小桐子油在亚临界水中水解反应的试验研究

以小桐子油为原料,对油脂在亚临界水-超临界甲醇两步法制备生物柴油的第一步水解反应中水解的影响因素和反应动力学进行了研究。试验结果表明,在小桐子油与水体积比为1:3,反应温度290℃,反应时间40min时,小桐子油水解反应最为合适,转化率为98.9%。对此水解反应进行了动力学分析,得到小桐子油在亚临界水中水解反应的平均反应级数为0.78,活化能为55.34kJ/mol,动力学模型为-(dc_A/dt)=7254.96e~(-55.34/RT)c_A~(0.78)。     

菜籽油在亚临界水中的水解反应动力学模型研究

以菜籽油为生物柴油制备原料,研究菜籽油在亚临界水中的水解反应动力学方程.实验结果表明：菜籽油在亚临界水中的最佳反应条件为：反应温度290℃,反应时间40 min,反应压力24 MPa,油水体积比为1∶3（摩尔比为1∶220）,转化率最高可达到97％.同时,对此最佳反应条件下的水解反应进行动力学分析,确定了菜籽油在亚临界水中水解反应动力学模型参数：平均反应级数为0.7766,活化能为61.49 kJ/mol,频率因子为7 261.     

小桐子油脂肪酸在超临界甲醇中酯化反应动力学的研究

以小桐子油完全水解制取的脂肪酸为原料,对亚临界-超临界两步法制备生物柴油的第二步脂肪酸在超临界甲醇中酯化反应的影响因素进行了研究。试验结果表明:在脂肪酸与甲醇体积比为1:2,反应温度290℃,反应时间20min时,小桐子油脂肪酸酯化反应较为合适,转化率为98.49%。由试验数据采用数学规划求解进行动力学分析,得到小桐子油脂肪酸在超临界甲醇中酯化反应的平均反应级数为1.4467,活化能为66.79kJ/mol,动力学模型为-(dc_A)/(dt))=5.65×10~5e~(-(66.79)/(RT))c_A~(1.4467)。     

基于Fe_3O_4的化学链制氢动力学特性

针对Fe3O4化学链制氢和CO2分离过程,研究了Fe3O4在CO气氛下还原以及铁在水蒸气下氧化的动力学特性.用Coats-Redfen单升温速率积分法、Ozawa组合升温速率法和lnln恒温分析法对反应机理进行了探讨,并计算了动力学参数.热重数据计算结果表明:在CO和N2体积分数分别为5%和95%时,还原反应属于一级反应,750～900,℃时反应活化能为112,kJ/mol;在CO、CO2和N2体积分数分别为42.9%、14.3%和42.8%时,还原反应可用Jander扩散模型描述,750,～950,℃时反应活化能为49.828,kJ/mol;经Ozawa法验证,加入CO2后的还原反应活化能明显降低.铁与水蒸气的氧化反应接近二维核生长模型,反应活化能较低,为29.633,kJ/mol,且随着温度升高,反应速率常数增大.     

玉米芯水解残渣热解焦ZnCl2活化动力学分析

为优化玉米芯水解残渣低温热解、ZnCl2活化制备活性炭的工艺过程,获取活化过程的优化工艺参数,在热分析仪上对残渣热解焦的ZnCl2活化过程进行了研究。通过对比ZnCl2溶液浸渍前后残渣热解焦的热重特性,分析了ZnCl2活化机理,采用分布活化能模型(DAEM)对浸渍热解焦活化过程进行了动力学分析。结果表明,经ZnCl2浸渍后的残渣热解焦热失重区间集中在450~650℃,且失重峰明显增强,固体残留质量大幅降低。DAEM计算结果表明,浸渍热解焦在活化过程中的活化能分布为190~280 kJ/mol,在E=210 kJ/mol时活化能分布函数达到最大值。     

