Hydroprocessing of stuart a (Australian) oil shale

Research on production of shale oil by direct hydrogenation of oil shale has been conducted in batch stirred autoclave reactors. The objective of the work has been to elucidate the effect of operating variables on conversion of organic carbon, and the resulting product yield structure (oil/gas). Yields of oil and gas (hydrocarbon and carbon oxide) have been quantified for hydroprocessing under a wide range of operating conditions using both hydrogen donor and pyrolysis oil (non-donor) solvents. The effects of temperature, reaction time, pressure, hydrogen partial pressure, and solvent characteristics on yield structure are described.     

NiW/Al-PILC催化剂的页岩油加氢性能

采用铝柱撑粘土为载体制备了NiW/Al—PILC催化剂,研究了在页岩油加氢中的催化性能,与催化剂NiW/γ-Al_2O_3的催化性能进行比较。对催化剂进行表征,并对页岩油加氢所得柴油馏分[(180～350)℃]进行分析,结果表明,NiW/Al—PILM催化剂催化性能优于NiW/γ—Al_2O_3催化剂,其铝柱撑粘土层间距d_(001)=1.962 nm、比表面积为264.3 m~2·g~(-1),在该催化剂上页岩油加氢柴油收率达52.8%,20℃运动黏度5.025 mm~2·s~(-1),凝点-3℃,冷凝点1℃,闪点84℃,十六烷值64.3,20℃密度0.832 7 g·cm~(-3)。     

Ring-opening metathesis polymerization of cyclohexenyl norbornene in air and protic media using ruthenium-based catalysts

Optimized ring-opening metathesis polymerization (ROMP) conditions for cyclohexenyl norbornene (CHNB) have been determined. ROMP of CHNB was carried out with ruthenium trichloride hydrate and ruthenium benzylidene catalysts. The effects of mol % catalyst, type of catalyst, use of a dissolution aid (for RuCl₃ · ×H₂O), reaction time and temperature on conversion and gel time were investigated. ROMP with 0.0027 mol % ruthenium benzylidene at room temperature gave CHNB conversions ranging from 97 to 99% with gel times of ca. 24 min. With ruthenium trichloride hydrate and using ethanol as a dissolution aid, only 60–80% conversions with gel times of ca. 43 min occurred at 55–60°C. The obtained polyCHNB's were crosslinked or not, epending on ROMP conditions. All polyCHNB' exhibited 5% weight loss at ca. 420 and 430°C under nitrogen and air atmospheres, respectively. The DSC measured glass transition temperature of all polyCHNB samples was 105°C. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 183–190, 1998     

苯选择性加氢钌催化剂的研究及应用进展

苯选择性加氢钌催化剂广泛用于合成环己醇/酮,进而制备己内酰胺、己二酸、尼龙、聚酰胺等高附加值的精细化工产品。与传统工艺路线相比,苯选择性加氢技术路线具有安全环保和节能高效的特点,其中,催化反应体系是该技术路线的关键要素。重点概述了近年来苯选择性加氢钌催化剂的研究进展、工业应用现状及市场前景。     

Hydrogenation of canola oil using chromium catalysts

Homogeneous, supported and precipitated chromium catalysts were prepared from chromium hexacarbonyl in an attempt to selectively hydrogenate canola oil. These chromium compounds showed low activity, lowering the iodine value of the oil by only 10 IV units. The concentration oftrans-isomers, however, was very low (<1% for most runs). Infrared spectroscopy revealed the presence of a Cr(CO)₃(diene) PPH₃ complex in two of the hydrogenated oils. The selectivity and the mechanism by which chromium catalysts hydrogenate unsaturates are discussed.     

