生物质闪速热裂解制取生物油的试验研究

基于生物质资源的高效清洁能源化利用目的，对生物质热裂解制取生物油这一具有重要应用前景的技术开展研究。结合流化床的优质和生物质的特殊性，自行研制成功给料速达5kg/h的流化床热裂解反应器，并制取得到产率高达60％的生物油。同时针对木屑和秸秆的系统试验研究得出了反应温度和原料种类等主要参数对生物质闪速热裂解制油的影响规律。     

生物质热裂解制取液体燃料的实验研究

在对生物质热裂解技术进行系统研究的基础上，率先在国内自行开发研制了以流化床反应器为主体的可连续运行的生物质热裂解制取游液体燃料系统，成功地制取出了产率高达60％的生物油。同时简要介绍了适合于生物油分析的GC－MS分析方法，得出生物油由于高水分含量和高含氧量需作进一步改性处理后才能投入实际应用。     

基于欧拉-欧拉多相流模型对生物质快速热裂解的数值模拟

基于欧拉-欧拉多相流方法,采用单步多元反应动力学模型研究了生物质在二维鼓泡流化床反应器中的快速热裂解反应,分析了反应器中颗粒流动、传热以及热裂解产物组成的分布规律。结果表明:气泡的流动有助于气体、石英砂和生物质的混合和热量交换;经过气体的对流换热和石英砂的接触导热,生物质温度迅速升高后发生热裂解,热裂解温度为750～850 K;计算得到的生物油、焦炭和不可冷凝气体的产率分别为59.2%、14.4%和22.1%。     

生物油热解及燃烧特性分析

对由木粉热解所得的生物油样品分别进行了氮气与氧气气氛下不同升温速率的热重分析试验.结果表明:生物油的热解分为两个阶段,第一阶段为生物油中低沸点有机物的挥发以及各组分间反应生成各类产物的过程,第二阶段为各种重组分的裂解过程;生物油的燃烧分为3个阶段,即前期的挥发与裂解和最后焦炭的燃烧过程.提高升温速率使氮气气氛中生物油样品的初始失重温度、失重峰值温度及对应的最大失重速率均有所增大,且在较高升温速率(20℃min)下,较少含炭残余物形成.随升温速率升高,生物油着火温度提高,最终失重率无变化.最后根据热重数据对热解与燃烧各段反应进行了动力学拟合.     

生物质及其热裂解产物生物油的特性分析

以红松、白松、落叶松、玉米秸秆等不同生物质为原料,对流化床反应器热裂解制取的生物油进行了研究试验,通过对生物油的物理特性及其成分的分析,得出的实验结果表明:红松制取的生物油品质最好,热值高,含水率低,更适合进一步改性研究和应用,并利用现代精密仪器GC-MS对生物油进行了组分分析,解释了生物油高含氧和高含水特性。     

移动床内高炉渣热载体与生物质热解液化实验研究

以移动床为高炉渣余热裂解生物质实验平台,研究高炉渣温度、粒径和生物质粒径等对生物质热解产物分布的影响。结果表明,生物油产率随着高炉渣温度的增加先增加后减小,当高炉渣热载体温度为650℃时,生物油产率最高;高炉渣粒径和生物质粒径越小,生物油的产率越大。炉渣温度650℃、粒径0~2mm,生物质粒径小于75μm,生物质油产率达到57.3%。生物油中含氧量和含水率较高,热值低,pH值为3.7。     

生物油催化裂解的动力学分析

以CaO·MgO混合物为催化剂,采用热重分析法探讨了混合物中MgO含量对生物油催化裂解反应速度和最终残留率的影响.实验结果显示,生物油的热重变化过程可以分为室温～200℃范围内的挥发阶段和200～520℃范围内的热裂解阶段.在热裂解阶段中,反应速率常数和温度的关系可以用Ardaenius方程式表示.在MgO含量为50%的CaO·MgO混合物的催化作用下,生物油热裂解反应活化能从无催化剂时的20.9kJ/mol降低到16.5kJ/mol,最终相对残留率降低到0.75.MgO含量为38.7%的煅烧白云石是有效的生物油裂解催化剂.     

