油页岩有机质的逐级热溶解聚及产物特性

依兰油页岩有机质经过四氢萘逐级热溶解聚,热溶解聚物分别经过GC-MS检测并归纳分类,并结合热溶解聚残渣的FT-IR和~(13)C NMR分析结果,旨在从分子水平上揭示依兰油页岩有机分子结构特征。结果表明,依兰油页岩有机质经过200~400℃逐级热溶解聚后,200、300、350、375和400℃温度条件下逐级热溶解聚物的收率分别为8.8%、9.9%、18.5%、19.2%和23.4%,总收率达79.8%。在可溶性组分中,脂肪烃化合物占比为36.9%(其中直链烷烃27.4%,支链烷烃8.7%),酚/醇类占比为5.5%,芳香烃占比为32.0%,酮类占比为12.7%,醚/酯类占比为5.4%,其他化合物占比为7.5%。呈现脂肪烃芳烃化合物酮类酚/醇酯/醚的规律分布状态,其中27.4%直链烷烃中碳数分布在14~30并在C_(16)和C_(26)呈现两个峰值。     

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。     

升温速率对油页岩热解特性的影响

采用热分析方法,在非等温条件下对茂名和桦甸的油页岩进行了热解试验研究。研究了从常温到900℃之间不同升温速率(10,20,40,50,100℃/m in)对油页岩热分解反应的影响以及油页岩的H/C,O/C,Cdaf,Vdaf等因素与(dw/dt)m ax之间的关系。根据试验数据建立了热解动力学模型,利用积分法求得表观活化能和频率因子等动力学参数。试验结果表明,油页岩热解可分为3个阶段,其中第2阶段(200—600℃)是热解反应最激烈的区域,挥发份几乎全部析出。而第3阶段是碳酸盐热解阶段,茂名油页岩由于碳酸盐含量低,此阶段变化甚微。     

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.     

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.     

大庆油页岩及干馏产物的利用途径分析

大庆油页岩的舍油率大部分都在10%以上,具有很好的经济开发价值.对大庆油页岩及其干馏产物性质的实验研究表明,油页岩的机械强度较低,应选择粉末、颗粒干馏炉进行加工处理;页岩油主要由柴油馏分和重油馏分组成,分别可加工成成品油和直接用作燃料油;热解干馏气热值约为17MJ/m3,可以在除作自身干馏所需的热量燃料外,用作城市煤气或工业锅炉的燃料;半焦着火点低,热值约为23 MJ/kg,可作为清洁燃料用于发电或民用;页岩灰的主要组分是氧化钙争氧化硅,可用于生产建筑材料.     

干馏条件对油页岩半焦孔隙结构的影响

油页岩干馏过程中发生挥发分物质的析出,导致颗粒的孔隙结构发生重大的变化,进而会对油页岩半焦的燃烧反应、成灰等特性产生重要的影响。利用扫描电镜、氮气吸附/脱附法对不同干馏温度、不同干馏时间下制备得到的桦甸油页岩半焦进行了孔隙分析,并与前人针对相同样品的油页岩半焦燃烧特性实验研究进行了对照分析。结果表明,在实验范围内,随干馏温度增加,受热解二次反应产生的焦炭对孔隙堵塞的影响,油页岩半焦孔隙比表面积和比容积先增加后减小;随干馏时间增加,伴随着小孔之间的合并,油页岩半焦孔隙比表面积先增加后减小,比容积单调增加。     

金属氧化物对油页岩热解产物收率及组成分布的影响

通过固定床反应器,对4种金属氧化物（Al₂O₃、MgO、CaO、Fe₂O₃）对油页岩热解所得油、气产率及成分的影响进行了研究。结果显示,碱性CaO对油、水、气、焦产率分布影响较为突出,可提高页岩油与半焦产率,并降低热解气产率;而酸性较强的Al₂O₃可同时提高页岩油、热解气和热解水的产率,有利于促进挥发分的析出;比较而言,MgO和Fe₂O₃的作用相对较弱。4种金属氧化物均可提高热解气中H₂、CH₄和C₂的产率;CaO作用下CO₂含量降低,而其他金属氧化物对CO₂的产生有不同程度的促进作用;Fe₂O₃可促进H₂产生;Al₂O₃作用下CH₄含量有所增加。4种金属氧化物均可促进页岩油中芳香烃的产生,并且CaO和MgO两种碱土金属氧化物作用下,短链（C₆~C₁₂）烷烃和烯烃含量均增加,而掺混Al₂O₃时页岩油中仅短链（C₆~C₁₂）烷烃含量增加。对此机理进行推测认为,碱性CaO和MgO首先与以脂肪酸形式存在的有机质进行酸碱反应,得到脱羧活性更高的羧酸盐,后者脱羧所得中间产物具有生成烷烃或烯烃两条可能路径,同时得到碳酸盐;而在具有Lewis酸特征的Al₂O₃作用下,脱羧产物为CO₂,并同时得到饱和烃产物。     