钌基碱性电解水制氢催化剂研究进展

碱性电解水具有操作易实现、设备费用低和寿命长的特点,是目前应用最广泛的将可再生资源转化为氢能的技术。但电解水存在能耗高的问题,因此需要高效催化剂提高能量转化效率。钌具有与铂相近的金属-氢键强度,是极具前景的制氢催化剂。综述了近年来钌基催化剂的制备及其碱性电解水制氢反应的最新研究进展。与廉价过渡金属材料相比,钌基催化剂具有优异的电化学活性和稳定性,是一种很有前景的析氢材料。以目前主要研究的钌金属及其合金、钌基磷化物、钌基硫化物、钌基硒化物为代表,分别进行了简要的介绍和评价,最后提出了钌基电催化剂在制氢应用中存在的问题和未来的发展方向。     

以MgO-AC为载体的钌基氨合成催化剂的制备研究

在氮气气氛下焙烧Mg(NO3)2-AC,制备MgO-AC复合材料,以此为载体制备铯促进的钌基催化剂,考察了焙烧前后催化剂活性的变化和不同的焙烧气氛对于催化剂活性的影响。结果表明,在较低的温度和压力下,以MgO-AC为载体的催化剂的活性高于单独以MgO或AC为载体的催化剂,也高于将MgO和AC机械混合为载体催化剂的活性。通过活性比较、热重分析和其他相应的表征手段,得出对于MgO-AC载体,MgO和AC之间存在着一定的相互作用,对提高氨合成催化剂活性起着一定的促进作用。     

Q-band e.p.r. spectra of oil shale,spent shale,and shale oil

Comparison of X-band (9.1 GHz) and Q-band (35.2 GHz) electron paramagnetic resonance (e.p.r.) spectra of oil shale, shale oil, and spent shale indicates that the organic free radical signal observed in all three types of samples is a composite spectrum.     

The formation of alite phase by using phosphogypsum and oil shale

This study aims at gaining in-depth knowledge for the cement clinker production by utilizing phosphogypsum (PG) and oil shale (OS) as raw materials. The raw mixtures (Raw Mixes I and II) were burnt in a muffle furnace and then analyzed by X-ray diffraction (XRD) to observe the phases obtained. While minor amounts of alite (C₃S) and major amounts of anhydrite phases were observed with the Raw Mix I containing 40.72% PG refined with water and lime wash by two and three times, respectively (PGR²³), in N₂ atmosphere at 1300 °C, minor amounts of alite (C₃S), free CaO and major amounts of anhydrite phases were formed in air atmosphere at 1300 °C with the Raw Mix II containing 40.72% PG refined with water and lime wash by three and four times, respectively (PGR³⁴). The change of burning medium and the increase in the number of wash with water and lime, respectively, resulted in any difference in terms of the formation of the alite peaks; however, the intensity and the amount of anhydrite peaks were decreased in N₂ atmosphere due to the more conversion of that to the oxide compared to that in air atmosphere.     

Cobalt-cement catalysts for the synthesis of motor fuel components from synthesis gas obtained from oil shale

Highly effective cobalt-cement catalysts for the synthesis of aliphatic hydrocarbons from CO and H₂, which are formed upon the thermolysis or gasification of oil shale or coals, are considered. The formation of the catalysts was studied.     

Prediction of oil yield from oil shale minerals using diffuse reflectance infrared Fourier transform spectroscopy

Multivariate analysis techniques, principal component analysis (PCA), principal component regression (PCR) and partial least square regression (PLSR), were employed to develop calibration and prediction models for the determination of oil yield from oil shale samples using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Data pre-processing included the use of second-derivative spectral data. Multi-component models were constructed and were effective in predicting oil yield with accurate predictions achieved using oil shale samples other than those used in the calibration set. DRIFTS with multivariate calibration modelling is demonstrated to provide a simple and rapid method of evaluating oil yield from oil shales compared with, and potentially replacing, the traditional modified Fisher assay (MFA) method.     