我国生物质热解液化技术的现状

文章主要阐述了我国生物质热解液化技术的研究现状，包括现有的热裂解液化装置、反应动力学模型、已检测出的不同原料裂解产生的生物油成分及其物理特性分析，提出了生物油精制的必要性和未来需要研究的问题。     

生物质热裂解技术的实验研究

以木屑为原料,利用从荷兰引进的旋转锥反应器闪速热裂解装置进行了热裂解试验。对热裂解产物的组成及反应的物质平衡进行了分析。结果表明：木屑热裂解产物由生物油、不可冷凝气体和木炭组成。其中,生物油成分复杂,低热值为１６ ５９５ｋＪ／ｋｇ;不可冷凝气体主要由ＣＯ,ＣＨ４ ,ＣＯ２ ,Ｈ２ 和Ｈ２Ｏ蒸汽组成。在反应器温度为６００℃,旋风机温度为５００ ℃,旋转锥频率为１０Ｈｚ 条件下,当木屑喂入率为２６．４２ｋｇ／ｈ 时,生物油、不可冷凝气体及木炭的得率分别为５３．３７％ ,２１ ．４５％ 和２５．１６％ 。     

CaO伴随纤维素快速热裂解的落体试验研究

采用自由落体-辐射加热的试验方法,对CaO伴随生物质快速热裂解制油的脱氧效果进行了研究.利用气相色谱/质谱联用仪(GC-MS)对油样进行分析,结果表明:纤维素一次裂解的主要产物是左旋葡聚糖(LG);纯纤维素以及33%和56%CaO伴随纤维素裂解油中LG的质量百分含量分别为59.1%、35.8%和25.1%;LG作为热解油中含氧量最高的成分,其质量百分含量随CaO的加入急剧下降,说明CaO的加入可降低热解油的含氧量.计算结果表明:33%和56%CaO伴随纤维素热裂解时,可分别降低油品含氧量约10%和12.5%,说明CaO可直接固定纤维素热裂解平行反应中CO2或类似中间基团,形成有利于葡萄糖单体分裂、重整路线进行的"化学汇"结果.     

Natural-gas fueled spark-ignition (SI) and compression-ignition (CI) engine performance and emissions

Natural gas is a fossil fuel that has been used and investigated extensively for use in spark-ignition (SI) and compression-ignition (CI) engines. Compared with conventional gasoline engines, SI engines using natural gas can run at higher compression ratios, thus producing higher thermal efficiencies but also increased nitrogen oxide (NO_x) emissions, while producing lower emissions of carbon dioxide (CO₂), unburned hydrocarbons (HC) and carbon monoxide (CO). These engines also produce relatively less power than gasoline-fueled engines because of the convergence of one or more of three factors: a reduction in volumetric efficiency due to natural-gas injection in the intake manifold; the lower stoichiometric fuel/air ratio of natural gas compared to gasoline; and the lower equivalence ratio at which these engines may be run in order to reduce NO_x emissions. High NO_x emissions, especially at high loads, reduce with exhaust gas recirculation (EGR). However, EGR rates above a maximum value result in misfire and erratic engine operation. Hydrogen gas addition increases this EGR threshold significantly. In addition, hydrogen increases the flame speed of the natural gas-hydrogen mixture. Power levels can be increased with supercharging or turbocharging and intercooling. Natural gas is used to power CI engines via the dual-fuel mode, where a high-cetane fuel is injected along with the natural gas in order to provide a source of ignition for the charge. Thermal efficiency levels compared with normal diesel-fueled CI-engine operation are generally maintained with dual-fuel operation, and smoke levels are reduced significantly. At the same time, lower NO_x and CO₂ emissions, as well as higher HC and CO emissions compared with normal CI-engine operation at low and intermediate loads are recorded. These trends are caused by the low charge temperature and increased ignition delay, resulting in low combustion temperatures. Another factor is insufficient penetration and distribution of the pilot fuel in the charge, resulting in a lack of ignition centers. EGR admission at low and intermediate loads increases combustion temperatures, lowering unburned HC and CO emissions. Larger pilot fuel quantities at these load levels and hydrogen gas addition can also help increase combustion efficiency. Power output is lower at certain conditions than diesel-fueled engines, for reasons similar to those affecting power output of SI engines. In both cases the power output can be maintained with direct injection. Overall, natural gas can be used in both engine types; however further refinement and optimization of engines and fuel-injection systems is needed.     

Decomposition of limestone in a solar reactor

The thermal decomposition of limestone has been selected as a model reaction for developing and testing an atmospheric open solar reactor. The reactor consists of a cyclone gas/particle separator which has been modified to let the concentrated solar energy enter through a windowless aperture. The reacting particles are directly exposed to the solar irradiation. Experimentation with a 60 kW reactor prototype was conducted at PSI's 90m² parabolic solar concentrator, in a continuous mode of operation. A counter-current flow heat exchanger was employed to preheat the reactants. Eighty five percent degree of calcination was obtained for cement raw material and 15% of the solar input was converted into chemical energy (enthalpy).The technical feasibility of the solar thermal decomposition of limestone was experimentally demonstrated. The use of solar energy as a source for high-temperature process heat offers the potential of reducing significantly the CO₂ emissions from lime producing plants. Such a solar thermochemical process can find application in sunny rural areas for avoiding deforestation.     

