第二代生物柴油制备的多相催化剂的结构设计及研究进展

生物柴油是一种重要的可再生清洁能源, 特别是经催化加氢脱氧等系列过程制备的第二代生物柴油, 在成分上与石油基燃料相似, 有望成为一种替代传统化石燃料的绿色能源. 在合成第二代生物柴油的研究中, 设计与制备兼具高活性与高稳定性的加氢脱氧多相催化剂是关键问题. 近年来, 研究者对于催化剂的种类与应用进行了探索, 并取得了一定的进展. 详细分析了加氢脱氧制备第二代生物柴油反应原料及反应参数、反应器对生产路径和产能的影响, 并对反应机理进行了介绍; 进一步从双金属位点、金属-酸性位点及金属-空位协同作用三个方面对催化剂结构设计进行了讨论和分析; 最后, 对第二代生物柴油领域的未来发展趋势进行了展望.     

油脂催化转化为绿色燃料的技术进展

油脂是一类非常重要的绿色可再生能源载体.运用催化技术将油脂高效地转化为液态燃料尤其是绿色烃类燃料是当前生物质转化利用中最具有工业化应用潜力的方向,因此备受关注.本文从油脂催化转化技术中的酯交换技术、催化裂化技术、硫化态和还原态金属加氢脱氧技术等方面阐述了国内外科研前沿领域在催化剂、工艺、反应路径及机理等方面的进展.对未来多种油脂原料转化为烃类燃料尤其是生物航煤的技术路线进行了分析与建议.     

甲烷氧化菌的高密度培养及其在生物柴油炼制中的应用

天然气是储量最丰富的能源之一,但限于勘探、运输、配置等问题,一直以来人们对它的利用都不是很合理.能源危机和环境问题推动了生物质能源的开发利用,甲烷氧化菌是以甲烷为唯一碳源和能源进行生长的一类细菌,具有炼制生物柴油的潜力.综述了近几年甲烷氧化菌在高密度培养及深加工炼制生物柴油的研究进展,着重分析了高密度培养和生物柴油炼制过程中在传质与反应器设计、菌种培养、脂质提取、加氢脱氧四个过程中面临的技术难点,给出了解决方法并展望了其在未来的发展.     

支撑未来炼油工业发展的若干关键技术(英文)

概述了未来炼油厂主要任务中关键技术的特点和使用效果. (1)提高轻质油收率, 关键在于重油的高效转化, 关键技术包括渣油加氢技术、重油加氢与催化裂化双向组合技术、多产轻质油的催化裂化蜡油选择性加氢工艺与选择性催化裂化工艺集成技术、浅度溶剂脱沥青-脱沥青油加氢处理-催化裂化技术; (2)生产清洁燃料, 主要是生产要求越来越高的清洁汽油和柴油, 关键技术有汽油选择性加氢脱硫技术、柴油超深度加氢脱硫技术、柴油超深度加氢脱硫催化剂; (3)生产优质化工原料, 关键技术主要是催化丙烯技术.     

木质素基酚类化合物加氢脱氧制取碳氢燃料

木质素是生物质中碳资源密度最高的组分.木质素到高品质液体燃料的转化主要通过其解聚的单环酚类化合物经加氢脱氧工艺来实现.来源于木质素的酚类化合物的加氢脱氧产物一般为C6~C10之间的碳氢化合物,与现有的商品汽油组分碳数分布一致,是理想的交通替代燃料.酚类化合物的加氢脱氧研究近年来发展迅速,文献报道数量激增.本文对硫化态Mo基催化剂、贵金属催化剂及非硫化非贵金属催化剂作用下单环酚类化合物的加氢脱氧反应特性分别进行了回顾,对典型酚类模型化合物在催化反应机理进行了简述,并对载体材料在加氢脱氧过程中的作用进行了介绍.随后,在此基础上总结了当前酚类化合物加氢脱氧过程中的难点,并对下一步的技术发展方向进行展望.     

脂肪酸(酯)脱氧制备生物燃料研究现状

随着全球能源消耗量的增长,传统化石燃料等不可再生能源将日趋枯竭且环境污染等弊端日益突显.利用绿色、可再生生物质资源,尤其是脂肪酸(酯)脱氧转化制备液体燃料已成为全球关注的热点.脂肪酸(酯)脱氧过程中氢源的不同,直接影响脱氧的反应路径、效率和成本.鉴于此,本文根据氢源的不同,综合分析了近年来脂肪酸(酯)的直接加氢脱氧、原位加氢脱氧、脱羧脱羰等过程的研究进展.提出了未来脱氧过程的主要发展方向和研究重点,为商业化脱氧技术的开发提供新的助力.     

生物柴油-柴油混合燃料的理化及排放特性研究

对生物柴油-柴油混合燃料的表面张力、运动黏度、抗磨性、氧化稳定性以及碳烟排放等特性进行了测试和研究.结果表明,生物柴油-柴油混合燃料的表面张力随生物柴油含量的增加呈抛物线趋势变化,并随温度升高呈幂函数曲线下降.生物柴油的磨斑直径小于柴油,最大卡咬极限压力大于柴油.生物柴油的质量分数为40％-70％,混合燃料的氧化稳定性...     

柴油加氢精制催化剂制备技术

柴油加氢精制催化剂制备技术的发展大致经历了3个阶段,由此形成了三代柴油加氢催化剂:单层分散的负载型金属硫化物催化剂,多层分散的负载型金属硫化物催化剂和非负载型金属硫化物催化剂.本文对金属硫化钼基柴油加氢精制催化剂的应用背景、制备思想及催化剂研究开发现状进行了系统的总结,对柴油加氢催化剂的发展方向进行了展望.     

柴油加氢精制催化剂制备技术

柴油加氢精制催化剂制备技术的发展大致经历了3个阶段,由此形成了三代柴油加氢催化剂:单层分散的负载型金属硫化物催化剂,多层分散的负载型金属硫化物催化剂和非负载型金属硫化物催化剂.本文对金属硫化钼基柴油加氢精制催化剂的应用背景、制备思想及催化剂研究开发现状进行了系统的总结,对柴油加氢催化剂的发展方向进行了展望.     

清洁燃料催化剂和工艺开发中的芳烃研究

为了保护环境,人们对车用燃料的环境质量要求越来越高.柴油中芳烃含量的高低不仅直接影响其燃烧性能,而且对大气质量会产生不同程度的影响,柴油中芳烃特别是重芳烃的存在对环境尤其有害.许多国家都对柴油中的芳烃含量提出了更高的要求.美国、日本和欧洲发动机制造商协会(EMA)于1998年6月提出的<世界燃料规范>中要求柴油中芳烃＜15 m%、多环芳烃≤2.0m%.我国的柴油质量指标与世界先进指标相比还有很大的差距,难以适应国际市场的需要和竞争,柴油的主要问题之一是芳烃含量高.研究人员正在研究柴油的深度脱芳催化剂和工艺技术,生产清洁燃料已成为当前国内炼油工业必须解决的重要问题.本文选择了两种原料油在同一种加氢处理催化剂上进行柴油加氢脱芳实验,并对反应前后油中的芳烃进行了分析和讨论.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.