木质纤维素基平台化合物催化转化制备液体燃料及燃料添加剂

随着不可再生的石化资源的不断消耗以及生态环境的不断恶化,可再生资源和能源的开发和利用受到越来越多的重视。木质纤维素是地球上最丰富的可再生生物质资源,蕴藏量和产量巨大,具有广阔的开发利用前景。本文在介绍国内外木质纤维素资源开发利用研究的基础上,结合当今世界生物质能领域的研发现状,分别概述了经由呋喃类化合物及乙酰丙酸等木质纤维素基平台化合物分子,制备液体燃料和燃料添加剂的最新研究进展。在总结归纳合成途径的同时,分析了现阶段面临的主要问题及可能的解决办法,以期能为木质纤维素类生物质能源化利用的研究提供有益的参考与借鉴。     

液体碳氢燃料蒸汽重整制氢催化剂研究进展

液体碳氢燃料具有能量密度高、氢含量大及便于储存和运输的特点,以其为原料经重整制氢并应用到移动式的燃料电池/加氢站对民用设备及国防武器等具有现实意义。本文首先对液体碳氢燃料蒸汽重整机理进行概述,明确当前催化剂面临的积炭、硫中毒等主要问题,从而指导高性能催化剂的设计和开发;其次,总结了几种典型液体碳氢燃料（汽油、煤油、柴油、焦油、含硫碳氢燃料等）蒸汽重整催化剂的相关进展,对比了不同催化剂在相应工艺条件下的活性及稳定性;最后,归纳了几类蒸汽重整过程强化技术包括等离子体重整、化学链重整、吸附增强重整及反应与分离耦合重整,说明了各类强化技术的优点及存在的不足,提出通过构建高效催化剂与蒸汽重整强化技术耦合有望实现液体碳氢燃料的高效转化制氢。希望本综述能为进一步研究液体碳氢燃料重整制氢提供相关指导。     

用于PEMFC的天然气水蒸气制氢系统

针对质子交换膜燃料电池（PEMFC）的应用要求,开发了一个包括天然气水蒸气重整、CO变换和变压吸附净化的制氢工艺过程,并着重对重整反应和变压吸附的操作条件进行了实验研究。考察了温度、空速和水碳比对重整反应的影响,得到适宜的工艺操作条件,实验结果表明：温度650℃、水碳比6、空速42h^-1时,氢气含量为70.21%,甲烷转化率为77.41%;分析了温度、流速对变压吸附脱除CO效果的影响,结果表明：在0.2MPa、40℃和吸附、脱附时间120s的条件下,产品气中CO浓度接近于1×10^-6,经过多次循环后产品气质量稳定,可以连续获得满足80W质子交换膜燃料电池要求的高纯度氢气。     

Ignition characteristics of liquid hydrocarbon fuels as single droplets

An investigation into the effects of fuel boiling point and chemical type on the autoignition of single droplets of a number of pure hydrocarbons is reported. Ignition delay times were measured using the suspended droplet technique, and a numerical model was developed to extract reaction rate constants for the fuels. The results show that both fuel boiling point and chemical kinetics are important contributors to the ignition delay.     

Syngas production from liquid fuels in a non-catalytic porous burner

This paper investigates rich combustion of n-heptane, diesel oil, kerosene and rapeseed-oil methyl ester (RME) bio-diesel for the purpose of producing syngas ready for the clean-up stages for fuel-cell applications or for traditional combustor enrichment. Rich flames have been stabilised in a two-layer inert porous medium combustor and a range of equivalence ratios and porous materials have been examined. n-heptane was successfully reformed up to an equivalence ratio of 3, reaching a conversion efficiency (based on the lower heating value of H₂ and CO over the fuel input) up to 75% for a packed bed of alumina beads. Similarly, diesel, kerosene and bio-diesel were reformed to syngas in a Zirconia foam burner with conversion efficiency over 60%. A preliminary attempt to reduce the content of CO and hydrocarbons in the reformate has been also conducted using commercial steam reforming and water-gas shift reaction catalysts, obtaining encouraging results. Finally, soot emission has been assessed, demonstrating particle formation for diesel oil above φ = 2, whereas bio-diesel showed the lowest soot formation tendency among all the fuels tested.     

