A new mechanism for the formation of meteoritic kerogen-like material

The carbon in ancient carbonaceous chondritic meteorites is mainly in a hydrocarbon composite similar to terrestrial kerogen, a cross-linked structure of aliphatic and aromatic hydrocarbons. Until recently, the composite has been commonly thought to have been produced in the early solar nebula by a Fischer-Tropsch-type process, involving the catalytic synthesis of hydrocarbons from carbon monoxide and hydrogen on grain surfaces. Instead, the aromatic hydrocarbons may form in gas-phase pyrolysis of simple aliphatics like acetylene and methane by a mechanism developed recently to explain formation of soot in combustion and of aromatic molecules in circumstellar envelopes. Nonequilibrium chemical kinetic calculations indicate that this mechanism can produce meteoritic aromatics if the initial concentration of simple hydrocarbons in the solar nebula was sufficiently but not unreasonably high.     

流化床生物质快速热解气组成及冷凝技术的研究进展

流化床生物质快速热解是最具有发展潜力的生物质能源转化技术之一,可将低品位的生物质转换为高品质、易运输的热解油产物,以制取燃料或化工产品。快速热解气的冷凝环节是该技术的重要步骤之一,对应的冷凝技术备受学者关注。在介绍了热解气组成成分的基础上,着重探析了其冷凝过程的传热机理,归纳了三类典型的冷凝方式,指出了生物质快速热解气冷凝技术的发展方向。     

Supported iron nanoparticles as catalysts for sustainable production of lower olefins

Lower olefins are key building blocks for the manufacture of plastics, cosmetics, and drugs. Traditionally, olefins with two to four carbons are produced by steam cracking of crude oil-derived naphtha, but there is a pressing need for alternative feedstocks and processes in view of supply limitations and of environmental issues. Although the Fischer-Tropsch synthesis has long offered a means to convert coal, biomass, and natural gas into hydrocarbon derivatives through the intermediacy of synthesis gas (a mixture of molecular hydrogen and carbon monoxide), selectivity toward lower olefins tends to be low. We report on the conversion of synthesis gas to C(2) through C(4) olefins with selectivity up to 60 weight percent, using catalysts that constitute iron nanoparticles (promoted by sulfur plus sodium) homogeneously dispersed on weakly interactive α-alumina or carbon nanofiber supports.     

Selective, nickel-catalyzed hydrogenolysis of aryl ethers

Selective hydrogenolysis of the aromatic carbon-oxygen (C-O) bonds in aryl ethers is an unsolved synthetic problem important for the generation of fuels and chemical feedstocks from biomass and for the liquefaction of coal. Currently, the hydrogenolysis of aromatic C-O bonds requires heterogeneous catalysts that operate at high temperature and pressure and lead to a mixture of products from competing hydrogenolysis of aliphatic C-O bonds and hydrogenation of the arene. Here, we report hydrogenolyses of aromatic C-O bonds in alkyl aryl and diaryl ethers that form exclusively arenes and alcohols. This process is catalyzed by a soluble nickel carbene complex under just 1 bar of hydrogen at temperatures of 80 to 120°C; the relative reactivity of ether substrates scale as Ar-OAr>Ar-OMe>ArCH(2)-OMe (Ar, Aryl; Me, Methyl). Hydrogenolysis of lignin model compounds highlights the potential of this approach for the conversion of refractory aryl ether biopolymers to hydrocarbons.     

Liquid hydrogen as a fuel for the future

The use of liquid hydrogen as a long-term replacement for hydrocarbon fuel for land and air transportation seems technically feasible. It is an ideal fuel from the standpoint of a completely cyclic system, serving as a "working substance" in a closed chemical and thermodynamic cycle. The energy-per-unit-weight advantage (a factor of 3) over gasoline or any other hydrocarbon fuel makes liquid hydrogen particularly advantageous for air craft and long-range land transport. As a pollution-free fuel, it must be seriously considered as the logical replacement for hydrocarbons in the 21st century.     

