracking was found not to be a first-order reaction, by showing a reduced conversion of heavy oil with reduced concentration of oil vapour. Retorting Stuart oil shale with heavy oil feeding and simultaneous cracking and coking showed a conversion of 19.1 g per 100 g feed heavy oil to 10.9 g light oil, 2.2 g gas and 6.0 g coke, with a net oil loss of 3.8 g per 100 g shale oil produced. These data were used to generate a set of parameters for a mathematical model which simulated a heavy oil recycle loop.     

物质对油砂热解特性的影响

油砂的开采和提炼是解决当前能源紧缺的重要途径。采用X射线衍射技术（XRD）和热重分析仪（TGA）分别对油砂酸洗前后样品的矿物质组分及其热解特性进行了研究,结果表明：油砂内在矿物质主要为方解石、石英、黄铁矿和黏土矿物等。经HCl/HF酸洗后,能够脱除油砂大部分内在矿物质组分;油砂热解过程可分为两个阶段,即脱水阶段和热裂解阶段;采用Coast-Redfern积分法求解出了油砂热解过程主要阶段的动力学参数活化能和指前因子,发现酸洗后油砂样品的活化能有着不同程度的增加。研究结果为油砂的工业化提供了一定的理论基础。     

Detailed kinetic analysis of oil shale pyrolysis TGA data

There are significant resources of oil shale in the western United States, which if exploited in an environmentally responsible manner would provide secure access to transportation fuels. Understanding the kinetics of kerogen decomposition to oil is critical to designing a viable process. A dataset of thermogravimetric analysis (TGA) of the Green River oil shale is provided and two distinct data analysis approaches—advanced isoconversional method and parameter fitting are used to analyze the data. Activation energy distributions with conversion calculated using the isoconversional method (along with uncertainties) ranged between 93 and 245 kJ/mol. Root mean square errors between the model and experimental data were the lowest for the isoconversional method, but the distributed reactivity models also produced reasonable results. When using parameter fitting approaches, a number of models produce similar results making model choice difficult. Advanced isoconversional method is better in this regard, but maybe applicable to a limited number of reaction pathways. © 2011 American Institute of Chemical Engineers AIChE J, 2012