热作用过程油页岩颗粒的碎裂/粉化特性

在固定床中定量研究了热作用过程多种工艺因素对油页岩颗粒的粒度分布及碎裂/粉化程度的影响。结果表明：温度由120℃升至900℃,固相产物中25~13 mm保持粒级比率由96.54%降至82.69%;13~1 mm碎裂粒群比率由2.01%增至10.63%（13~6 mm粒级增幅最高）;<1 mm粉化粒群比率由1.45%增至6.68%（<0.075 mm粒级变化最显著）。颗粒尺度的增加及保温时间的延长亦使得油页岩的碎裂及粉化程度加剧。多因素灰色关联分析结果显示：对油页岩碎裂程度的影响为：温度>粒度>时间;对粉化程度的影响为：温度>时间>粒度。通过对油页岩的多种测试表征（TGA、XRF、XRD、SEM-EDS）,揭示了上述因素影响油页岩热碎的内在诱因（水汽行为、挥发分析出行为、方解石分解行为、时间间接强化、颗粒内部气阻/材料抗力的影响）,并基于此构建了油页岩热作用过程碎裂-粉化历程描述模型。     

油页岩及其半焦混烧特性的热重试验研究和动力学分析

利用热重分析仪对桦甸油页岩燃烧时的双峰现象以及与其500℃半焦按不同比例混烧时单样相互影响程度、颗粒特性、着火温度和燃烧特性指数进行了考察;利用DAEM模型解析了混烧动力学参数。结果表明：油页岩燃烧DTG曲线在500℃附近的双峰活性参数值相差不大,分别为0.79和0.73,反映油页岩燃烧DTG曲线双峰归因于脂类有机质与干酪根中芳香烃的燃烧;混样中各单样在不同温度段相互影响程度不同,表观影响程度系数f的值均小于1。在燃烧过程中颗粒的缩核形状和表面分形维数并不是固定不变的,在低温段接近长圆柱体,在高温段接近平板,当浓度级次β=0.6时,低温段分形维数接近3,在高温段接近1;着火温度随半焦掺混量的增加呈线性递增;混样燃烧特性指数介于单烧之间并且存在掺混效果明显区;试样表观活化能在燃烧前期变化比较缓慢并呈下降趋势,大约在60～90 kJ·mol^-1之间,在后期剧烈增加,当转化率在0.60～0.75之间时表观活化能从80 kJ·mol^-1剧增到200 kJ·mol^-1。     

桦甸油页岩的二级萃取溶解行为

以吉林桦甸油页岩为研究对象,通过二氯甲烷、石油醚两级萃取,对油页岩原矿、两级萃余物进行SEM扫描,对二氯甲烷萃取液、石油醚萃取液进行GC/MS检测,研究桦甸油页岩在两级溶液的溶解行为以及各级萃余物表面物理形貌。结果表明,随着萃取的加深,油页岩颗粒相对光滑的片层结构逐渐消失,颗粒粒径趋于细小,表面沟壑逐渐增多,后级萃取时液固接触面积增加。二氯甲烷和石油醚对油页岩中烷烃溶出能力较强。两级萃取物组分主要由C15～C28饱和烷烃构成。溶剂萃取法可以有效地提取油页岩中一类或相似的化合物群,对研究油页岩构成及提取高经济价值成分有重要意义。     

Insight into the structural features of organic species in Fushun oil shale via thermal dissolution

Fushun oil shale (FOS) was subjected to thermal dissolution (TD) under different conditions. The results show that the optimal solvent, temperature, time, and ratio of solvent to FOS are ethanol, 300℃, 2 h, and 5 ml·g^-1, respectively and the corresponding yield of the soluble portion (SP) is 32.2% (daf), which is much higher than the oil content of FOS (ca. 6%), suggesting that TD in ethanol is an excellent way to extract organics from FOS. According to 3 direct analyses, aliphatic moieties in FOS are the most abundant followed by C-O-containing moieties and each cluster in FOS has 3 conjugated aromatic rings on average with fewer substituents. According to the analysis with a gas chromatograph/mass spectrometer, alkanes are predominant in all the SPs. A number of alkenes were identified in the SPs from the TD, while none of the alkenes were detected in acetone-SP obtained at room temperature, implying that the TD can destroy the π-π and intertwining interactions between alkenes and macromolecular structures in FOS. Moreover, a small amount of alkyl-substituted phenols and alkoxysubstituted phenols were detected in ethanol-SP from the TD, which could be the products from ethanolyzing the macromolecular moiety of FOS.     