黑液木质素焦热解动力学分析

在N_2的气氛下,以10℃/min、20℃/min、30℃/min、40℃/min和50℃/min的升温速率分别对黑液木质素焦进行热重实验,研究升温速率对其热解反应的影响。结果表明,黑液木质素焦的热解过程主要分为三个阶段:180～380℃、380～570℃以及570～800℃;TG和DTG曲线随着升温速率增大逐渐向高温侧偏移,高升温速率不利于热解反应进行;采用Coats-Redfern法、Ozawa法和Kissinger法求得活化能分别为93～251 kJ/mol、111～122 kJ/mol和110～134 kJ/mol。     

两种玉米秸秆热解过程动力学模型的比较

介绍了生物质热解的简单一级动力学模型和分布活化能模型,并利用这两种模型分别对玉米秸秆在15、25、30K/min升温速率下的热重分析数据进行了研究。利用简单一级动力学模型计算的活化能数值在7～54kJ/mol之间,指前因子在2.8×10~4～3.3×10~4min~(-1)之间;利用分布式活化能模型计算的活化能数值在65～80kJ/mol之间,指前因子在1.9×10~5～3.0×10~5min~(-1)之间。同时,分析了产生上述差异的原因,并通过研究分布活化能模型的计算结果得出分布活化能模型更能反映生物质热解动力学过程的结论。     

钴铜锂复合金属氧化物热化学储热温度调控特性研究

提出通过掺杂的方法,调控复合金属氧化物的热化学反应温度,试验结果表明钴铜锂三元复合氧化物的还原起始反应温度可从850℃降低到795℃,氧化反应起始温度也可降低35～50℃。XRD和反应动力学分析表明,复合相CoLiO₂的出现使还原反应活化能均值从911 kJ/mol降低到602 kJ/mol,这是反应温度降低的主要原因。经过105个循环后,钴铜锂三元复合氧化物的氧化还原反应循环的比例仍保持在80%以上。     

粉末与颗粒状木质燃料燃烧动力学特性研究

为掌握粉末状与颗粒状木质燃料的动力学特性,选用同一木质成型燃料,通过热重分析仪和管式加热炉系统分别对其粉末状和颗粒状原料进行实验研究。采用双步双等法、等温法等进行动力学拟合推断,求解两者燃烧动力学三因子并进行比较。结果表明:由于燃料内部传热传质性质差异较大,粉末状与颗粒状木质燃料的最概然机理函数并不相同,前者燃烧全过程的燃烧机理基本一致,后者挥发分燃烧阶段与焦炭燃烧阶段的燃烧机理差异较大;粉末与颗粒状活化能值分别为92.33 kJ/mol和71.20 kJ/mol,两者相差21.13 kJ/mol;指前因子值分别为2.55×10~8 s~(-1)和78.55 s~(-1),前者远大于后者,两者相差7个数量级。     

废弃物干酒糟生物质热解特性及动力学研究

酒糟（DG）的组成成分以及在50~900 ℃范围内的热解进行研究。TG/DTG实验结果表明,DG的开始热解温度为137 ℃,热解温度在305 ℃时热解速率最快,为6%/min。傅里叶变换红外光谱（FTIR）数据表明,DG的主要气态产物为CO₂、CH₄、酮、醛、酸和胺。通过分布式活化能模型（DAEM）与无模型积分（Flynn-Wall-Ozawa,FWO）方法对DG的动力学行为分析发现,DG在热解初始阶段活化能为76.49 kJ/mol,平稳阶段活化能为160 kJ/mol。随着热解反应的进行,DG的热解活化能逐渐升高。     

Performance assessment of some ice TES systems

In this paper, a performance assessment of four main types of ice storage techniques for space cooling purposes, namely ice slurry systems, ice-on-coil systems (both internal and external melt), and encapsulated ice systems is conducted. A detailed analysis, coupled with a case study based on the literature data, follows. The ice making techniques are compared on the basis of energy and exergy performance criteria including charging, discharging and storage efficiencies, which make up the ice storage and retrieval process. Losses due to heat leakage and irreversibilities from entropy generation are included. A vapor-compression refrigeration cycle with R134a as the working fluid provides the cooling load, while the analysis is performed in both a full storage and partial storage process, with comparisons between these two. In the case of full storage, the energy efficiencies associated with the charging and discharging processes are well over 98% in all cases, while the exergy efficiencies ranged from 46% to 76% for the charging cycle and 18% to 24% for the discharging cycle. For the partial storage systems, all energy and exergy efficiencies were slightly less than that for full storage, due to the increasing effect wall heat leakage has on the decreased storage volume and load. The results show that energy analyses alone do not provide much useful insight into system behavior, since the vast majority of losses in all processes are a result of entropy generation which results from system irreversibilities.     