Biohydrogen production by Anabaena sp. PCC 7120 wild-type and mutants under different conditions: Light, nickel, propane, carbon dioxide and nitrogen

Increasing awareness of environmental problems caused by the current use of fossil fuel-based energy, has led to the search for alternatives. Hydrogen is a good alternative and the cyanobacterium Anabaena sp. PCC 7120 is naturally able to produce molecular hydrogen, photosynthetically from water and light. However, this H₂ is rapidly consumed by the uptake hydrogenase.This study evaluated the hydrogen production of Anabaena sp. PCC 7120 wild-type and mutants: hupL⁻ (deficient in the uptake hydrogenase), hoxH⁻ (deficient in the bidirectional hydrogenase) and hupL⁻/hoxH⁻ (deficient in both hydrogenases) on several experimental conditions, such as gas atmosphere (argon and propane with or without N₂ and/or CO₂ addition), light intensity (54 and 152 ??Em⁻²s⁻¹), light regime (continuous and light/dark cycles 16 h/8 h) and nickel concentrations in the culture medium.In every assay, the hupL⁻ and hupL⁻/hoxH⁻ mutants stood out over wild-type cells and the hoxH⁻ mutant. Nevertheless, the hupL⁻ mutant showed the best hydrogen production except in an argon atmosphere under 16 h light/8 h dark cycles at 54 ??Em⁻²s⁻¹ in the light period, with 1 ??M of NiCl₂ supplementation in the culture medium, and under a propane atmosphere.In all strains, higher light intensity leads to higher hydrogen production and if there is a daily 1% of CO₂ addition in the gas atmosphere, hydrogen production could increase 5.8 times, related to the great increase in heterocysts differentiation (5 times more, approximately), whereas nickel supplementation in the culture medium was not shown to increase hydrogen production. The daily incorporation of 1% of CO₂ plus 1% of N₂ did not affect positively hydrogen production rate.     

Investigation of the thermodynamic and kinetic properties of La–Fe–B system hydrogen-storage alloys

La–Fe–B hydrogen-storage alloys were prepared using a vacuum induction-quenching furnace with a rotating copper wheel. The thermodynamic and kinetic properties of the La–Fe–B hydrogen-storage alloys were investigated in this work. The P–C–I curves of the La–Fe–B alloys were measured over a H₂ pressure range of 10⁻³ MPa to 2.0 MPa at temperatures of 313, 328, 343 and 353 K. The P–C–I curves revealed that the maximum hydrogen-storage capacity of the alloys exceeded 1.23 wt% at a pressure of approximately 1.0 MPa and temperature of 313 K. The standard enthalpy of formation ΔH and standard entropy of formation ΔS for the alloys' hydrides, obtained according to the van't Hoff equation, were consistent with their application as anode materials in alkaline media. The alloys also exhibited good absorption/desorption kinetics at room temperature.     

The Solar Office in context

The goal of sustainability in buildings can only hope to be realised if buildings are designed to both conserve and generate energy. The Solar Office at Doxford International is designed to minimise the use of energy while its external fabric is designed to replace such energy that is used. The recently completed building is now subject of a comprehensive monitoring programme. The programme covers both the performance of the 73 kW_p photovoltaic installation and the environmental conditions within the building as a whole. Hour by hour findings are posted on a dedicated web site. Photovoltaics could have the same impact on building form and layout as the invention of the passenger lift at the end of the last century.     

Hydrogen recovery from the photovoltaic electroflocculation-flotation process for harvesting Chlorella pyrenoidosa microalgae

In this paper, an integrated process using photovoltaic power to harvest microalgae by electro-flocculation (EF) and hydrogen recovery is presented. It is mainly favorable in regions with high solar radiation. The electro-flocculation efficiency (EFE) of Chlorella pyrenoidosa microalgae was investigated using various types of electrodes (aluminum, iron, zinc, copper and a non-sacrificial electrode of carbon). The best results regarding the EFE, and biomass contamination were achieved with aluminum and carbon electrodes where the electrical energy demand of the process for harvesting 1 kg of algae biomass was 0.28 and 0.34 kWh, respectively, while the energy yield of harvested hydrogen was 0.052 and 0.005 kWh kg^?1, respectively. The highest harvesting efficiency of 95.83 ± 0.87% was obtained with the aluminum electrode.The experimental hydrogen yields obtained were comparable with those calculated from theory. With a low net energy demand, microalgae EF may be a useful and low-cost technology.     

