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势反映了终产物的生成速率变化；H₂、CH₄和C₂~C₅组分主要来自热沥青中脂肪烃的芳构化、芳香族化合物烷基侧链的断裂及含氧化合物的缩聚等，干酪根热解产生的烷烃和烯烃类化合物是产油气的主要组分。干酪根和页岩油的自由基自旋浓度明显低于热沥青和半焦；半焦g值最大，干酪根次之，热沥青和页岩油的g值偏低。     

Robust optimal operation of continuous catalytic reforming process under feedstock uncertainty

The continuous catalytic regenerative (CCR) reforming process is one of the most significant sources of hydrogen production in the petroleum refining process. However, the fluctuations in feedstock composition and flow rate could significantly affect both product distribution and energy consumption. In this study, a robust deviation criterion based multi-objective optimization approach is proposed to perform the optimal operation of CCR reformer under feedstock uncertainty, with simultaneous maximization of product yields and minimization of energy consumption. Minimax approach is adopted to handle these uncertain objectives, and the Latin hypercube sampling method is then used to calculate these robust deviation criteria. Multi-objective surrogate-based optimization methods are next introduced to effectively solve the robust operational problem with high computational cost. The level diagram method is finally utilized to assist in multi-criteria decision-making. Two robust operational optimization problems with different objectives are solved to demonstrate the effectiveness of the proposed method for robust optimal operation of the CCR reforming process under feedstock uncertainty.     

煤基高能量密度燃料的合成及表征

高能量密度燃料是为新型高性能飞行器提供动力保障的关键,其合成及应用研究具有重要的前瞻性和重大战略意义。煤炭是我国的主体能源和重要原料,通过煤直接转化获取的煤基油,充分保留了煤中特有的环状分子化学结构,具有良好的热安定性和较高的能量密度,被认为是高超音速飞行器的优选燃料。以煤直接液化工艺生产的煤液化石脑油馏分为起始原料,通过富集轻质芳烃、化学合成、催化加氢稳定和产物分离提纯等方法制备煤基高能量密度燃料,并对其产物进行分子结构表征和性能评价。结果表明,煤直接液化生产的石脑油馏分是一种优异的催化重整原料,经催化重整富集轻质芳烃后,其轻质芳烃质量分数高达71.05%。Diels-Alder化学合成主产物是由多个封闭环平面组成且具有空间立体构型的二环或三环烃类物质,质量分数为46.18%,因分子内存在较大的张力能,结构紧凑,其拥有更大的密度和体积热值。煤基高能量密度燃料的密度和体积热值分别为0.8990 g/cm3与38.06 MJ/L,均大大超过现行的国内石油基喷气燃料(RP-3和RP-6)、煤基大比重喷气燃料、美国和俄罗斯军用标准。与单一纯物质合成高能量密度燃料(JP-10和T-10)比较,其密度与体积热值偏小。究其原因主要是轻质芳烃的富集度仅为71.05%,需进一步提高其轻质芳烃质量分数。另外,制备的煤基高能量密度燃料种类复杂,其主产物质量分数仅46.18%,下一步可重点调控合成产物的分子构型和纯化分离。     

Advanced Understanding of the Electron Transfer Pathway of Cytochrome P450s

Cytochrome P450s are heme-thiolate enzymes that participate in carbon source assimilation, natural compound biosynthesis and xenobiotic metabolism in all kingdoms of life. P450s can catalyze various reactions by using a wide range of organic compounds, thus exhibiting great potential in biotechnological applications. The catalytic reactions of P450s are driven by electron equivalents that are sourced from pyridine nucleotides and delivered by cognate or matching redox partners (RPs). The electron transfer (ET) route from RPs to P450s involves one or more redox center-containing domains. As the rate of ET is one of the main determinants of P450 efficacy, an in-depth understanding of the P450 ET pathway should increase our knowledge of these important enzymes and benefit their further applications. Here, the various P450 RP systems along with current understanding of their ET routes will be reviewed. Notably, state-of-the-art structural studies of the two main types of self-sufficient P450 will also be summarized.     