Acid dissolution of mineral matrix in Green River oil shale

The mineral matrix in Green River oil shale was partially removed by treatment with dilute HCl. The major ionic species in the solution from acid treatment (AT) were identified as Na⁺, Al³⁺, Fe²⁺, Mg²⁺, and Ca²⁺. The ion yields expected from reaction stochiometry, gravimetric analyses and comparison of calculated CO₂ yields with measured levels were consistent with the fact that Na⁺ and Al³⁺ originated primarily from analcite: Fe²⁺ and Mg²⁺ from dolomitic ankerite and Ca²⁺ from both dolomitic ankerite and calcite. Temperature and shale particle size were important parameters in the efficacy of AT. An increase in temperature and a decrease in particle size increased the rate of mineral dissolution. Fe²⁺ showed an anomalous trend in that the rate initially declined with increasing temperature after which it showed the usual increase with temperature. The kinetics of ion build-up in the solution from AT were analysed in detail for the case of Al³⁺. The Arrhenius expression was found to be valid only for finer particle sizes (e.g., ?35, +45 US mesh shale). A simple model is finally presented to account for the combined effect of temperature and shale particle size on mineral dissolution rates.     

Selective removal of nitrogen compounds from shale oil

A solid extraction process for selectively removing nitrogen from alternative refinery feedstock has been developed. It has been demonstrated that solid CuCl₂ · xH₂O can reduce the nitrogen content of shale oils to acceptable levels for some refineries. In a simple single-stage process, the nitrogen content was reduced by more than 85% to levels below 0.2 wt%. The solid extraction process was remarkably selective and produced high oil recovery yields corresponding to ≈98% of the theoretical limit. Experiments with model systems have shown complete selectivity for the nitrogen compounds and have demonstrated that the entire bulk of the solid is involved in the extraction process. Many other solids have been shown to be effective, namely transition metal halides, nitrates, sulphates, acetates, fluoroborates, and phosphates.     

Chemical depolymerization of oil shale

The chemical structure of the organic matter from Krassava oil shale has been investigated by means of chemical degradation with metallic sodium in liquid ammonia and with phenol in the presence p-toluenesulphonic acid. The former reaction yielded 20 wt% of pyridine-soluble material and the latter ≈ 65 wt%. Extensive depolymerization of the oil shale was achieved by a combination of both methods in which case the solubility of the organic matter was increased to 85–95 wt%. The characterization of soluble and insoluble products by pyrolysis g.c. and elemental analysis indicated that aliphatic chains were prevalent in the organic matter of the Krassava oil shale.     

抚顺页岩油新型加工工艺研究

以糠醛为溶剂萃取剂,对抚顺页岩原油的溶剂精制进行了研究。结果表明,随着剂/油质量比的增大或温度的升高,抽余油的收率不断下降,抽出油收率逐渐升高,但是所得的抽余油质量更好。抽出油重组分调合制备重交及建筑等不同牌号的沥青,抽出油轻组分用于非烃化合物的分离;经过脱氮后的抽余油进行催化裂化,得到各种轻质燃料,脱除的氮化合物也可用于非烃化合物的分离。     

Determination of polar compounds in Rundle shale oil

The acidic and basic components of three distillate fractions (light, middle and heavy) of shale oil from the Rundle (Queensland, Australia) deposit were selectively extracted. Capillary gas chromatography/mass spectrometry was used to identify individual polar components. The major nitrogen-containing polar compounds in the light fraction were alkyl-substituted pyridines, and substituted quinolines were more abundant in the middle and heavy fractions. Significant quantities of pyrrole derivatives were also identified. Small quantities of anilines and benzoquinolines made up the remainder of the bases. The oxygen-containing compounds were mainly phenolic in nature; alkyl-substituted phenols were the major components, but significant quantities of naphthols and traces of fluorenols were identified.     

不同有机溶剂对新疆油砂沥青的组成性质影响

油砂作为一种非常规石油资源,越来越受到人们的重视。油砂沥青的含量和性质对其开发有着重要的影响。有机溶剂抽提可以测定油砂沥青的含量。本文研究了3种溶剂对新疆油砂的抽提能力,并对不同溶剂抽提得到的新疆油砂沥青进行了性质分析。结果表明,新疆油砂含油率（甲苯测）为11.75%,属于中品位油砂矿;甲苯、氯仿和石油醚3种不同溶剂对新疆油砂沥青进行抽提,发现3种溶剂抽提能力的大小关系为氯仿＞甲苯＞石油醚;抽提过程中,氯仿表现出对胶质和沥青质较强的萃取能力,而石油醚对沥青质的萃取能力几乎为0,采用氯仿可以更准确地测定油砂沥青的含量。氯仿抽提得到新疆油砂沥青及其组分的杂原子含量和分子量高于甲苯和石油醚抽提的。由红外谱图发现,氯仿抽提得到的油砂沥青的含氧、含硫官能团的吸收峰强度大于甲苯和石油醚抽提的,表明氯仿对油砂沥青中极性物质的抽提能力更强。     

Acid dissolution of mineral matrix in Green River oil shale.: 2. Effect of ultrasonic field

An ultrasonic field was found to enhance the rate of mineral dissolution from Green River oil shale matrix when treated with dilute HCl. This effect was most pronounced forcoarse particles and minimal for finely pulverized shale. Data comparing the behaviour in an ultrasonic field with control specimens are presented in terms of gas evolution profiles, ion concentrations and gravimetric analyses.