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.     

Effect of co-cultivation of Chlamydomonas reinhardtii with Azotobacter chroococcum on hydrogen production

Chlamydomonas reinhardtii cc124 and Azotobacter chroococcum bacteria were co-cultured with a series of volume ratios and under a variety of light densities to determine the optimal culture conditions and to investigate the mechanism by which co-cultivation improves H₂ yield. The results demonstrated that the optimal culture conditions for the highest H₂ production of the combined system were a 1:40 vol ratio of bacterial cultures to algal cultures under 200 μE m^?2 s^?1. Under these conditions, the maximal H₂ yield was 255 μmol mg^?1 Chl, which was approximately 15.9-fold of the control. The reasons for the improvement in H₂ yield included decreased O₂ content, enhanced algal growth, and increased H₂ase activity and starch content of the combined system.     

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.     

Exergetic evaluation of 5 biowastes-to-biofuels routes via gasification

This paper presents the exergy analysis results for the production of several biofuels, i.e., SNG (synthetic natural gas), methanol, Fischer–Tropsch fuels, hydrogen, as well as heat and electricity, from several biowastes generated in the Dutch province of Friesland, selected as one of the typical European regions. Biowastes have been classified in 5 virtual streams according to their ultimate and proximate analysis. All production chains have been modeled in Aspen Plus in order to analyze their technical performance. The common steps for all the production chains are: pre-treatment, gasification, gas cleaning, water–gas-shift reactions, catalytic reactors, final gas separation and upgrading. Optionally a gas turbine and steam turbines are used to produce heat and electricity from unconverted gas and heat removal, respectively. The results show that, in terms of mass conversion, methanol production seems to be the most efficient process for all the biowastes. SNG synthesis is preferred when exergetic efficiency is the objective parameter, but hydrogen process is more efficient when the performance is analyzed by means of the 1st Law of Thermodynamics. The main exergy losses account for the gasification section, except in the electricity and heat production chain, where the combined cycle is less efficient.     

液压系统常见的故障诊断及处理

任何工程机械式液压设备使用时出现故障是不可避免的。但是怎样确定故障的原因及找到好的解决方法，这是使用者最关心的问题。讲述了液压系统常见的故障及其排除方法。     

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.     

Economie d'énergie en trigénération

Trigeneration is defined as the production of three useful forms of energy—heat, cold and power—from a primary source of energy such as natural gas or oil. For instance, trigeneration systems typically produce electrical power via a reciprocating engine or gas turbine and recover a large percentage of the heat energy retained in the lubricating oil, exhaust gas and coolant water systems to maximize the utilization of the primary fuel. The heat produced can be totally or partially used to fuel absorption refrigerators. Therefore, trigeneration systems enjoy an inherently high efficiency and have the potential to significantly reduce the energy-related operation costs of facilities. In this paper, we describe a model of characterization of trigeneration systems trough the condition of primary energy saving and the quality index, compared to the separate production of heat, cold and power. The study highlights the importance of the choice of the separate production reference system on the level of primary energy saving and emissions reduction.     

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.     

Mineralogical characterization of the intraseam layers of Lofoi lignite deposits in Florina basin (western Makedonia,northwest Greece)

The mineralogical composition of intraseam layers from Lofoi lignite deposits (northwest Greece) is the subject of the present study. The samples were examined by means of X-ray diffraction (XRD), thermo-gravimetric (TG/DTG) and differential thermal analysis (DTA), and Fourier transform infrared (FT-IR) spectrometry. The clay minerals prevail in most samples, with illite-muscovite being the dominant phase, and kaolinite and chlorite being the other major clay components. No smectite was found. Quartz and feldspars, dominate in two cases. The studied materials are characterized as clays to clayey sands, showing significant similarities with the intraseam layers of the adjacent Achlada lignite deposits.