催化共振光散射法测定空气中痕量甲醛的研究

吖啶橙分子聚集体微粒可在513nm波长处出现最大的共振光散射强度(RLS)。在稀硫酸介质中,甲醛能催化溴酸钾氧化吖啶橙的反应,促使其RLS强度减弱。在最佳实验条件下,甲醛质量浓度ρ在0.020～0.25μg/mL的范围内与△I值呈良好的线性关系,线性回归方程为△I=1113.99ρ+49.23,线性相关系数r为0.9986。本法与国标法进行对照,在置信度等于95%时,用Cochran检验,两种方法间不存在显著性差异,方法操作简单、灵敏度高,用于室内外空气中甲醛测定,结果满意。     

渣油催化临氢热转化钼铁双金属催化剂的研究

Replacement of precious single metal catalysts with cost-effective, highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies. Organic metals were added to the feed as the oil-soluble precursors, and transformed into the catalytic active phases in this work. Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope and transmission electron microscopy. The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both model compound and residue. Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system. Results showed that under the test conditions in the article, the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.     

不同热解工艺下半焦的微观结构特点及其对燃烧性能的影响

摘要：对比研究了3种直立内热炉半焦(熄焦方式分别为水泡熄焦、喷水熄焦及烟气干熄焦)及一种流化床热解半焦的微观结构及燃烧性能。通过对半焦组成、孔隙结构、有机官能团、碳化学结构及半焦微晶结构分析，获得了不同低温热解工艺半焦的组成及微观结构特点，明确了组成及微观结构与燃烧性能之间的关系。结果表明，不同热解工艺半焦的组成和微观结构差异明显，其对半焦的燃烧性能影响显著。干熄焦碳化学结构缺陷比例大，快速热解半焦孔隙结构发0达、挥发分高，与水喷焦相比水泡焦石墨化程度低；水喷焦燃烧性能优于水泡焦，干法所得半焦的燃烧性优于湿法；半焦的挥发分含量决定其燃点，在快升温速率条件下孔隙结构对半焦的燃烧性能影响较大，而慢升温速率条件下有序化度对半焦的燃烧性能影响较大。     

利用热解-气相色谱/质谱联用仪研究减压渣油及其胶质亚组分的热解规律

以长庆减压渣油及其胶质亚组分为原料，利用热解-气相色谱/质谱联用仪对其在不同条件下热解的产物进行分析，考察反应温度和升温速率对减压渣油热解的影响。结果表明：随着反应温度升高，热解产物中低碳烯烃含量增加，汽柴油馏分含量先增加后减小，在700 ℃ 时达到峰值；升温速率为1℃/ms时，汽柴油馏分含量最高；芳碳率越大、缩合程度越高的重胶质裂解能力越差。     

Microwave-assisted metal-catalyzed pyrolysis of low-rank coal: Promising option towards obtaining high-quality products

Microwave-assisted catalytic pyrolysis is considered to be a promising technology for coal-staged conversion due to its high efficiency and selectivity. This work was undertaken to investigate the pyrolysis behavior and products quality of microwave-assisted pyrolysis of low rank coal catalyzed by metallic catalysts (K, Ca and Fe) with both dielectric response and catalytic effect via a microwave tube furnace. The mechanism of metallic catalysts on catalytic cracking tar under microwave radiation was also investigated. The dielectric properties and physicochemical structure of coal chars were characterized by a vector network analyzer, XRD, FT-IR, SEM, EDS, and Raman. The chemical structure characteristics of generated tars were determined by FT-IR and GC-MS. Results manifested that microwave interacted preferentially with metal catalysts by polarization and conductivity loss could efficiently induce the occurrence of catalytic pyrolysis reactions to generate high yield syngas (CO + H₂). Specifically, the dielectric loss factor of resultant chars was considerably improved with the introduction of metallic catalysts especial for Ca and Fe. Furthermore, it is found that metal catalysts dramatically enriched the amorphous carbon structure in produced chars whereas in favour of suppressing the trend of carbon graphitization. Additionally, the transformation of larger polycyclic aromatic compounds into lighter tar species was catalytically accelerated, resulting in the large proportion of single-ring aromatics in tar under the synergistic effect between microwave and metal catalysts.     

Activated Carbon Supported CaO from Waste Shells as a Catalyst for Biodiesel Production

In the wake of increasing environmental constraints, this work is aimed at developing a catalyst purely prepared from waste biomass source as the raw material. The catalyst is investigated for its applicability in transesterification of vegetable oil with the objectives: (i) to use waste shells of mollusk as raw material for the preparation of activated carbon and CaO; (ii) to use it as heterogeneous catalyst in the transesterification of waste cooking oil; (iii) to optimize the different parameters affecting the transesterification reaction; and (iv) to study its reusability. Under optimized conditions it was observed that a conversion >90% was possible and the catalyst could be reused five times with a slight loss in activity. This study indicates that the biomass source could also be used as a potential raw material in the synthesis of environmentally benign catalysts.