Fischer-Tropsch synthesis catalysts for the production of liquid fuels from various raw materials

The properties of cobalt catalysts for the Fischer-Tropsch synthesis used in XTL processes (the conversion of any organic raw materials into liquid hydrocarbons) are considered. It is shown that the catalysts used for the production of synthetic petroleum are characterized by a relatively low activity in polymerization reactions, and they make it possible to obtain hydrocarbon mixtures with the concentration of solid paraffins no higher than 10%. The catalysts used for conducting the synthesis of middle oil distillates are characterized by high polymerizing activity (alpha of 0.9 or higher) and by the high yields of C₅₊ hydrocarbons.     

Ignition of aluminum powders mixed with liquid hydrocarbon fuels in air

The feasibility of ignition of aluminum powders in air is studied by examining a number of hydrocarbon fuels, promoter additives in them, and hybrid systems of liquid mixtures and powders in shock waves. Data are obtained on the ignition delays for each of the components and mixtures of them. It is shown that for temperatures of 1000–2000 K, ignition is possible, with delays of less than 2 msec, in hybrid systems of Al powders having a dispersity of 5–10 μm with diesel fuel and added fatty-alcohol nitrates. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 1, pp. 35–40, January–February 1999.     

Steam reforming of liquid hydrocarbon fuels for micro-fuel cells. Pre-reforming of model jet fuels over supported metal catalysts

The present work deals with pre-reforming of logistic hydrocarbon fuel (jet fuel) as a part of an integrated approach to developing an on-board fuel reformer for use in a micro-solid-oxide fuel cell system. The purpose of doing pre-reforming is to ensure carbon-free reformulation of JP-8 jet fuel into hydrogen and carbon monoxide for use in a micro-solid-oxide fuel cell. Several model jet fuels have been tested for the pre-reforming at low temperature (450–550 °C) in a lab-scale reforming reactor. Proper temperature control and pre-mixing of feed fuels and steam have been found to be important for the prevention of coke formation prior to pre-reforming. Both noble metal and base-metal catalysts have been prepared and tested. As compared with an Al₂O₃-supported Ni catalyst, supported Rh catalysts show not only high activity but also high resistance to deactivation due to carbon formation. Removal of residual Cl⁻ from Rh/CeO₂–Al₂O₃ improves the metal dispersion and the pre-reforming activity. The reformates from the current pre-reformer contain mainly CH₄, CO, H₂, in which CH₄ can be further converted to H₂ and CO by subsequent main-reforming.     

化学链燃烧耦合甲烷重整制液体燃料工艺

为探讨能量的高效利用,提出了化学链燃烧耦合甲烷重整制液体燃料工艺,并利用Aspen Plus软件进行工艺模拟。研究了重整单元进料甲烷/二氧化碳/水蒸气的摩尔比(M/C/S)、反应温度(T)以及费托合成气相循环比(R)对CO2转化率、合成气氢碳比、能量效率、费托合成火用损等系统性能指标的影响,并以能量效率最高为目标,对系统参数进行了优化。研究表明,当M/C/S=3/1/2、T=800℃、R=0. 9时,生成的合成气氢碳比为2. 1,系统的总能量效率和液体燃料生产效率最高,分别为57. 0%和50. 0%,系统能源节约率为9. 0%。     

化学链燃烧耦合甲烷重整制液体燃料工艺

为探讨能量的高效利用,提出了化学链燃烧耦合甲烷重整制液体燃料工艺,并利用Aspen Plus软件进行工艺模拟。研究了重整单元进料甲烷/二氧化碳/水蒸气的摩尔比(M/C/S)、反应温度(T)以及费托合成气相循环比(R)对CO2转化率、合成气氢碳比、能量效率、费托合成火用损等系统性能指标的影响,并以能量效率最高为目标,对系统参数进行了优化。研究表明,当M/C/S=3/1/2、T=800℃、R=0. 9时,生成的合成气氢碳比为2. 1,系统的总能量效率和液体燃料生产效率最高,分别为57. 0%和50. 0%,系统能源节约率为9. 0%。     

Supported silver adsorbents for selective removal of sulfur species from hydrocarbon fuels