Electrochemical behavior of Mg–Li,Mg–Li–Al and Mg–Li–Al–Ce in sodium chloride solution

Mg–Li, Mg–Li–Al and Mg–Li–Al–Ce alloys were prepared and their electrochemical behavior in 0.7 M NaCl solutions was investigated by means of potentiodynamic polarization, potentiostatic current–time and electrochemical impedance spectroscopy measurements as well as by scanning electron microscopy examination. The effect of gallium oxide as an electrolyte additive on the potentiostatic discharge performance of these magnesium alloys was studied. The discharge activities and utilization efficiencies of these alloys increase in the order: Mg–Li < Mg–Li–Al < Mg–Li–Al–Ce, both in the absence and presence of Ga₂O₃. These alloys are more active than commercial magnesium alloy AZ31. The addition of Ga₂O₃ into NaCl electrolyte solution improved the discharging currents of the alloys by more than 4%, and enhanced the utilization efficiencies of the alloys by more than 6%. It also shortened the transition time for the discharge current to reach to a steady value. Electrochemical impedance spectroscopy measurements showed that the polarization resistance of the alloys decreases in the following order: Mg–Li > Mg–Li–Al > Mg–Li–Al–Ce. Mg–Li–Al–Ce exhibited the best performance in term of activity, utilization efficiency and activation time.     

Temperature dependence of the enthalpy of formation of metal hydrides characterized by an excess volume

A universal framework to calculate the temperature dependence of the excess enthalpy present in regions characterized by an excess volume is calculated for metals and metal hydrides. At high temperatures, the different contributions from the pressure–volume, heat capacity, entropy and work associated with the thermal expansion are studied separately and their magnitudes and signs are compared. It is found that the pressure–volume contribution opposes and dominates the other three contributions at both high temperature and excess volume, and it is thus found that this contribution becomes the leading temperature dependent contribution to the enthalpy of a material. The conditions under which a temperature change will reduce the enthalpy of formation of metal hydrides are also given and the Mg/MgH₂ system is studied as an example. Excluding the heat capacity contribution, an increase in temperature tends to offset the effect of the excess volume on the enthalpy of formation. It is also demonstrated that the impact of temperature will be more favorable to a reduction of the enthalpy of formation if a large fraction of the metal hydride is in a state of small excess volume compared to a small fraction of the hydride in a state of high excess volume.     

Ash-forming elements in four Scandinavian wood species. Part 1: Summer harvest

Woody biomass in Finland and Sweden comprises mainly four wood species: spruce, pine, birch and aspen. To study the ash, which may cause problems for the combustion device, one tree of each species were cut down and prepared for comparisons with fuel samples. Well-defined samples of wood, bark and foliage were analyzed on 11 ash-forming elements: Si, Al, Fe, Ca, Mg, Mn, Na, K, P, S and Cl. The ash content in the wood tissues (0.2–0.7%) was low compared to the ash content in the bark tissues (1.9–6.4%) and the foliage (2.4–7.7%). The woods’ content of ash-forming elements was consequently low; the highest contents were of Ca (410–1340 ppm) and K (200–1310), followed by Mg (70–290), Mn (15–240) and P (0–350). Present in the wood was also Si (50–190), S (50–200) and Cl (30–110). The bark tissues showed much higher element contents; Ca (4800–19,100 ppm) and K (1600–6400) were the dominating elements, followed by Mg (210–2400), P (210–1200), Mn (110–1100) and S (310–750), but the Cl contents (40–330) were only moderately higher in the bark than in the wood. The young foliage (shoots and deciduous leaves) had the highest K (7100–25,000 ppm), P (1600–5300) and S (1100–2600) contents of all tissues, while the shoots of spruce had the highest Cl contents (820–1360) and its needles the highest Si content (5000–11,300). This paper presented a new approach in fuel characterization: the method excludes the presence of impurities, and focus on different categories of plant tissues. This made it possible to discuss the contents of ash element in a wide spectrum of fuel-types, which are of large importance for the energy production in Finland and Sweden.     

Tailored solar optics for maximal optical tolerance and concentration

Recently identified fundamental classes of dual-mirror double-tailored nonimaging optics have the potential to satisfy the pragmatic exigencies of concentrator photovoltaics. Via a comprehensive survey of their parameter space, including raytrace verification, we identify champion high-concentration high-efficiency designs that offer unprecedented optical tolerance (i.e., sensitivity to off-axis orientation) - a pivotal figure-of-merit with a basic bound that depends on concentration, exit angle, and effective solar angular radius. For comparison, results for the best corresponding dual-mirror aplanatic concentrators are also presented.