城市污泥热解液体产物研究

利用外热式固定床反应器,在400～700℃温度范围内对城市污泥进行热解试验。结果表明,随热解温度的增加,热解液的产率逐渐升高,在550℃时达到最大值,但热解温度继续升高,热解液产率却不断减小;利用GC/MS联用仪对550℃时的热解油进行成分分析,其主要组分为杂环化合物(呋喃、吡啶等)的衍生物、酮类衍生物、苯酚衍生物、苯衍生物、长链脂肪烃衍生物和甾族化合物,其中胆甾烷和甲苯含量较高,分别达15.9%和11%。总之,利用热解法处理城市污泥是可行的,其热解油通过综合分析和分离提纯,可以作为潜在化工原料,具有较高的利用价值。     

生物质居里点热裂解研究

[目的]为生物质裂解的机理分析提供理论基础。[方法]利用JHP-5型居里点裂解仪,在不同的居里点温度下研究杨木屑及其磨木木质素的裂解。同时,在试验的裂解温度范围内研究温度对主要裂解液相产物的影响。[结果]通过GC-MS在线分析裂解的液相产物显示2,种原料的液相产物都为酚类物质,产物基本相同,只是杨木屑的酚类物质种类较多,并且有糠醛产生。液相产物的相对含量随温度的升高都表现为先增加后减少的变化规律,温度为445～590℃时液相主要产物的相对含量较大。[结论]居里点热裂解与气质联用分析技术已成为木质化学研究领域一个固定的技术。     

Py-GC-MS法研究硼及磷化合物对木质素热解产物的影响

采用裂解-气相色谱-质谱(Py-GC-MS)联机分析技术,研究了含硼及磷的化合物对紫椴(Tilia amurensis)木质素热解产物组成的影响。结果表明:木质素在裂解过程中,产生大量的CO2、CO、H2O,其主要原因是高温时羰基、羧基、羟基、甲基等脱除反应以及多环芳香族化反应的深入进行,而所选用的阻燃剂大多数都促进了CO2、CO和H2O的产生。没有经过阻燃处理的木质素热解产物中脂肪族可挥发有机化合物的比例较大,硼酸和有机磷酸盐处理过的木质素在裂解过程中这些化合物的比例明显减少。无机磷酸盐和硼砂有效降低木质素热解过程中芳香族化合物及杂环化合物的比例。FRW阻燃剂中GUP和硼酸对木质素热解过程的影响,并不是简单的加和作用,而表现出协同效应,并初步鉴定了紫椴木质素裂解产物中94种化合物的结构。     

Oil pollution: persistence and degradation of spilled fuel oil

In September 1969, approximately 600 metric tons of number 2 fueloil were spilled in Buzzards Bay, Massachusetts. Two years later, fuel oil hydrocarbons still persisted in the marsh and in offshore sediments. Hydrocarbon degradation is slow, especially below the immediate sediment surface and appears to proceed principally through microbial utilization of alkanes and through partial dissolution of the lower-boiling aromatic hydrocarbons. The boiling range of the spilled oil and the relative abundances of homologous hydrocarbons (for example, phytane and pristane) have been well preserved. The findings are in agreement with the known geochemical stability of hydrocarbons. Fuel oil is an appreciable fraction of whole crude oil. This fact suggests that oil products and crude oils have a considerable environmental persistence.     

Synthesis gas: a raw material for industrial chemicals

Rapid increases in the price of imported crude oil have accelerated a shift in the raw material base for chemical feedstocks from natural gas to crude oil to coal. Widespread use of ethylene as a feedstock has depended on the availability at attractive prices of natural gas and petroleum. As the resource base shifts from natural gas and petroleum to coal, ethylene is being replaced by synthesis gas (a mixture of hydrogen and carbon monoxide of varying composition), which can be manufactured directly from any of these carbonaceous sources. This trend is expected to accelerate in the 1980's. Organics likely to be produced from synthesis gas include ethanol, ethylene glycol, and vinyl acetate.     