Dispersed silver oxides on supports such as TiO₂, γ-Al₂O₃ and SiO₂ were observed to be effective desulfurizing agents for refined fuels at ambient conditions. TiO₂ was determined to be the most stable support for silver oxide. Ag (4 wt%)/TiO₂ demonstrated a saturation sulfur capacity of 6.3 mgS/g for JP5 fuel containing 1172 ppmw sulfur. This high affinity for sulfur translated to one sulfur heterocycle associated with every two surface Ag atoms in the sorbent even in the presence of a 160-fold excess of other aromatics found in the fuel. A unique attribute of these sorbents was that they were thermally regenerable at 450 °C using air as a stripping medium over multiple cycles. Desulfurization characteristics also varied with fuel composition. Variation in desulfurization performance between JP5, JP8 and a light fraction JP5 were established and associated with the differences in sulfur composition of these fuels. The effects of surface area, porosity and crystal structure of the sorbent on sulfur capacity are also presented.     

Catalyst design and development for upgrading hydrocarbon fuels

Hydrogenation and hydrocracking catalysts were designed and synthesized based on findings from catalyst characterization and model reactions. Two types of the synthesized catalysts were then tested using two stage upgrading of unconventional feedstocks. The causes of catalyst deactivation were studied in order to prepare a practical catalyst with a long life.     

Production of liquid fuels from waste plastics

Exploratory work was carried out to develop a process for conversion of mixed plastic wastes into liquid transportation fuels or petrochemicals. The concept used is based on thermal depolymerization of the polymers in a suitable solvent followed by catalytic conversion of the resulting polymeric fragments into hydrocarbons with boiling points below 525°C. The process is carried out batch-wise over a zeolite catalyst at temperatures from 350°C to 450°C and at atmospheric pressure. No hydrogen is used and volatile products formed are continuously removed from the reactor. Tests were carried out on polyethylene and polypropylene alone, and on mixtures of the two. Finally, a synthetic mixture of four different plastics was tested. From 90% to 98% of the plastic was converted to gases or distillable hydrocarbons. Of this yield, from 20% to 55% was gas, primarily propylenes and butylenes, and from 32% to 70% was a light hydrocarbon oil. Very little non-distillable coke or residue was formed. The use of mixtures did not affect the high conversions obtained, but the results could only be approximately predicted based on a pro-rating of results for the individual components.     

Conversion and uses of liquid fuels from coal

This general paper surveys recent developments in converting coal, mainly into hydrocarbons for use in the transport and chemical industries. Primary conversions by direct, i.e. solvent extraction, and indirect methods are described, together with some of the subsequent refining procedures required to make acceptable products. Though it is unlikely that there will be an overnight world shortage of crude petroleum, political instabilities do not rule this out and ‘local’ shortages might be very acute. Most probably there will be a transitional period in which coal and oil contribute in complementary ways. As oil supplies diminish, coal will be needed increasingly for making essential transport distillates and chemical intermediates. Most conversion processes under development aim to make product oils which can be readily fitted into existing markets. However, coals differ considerably from crude oils in chemical composition and complexity. Thus, in making motor spirit, relatively few technical problems are expected, but in other areas, e.g. in diesel fuels and some ‘petrochemical’ intermediates, coal-conversion products are much less suited to current uses without further (usually expensive) processing. The relative merits of various processing methods are discussed. The paper also considers replacement sources for ‘petrochemicals’ and discusses the wider implications of making olefins. The scope for making intermediate chemicals by coal gasification and subsequent synthesis is outlined. Some areas of future difficulty including technical, economic and environmental matters, are discussed.     

Catalytic chemistry of preparation of hydrocarbon fuels from vegetable oils and fats

The problem of preparing engine fuels from renewable feedstocks via the catalytic processing of inedible vegetable oils and fats is considered. Different types of inedible feedstocks are described, including algae, inedible plants, wood processing products, and waste fats and oils. Catalytic processes are considered for preparing the second generation biodiesel through the hydrodeoxygenation and deoxygenation of triglycerides and fatty acids, and of their derivatives. Brief information on catalysts for the deoxygenation of fatty acids is given. Special attention is given to analyzing the mechanism and kinetics of the deoxygenation reaction. Based on conducted kinetic and quantum-chemical investigations and using the literature data, a deoxygenation mechanism is proposed by the authors that explains the observed dependences of decarboxylation and decarbonylation contributions on the reaction conditions (the stearic acid, water, and catalyst concentrations, the hydrogen and CO pressures, and the temperature). Examples of the application of hydrocarbon biodiesel in transport are presented.