油页岩的综合利用

阐述了世界油页岩的储量和利用情况 ;介绍了抚顺矿业集团利用油页岩进行低温干馏生产页岩油、利用页岩废渣生产建材制品、将油页岩用作电厂燃料发电等综合利用情况     

Kinetics of oil generation from Colorado oil shale

Isothermal and nonisothermal methods have been used to investigate the kinetics of oil generation during decomposition of 91.7 ml/kg (22 U.S. gal/short ton) Colorado oil shale. The result from the nonisothermal method gives an apparent activation energy of 219.4 kJ/mol and a frequency factor of 2.81 × 10¹³s^?1. Furthermore, the process is found to be first-order to within experimental error. These results compare favourably with isothermal data reported here and in the literature. The results show the reliability and convenience of nonisothermal kinetic experiments in studying oil-shale decomposition reactions. The principal advantages are short-term experiments and the lack of initial heat-up periods. Moreover, nonisothermal experiments more accurately simulate actual conditions of above-ground and in situ oil-shale retorting. These kinetics are ‘effective’ values and can only properly be used to describe the macroscopic oil-production process rather than the complex microchemistry.     

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.     

Transesterification of soybean frying oil to biodiesel using heterogeneous catalysts

In the present work, the transesterification reaction of soybean frying oil with methanol, in the presence of different heterogeneous catalysts (Mg MCM-41, Mg-Al Hydrotalcite, and K⁺ impregnated zirconia), using low frequency ultrasonication (24 KHz) and mechanical stirring (600 rpm) for the production of biodiesel fuel was studied. Selection of catalysts was based on a combination of porosity and surface basicity. Their characterization was carried out using X-ray diffraction, Nitrogen adsorption-desorption porosimetry and scanning electron microscopy (SEM) with energy dispersive spectra (EDS). The activities of the catalysts were related to their basic strength. Mg-Al hydrotalcite showed particularly the highest activity (conversion 97%). It is important to mention that the catalyst activity of ZrO₂ in the transesterification reaction increased as the catalyst was enriched with more potassium cations becoming more basic. Use of ultrasonication significantly accelerated the transesterification reaction compared to the use of mechanical stirring (5 h versus 24 h).     

钌基氨合成催化剂作用机理及氧化物负载钌催化体系研究

介绍了钌基氨合成催化剂的最新研究进展,结合密度泛函理论计算综述了钌基氨合成催化剂的作用机理,包括钌表面对氮分子的吸附活化以及钌基氨合成催化剂上的氨合成反应动力学模型方面的研究成果。对氧化物载体的制备方法、修饰和复合手段、助剂种类及其在催化反应中的作用机理等进行了总结,探讨了钌基氨合成催化剂理论研究以及氧化物催化剂体系目前存在的问题。     

油页岩低温干馏过程的Aspen Plus模拟

利用Aspen Plus系统流程模拟软件模拟油页岩的低温干馏,并按照含油率测定实验工况来设置系统流程,以探讨将Aspen Plus应用于油页岩热解领域的可行性。针对吉林地区桦甸一矿4层和二矿11层的油页岩试样进行模拟,并将所得的含油率、含水率、半焦产率、干馏气体产率及半焦中各元素含量等模拟数据与实验值进行对比分析,模拟结果与实测值间的误差均控制在合理范围之内。对比结果表明,系统流程的建模及物性参数设置是正确合理的,可为后期构建完整的油页岩综合利用系统提供参考。     

Utilization of Estonian oil shale semicoke

In thermal processing of oil shale in vertical retorts huge quantities of a solid waste — semicoke are formed. It has been shown that circulating fluidized bed combustion of semicoke could be a promising technology allowing utilization of its high residual energy potential. The main parameters of combustion process and the additional heat produced were calculated and verified by combustion tests in a fluidized bed device with a thermal capacity of 50 kW_th. The experiments indicated that semicoke with low moisture content can be burnt directly in fluidized bed. For the combustion of semicoke with higher moisture content (over 10%) about 10% of oil shale must be added. In addition, possibilities for utilizing residual carbon present in semicoke by obtaining carbon-rich materials with further production, for example, activated carbon were discussed. A series of experiments accompanied by SEM and EDAX analysis was carried out in order to elucidate the distribution of carbon and mineral part in semicoke and to find possibilities for their separation and subsequent enrichment. Different separation methods — selective grinding and subsequent screening, pneumatic separation and triboelectroseparation method were analyzed. It was shown that due to close integration of mineral and organic part in semicoke, the separation of carbon-rich ingredients by these methods was not enough effective to obtain enriched products suitable for the production of activated carbon.