生物质热解液化技术的生命周期评价

为探究生物质热解液化技术能源转化过程的效率、经济性及温室气体排放,依据全生命周期评价分析原理,建立废弃秸秆热解制备液体燃料技术全生命周期模型,对该过程进行全生命周期分析,评价范围包括秸秆的收集和运输、干燥和粉碎、生物质热解、木炭加工和余热利用。结果表明：生物质热解液化技术的能量产出投入比为20.43;处理湿秸秆的纯利润约为289.38元/t,销售利润率达52.11%;CO₂当量排放为34.10 g/MJ。生物质热解液化是一种兼具能量效益、经济效益和环境效益等极具潜力的生物质利用技术。     

Review of the direct thermochemical conversion of lignocellulosic biomass for liquid fuels

Increased demand for liquid transportation fuels, environmental concerns and depletion of petroleum resources requires the development of efficient conversion technologies for production of second-generation biofuels from non-food resources. Thermochemical approaches hold great potential for conversion of lignocellulosic biomass into liquid fuels. Direct thermochemical processes convert biomass into liquid fuels in one step using heat and catalysts and have many advantages over indirect and biological processes, such as greater feedstock flexibility, integrated conversion of whole biomass, and lower operation costs. Several direct thermochemical processes are employed in the production of liquid biofuels depending on the nature of the feedstock properties: such as fast pyrolysis/liquefaction of lignocellulosic biomass for bio-oil, including upgrading methods, such as catalytic cracking and hydrogenation. Owing to the substantial amount of liquid fuels consumed by vehicular transport, converting biomass into drop-in liquid fuels may reduce the dependence of the fuel market on petroleumbased fuel products. In this review, we also summarize recent progress in technologies for large-scale equipment for direct thermochemical conversion. We focus on the technical aspects critical to commercialization of the technologies for production of liquid fuels from biomass,including feedstock type, cracking catalysts, catalytic cracking mechanisms, catalytic reactors, and biofuel properties. We also discuss future prospects for direct thermochemical conversion in biorefineries for the production of high grade biofuels.     

生物质炭可溶性有机物化学组成及生物活性意义

生物质热解炭化过程中,有机可挥发组分从固相逸出,冷凝后重新吸附于生物质炭,成为其中的可溶性有机物。生物质炭可溶性有机物化学组成复杂,主要含小分子有机物与芳香类化合物且含有丰富的官能团,具有较高的化学反应活性和生物活性,可显著地改变土壤中养分元素和污染物的形态与有效性,影响土壤微生物组成与丰度,调控作物的生长与健康。依生物质原料和热解条件的差异,生物质炭可溶性有机物的化学结构与生物活性功能也不尽相同。生物质炭可溶性有机物的生物活性意义主要表现为对生物的刺激作用,但部分生物质炭可溶性有机物可能具有一定的潜在毒性风险。通过提取生物质炭可溶性有机物可生产具有生物刺激作用的商品液体有机肥,从而实现生物质炭的分值利用。未来需要进一步加强生物质炭可溶性组分的生物活性或毒性物质的鉴定及其形成机制的研究,这对于生物质炭产品的优化是十分必要的,也是应用生物质炭尽量避免环境风险的要求。     

Powering fuel cells with CO via aqueous polyoxometalates and gold catalysts

Electricity was produced by catalytic oxidation of carbon monoxide (CO) by using gold catalysts at room temperature. The observed rates are faster than conventional processes operating at 500 kelvin or higher for the conversion of CO with water to produce hydrogen and carbon dioxide through the water-gas shift (WGS). By eliminating the WGS reaction, we remove the need to transport and vaporize liquid water in the production of energy for portable applications. This process can use CO-containing gas streams from the catalytic reforming of hydrocarbons to produce an aqueous solution of reduced polyoxometalate compounds that can be used to generate power. The reduced polyoxometalate can be reoxidized in fuel cells that contain simple carbon anodes.     

An octane-fueled solid oxide fuel cell

There are substantial barriers to the introduction of hydrogen fuel cells for transportation, including the high cost of fuel-cell systems, the current lack of a hydrogen infrastructure, and the relatively low fuel efficiency when using hydrogen produced from hydrocarbons. Here, we describe a solid oxide fuel cell that combines a catalyst layer with a conventional anode, allowing internal reforming of iso-octane without coking and yielding stable power densities of 0.3 to 0.6 watts per square centimeter. This approach is potentially the basis of a simple low-cost system that can provide substantially higher fuel efficiency by using excess fuel-cell heat for the endothermic reforming reaction.     

Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes

It is imperative to develop more efficient processes for conversion of biomass to liquid fuels, such that the cost of these fuels would be competitive with the cost of fuels derived from petroleum. We report a catalytic approach for the conversion of carbohydrates to specific classes of hydrocarbons for use as liquid transportation fuels, based on the integration of several flow reactors operated in a cascade mode, where the effluent from the one reactor is simply fed to the next reactor. This approach can be tuned for production of branched hydrocarbons and aromatic compounds in gasoline, or longer-chain, less highly branched hydrocarbons in diesel and jet fuels. The liquid organic effluent from the first flow reactor contains monofunctional compounds, such as alcohols, ketones, carboxylic acids, and heterocycles, that can also be used to provide reactive intermediates for fine chemicals and polymers markets.     

Biomass as a source of chemical feedstocks: an economic evaluation

It is suggested that the raw materials and technology exist for basing a major fraction of the U.S. chemical industry on four fermentation products, used in the proper portions: ethanol, isopropanol, n-butanol, and 2,3-butanediol. The primary route for introduction of these materials is dehydration of the alcohols and diols to olefins, which would cause little disruption of the existing industry downstream from the olefins. The proposed substitution has the advantages that it would provide a smooth transition toward renewable feedstocks, while decreasing dependence on fossil sources of organic material and use of toxic materials. However, to make these materials attractive as feedstocks or intermediates in chemical production, their current prices must be substantially reduced. Even with the optimum mix, their largeseale utilization will only occur at about 20 to 40 percent of their estimated chemical prices.     

广西不同产地岗松的生物量和得油率研究

[目的]筛选广西生物量高、含油率高的岗松品种。[方法]2016年10月,通过对广西11个产地岗松的生物量和得油率进行测定。[结果]钦州地区的岗松绝干得油率最高,为1.49%,生物量较高的岗松也是在钦州等沿海地区。岗松优良单株的选择不仅取决于生物量和得油率,还要考虑其挥发油的主要化学成分含量。[结论]该研究可为岗松的选优及推广种植提供借鉴。     

温度梯度对秸秆炭化物质产率及特性的影响

在300～700℃温度区间,玉米秸秆、水稻秸秆以每100℃为间隔,大豆秸秆以200℃为间隔,研究炭化热解,量化对比产物。结果表明,秸秆热解炭比表面积、总孔容积、pH和碱式官能团随温度升高而增加,孔径和酸式官能团随温度升高而降低;热解液随热解温度升高,酸度降低;热解气中氢气和甲烷含量随温度升高而增加。热解温度平均每升高100℃,热解炭产率平均减少9.31%,热解液产率平均增加4.55%,热解气产率平均增加4.35%。玉米秸秆热解炭、热解液和热解气产率拐点分别为600、611和666℃,水稻秸秆热解炭、热解液和热解气产率拐点分别为666、600和666℃。量化参数可为优化秸秆炭化工艺提供技术支持。     

水稻秸秆成型燃料热解特性试验研究

秸秆是我国最主要的生物质资源,对其进行热解是将生物质能转换为高效高品位清洁能源的最有效措施之一。利用热重分析方法对水稻秸秆及木屑成型燃料热解特性及其动力学规律进行了研究,分析了试样以不同升温速率在氩气气氛下进行热解的试验结果。结果表明:水稻秸秆成型燃料热解过程划分为三个重要阶段,即预热解、快速热解和慢速热解阶段;热解最大速率会随着热解升温速率的升高而增大,有利于热解进行,但会造成反应不彻底等问题,因此温升速率不宜过高;通过对比两种成型燃料的热解性能得到,木屑成型燃料的热稳定性优于水稻秸秆成型燃料;对水稻秸秆成型燃料热解进行动力学参数计算得到:活化能和指前因子会随着升温速率的升高而增大,线性拟合系数均在0.99之上,说明主反应阶段符合一级反应模型。