生物质能源的开发与利用

本文概述了生物质能源的特征以及发展生物质能源的意义,综述了国内外生物质能源开发与利用的现状,简介了中国石油天然气股份有限公司生物质能源的发展思路、部署及工作进展.中国石油天然气股份有限公司生物质能源发展策略重点放在发展生物柴油和燃料乙醇.本文结合公司生物质能源长期发展战略以及实际工作开展情况分别从生物柴油、燃料乙醇两个方面详细探讨了所面临的生物质能源化工关键技术的需求,并提出相关发展建议.     

生物质能源的开发与利用

本文概述了生物质能源的特征以及发展生物质能源的意义,综述了国内外生物质能源开发与利用的现状,简介了中国石油天然气股份有限公司生物质能源的发展思路、部署及工作进展。中国石油天然气股份有限公司生物质能源发展策略重点放在发展生物柴油和燃料乙醇。本文结合公司生物质能源长期发展战略以及实际工作开展情况分别从生物柴油、燃料乙醇两个方面详细探讨了所面临的生物质能源化工关键技术的需求,并提出相关发展建议。     

编者按

面对日益严重的能源与环境问题，为保障能源安全，保护生态环境，实现可持续性发展，我国和世界其它国家都十分重视可再生能源的开发和利用。国务院关于替代能源的发展思路是：以新能源替代传统能源，以优势能源替代稀缺能源，以可再生能源替代化石能源，逐步提高替代能源在能源结构中的比重。我国把车用燃料和替代石油产品作为发展重点，因而利用农林生物质发展燃料乙醇和生物柴油等可再生能源具有重要意义。2007年6月7日，国务院总理温家宝主持召开国务院常务会议，审议并原则通过了《可再生能源中长期发展规划》。规划中明确提出，发展可再生能源不得占用耕地，不得消耗大量粮食，不得破坏生态环境。因此，发展燃料乙醇、生物柴油产业必须主要以非粮农林生物质为原料，采用先进的清洁生产技术。     

生物柴油的发展概况与应用前景

石化燃料是当前人类使用的主要能源,但其使用造成了严重的温室效应和环境污染．生物柴油具有安全、无污染、燃烧好、可再生等优点而被当作石化燃料的绿色替代品．本文阐述了生物柴油的本质及其相对于石化柴油在使用上的优良特性,综述了国内外生物柴油技术的研究、应用及产业发展概况,论述了生物柴油研究的重要意义．根据菜油的特点及油菜在我国的发展前景,认为油菜可能是我国发展生物柴油的理想原料．     

新发现一类酶可“消化”难降解的生物质

<正>据物理学家组织网报道,加拿大约克大学和法国马赛第一大学的研究人员在拓展开发第二代生物燃料方面取得了显著进步。他们发现,有一种酶家族能够把在自然界中"难以消化"的生物质降解为自身糖的成分。该研究结果刊登在2012年12月22日的《自然·化学生物学》上。第一代生物燃料对于寻找可再生能源和能源安全产生了一定影响,特别是利用自然界中"易于消化"的生物质如玉米淀粉来制造生物乙醇。但这种方法需要大量能源作物,由此占用了宝贵的可耕土地,进而危及到食品价格的稳定,     

利用可再生农林生物质资源的炼油厂——推动化学工业迈入“碳水化合物“新时代

本文首先介绍了国外以玉米、废弃生物质为原料发展生物炼油厂的设想;然后根据我国国情和已有技术基础,设想了以甜高梁、木薯为原料生产乙醇车用汽油和化工产品的生物炼油厂,以及以菜籽油、棉籽油为原料生产生物柴油和化工产品的生物炼油厂;最后探讨了遇到的问题和采取的对策.     

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...     

利用可再生农林生物质资源的炼油厂——推动化学工业迈入“碳水化合物”新时代

本文首先介绍了国外以玉米、废弃生物质为原料发展生物炼油厂的设想;然后根据我国国情和已有技术基础,设想了以甜高梁、木薯为原料生产乙醇车用汽油和化工产品的生物炼油厂,以及以菜籽油、棉籽油为原料生产生物柴油和化工产品的生物炼油厂;最后探讨了遇到的问题和采取的对策。     

利用可再生农林生物质资源的炼油厂--推动化学工业迈入"碳水化合物"新时代

本文首先介绍了国外以玉米、废弃生物质为原料发展生物炼油厂的设想；然后根据我国国情和已有技术基础，设想了以甜高梁、木薯为原料生产乙醇车用汽油和化工产品的生物炼油厂，以及以菜籽油、棉籽油为原料生产生物柴油和化工产品的生物炼油厂；最后探讨了遇到的问题和采取的对策。     

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.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.