铝–油酸/正庚烷基纳米浆体燃料液滴着火燃烧特性

采用液滴悬挂法研究了正庚烷液滴、油酸/正庚烷混合燃料液滴、含20wt%纳米铝粉的铝–油酸/正庚烷基纳米浆体燃料液滴在不同温度下(600~800℃)的着火燃烧特性。用高速摄像机观测液滴进入管式电阻炉后的着火燃烧过程,使用热电偶记录液滴周围的气相温度变化,同时通过对应的温度曲线计算液滴的着火延迟时间。结果表明,纳米铝粉和油酸的添加均能降低正庚烷液滴的着火延迟时间。随温度升高,正庚烷、油酸/正庚烷混合燃料、铝–油酸/正庚烷基纳米浆体燃料液滴的着火延迟时间显著降低,但变化趋势逐渐趋于平缓。铝–油酸/正庚烷基纳米浆体燃料液滴的着火延迟时间与环境温度满足阿累尼乌斯方程。与纯正庚烷、油酸/正庚烷混合液滴的燃烧过程相比,铝–油酸/正庚烷基浆体燃料液滴的燃烧过程有显著差异,其燃烧经历3个阶段：正庚烷稳定燃烧阶段、正庚烷微爆炸阶段和表面活性剂微爆炸阶段。铝–油酸/正庚烷基浆体燃料液滴燃烧时间延长,火焰熄灭后又复燃,且燃烧过程中发生剧烈的火焰形变和铝颗粒溅射现象,大部分铝以团聚体形式在第三阶段完成氧化还原反应。     

钯基催化剂应用于甲酸电氧化反应的研究进展

甲酸是一种很有前途的化学储氢材料,可作为低温液体燃料电池的直接燃料。钯基催化剂作为直接甲酸燃料电池（DFAFC）阳极材料,对甲酸氧化具有良好的催化活性,能克服一氧化碳的毒化,在甲酸电化学氧化反应中主要按直接途径进行。降低贵金属含量、提高催化活性、提升稳定性是当前钯基催化材料研究领域的主要方向。主要介绍了当前研究中钯催化剂对甲酸电氧化的催化机理,综述了近5 a的钯合金催化剂制备、特殊形貌控制、碳负载对甲酸氧化活性增强的研究,对钯基催化剂的持续开发具有实际应用意义。     

Formic acid oxidation by carbon-supported palladium catalysts in direct formic acid fuel cell

The oxidation of formic acid by the palladium catalysts supported on carbon with high surface area was investigated. Pd/C catalysts were prepared by using the impregnation method. 30 wt% and 50 wt% Pd/C catalysts had a high BET surface area of 123.7 m²/g and 89.9 m²/g, respectively. The fuel cell performance was investigated by changing various parameters such as anode catalyst types, oxidation gases and operating temperature. Pd/C anode catalysts had a significant effect on the direct formic acid fuel cell (DFAFC) performance. DFAFC with Pd/C anode catalyst showed high open circuit potential (OCP) of about 0.84 V and high power density at room temperature. The fuel cell with 50 wt% Pd/C anode catalyst using air as an oxidant showed the maximum power density of 99 mW/cm². On the other hand, a fuel cell with 50 wt% Pd/C anode catalyst using oxygen as an oxidant showed a maximum power density of 163 mW/cm² and the maximum current density of 590 mA/cm² at 60 °C.     

Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters

Biodiesel, defined as the mono-alkyl esters of vegetable oils or animal fats, is an “alternative” diesel fuel that is becoming accepted in a steadily growing number of countries around the world. Since the source of biodiesel varies with the location and other sources such as recycled oils are continuously gaining interest, it is important to possess data on how the various fatty acid profiles of the different sources can influence biodiesel fuel properties. The properties of the various individual fatty esters that comprise biodiesel determine the overall fuel properties of the biodiesel fuel. In turn, the properties of the various fatty esters are determined by the structural features of the fatty acid and the alcohol moieties that comprise a fatty ester. Structural features that influence the physical and fuel properties of a fatty ester molecule are chain length, degree of unsaturation, and branching of the chain. Important fuel properties of biodiesel that are influenced by the fatty acid profile and, in turn, by the structural features of the various fatty esters are cetane number and ultimately exhaust emissions, heat of combustion, cold flow, oxidative stability, viscosity, and lubricity.     

Highly effective anode structure in a direct formic acid fuel cell

We report the mass transport characteristics of formic acid and performance enhancement in a direct formic acid fuel cell in terms of the property of anode components. The effect of hydrophobicity of anode diffusion media as well as catalyst layer was investigated applying different cell temperature and fuel concentration. The operation over 80 °C and concentrated formic acid is of great advantage to the enhancement of catalytic activity and better water management. On the other hand, the conductivity of formic acid decreases by means of the formation of more complex chains of formic acid and the fuel cell resistance increases by membrane dehydration effect due to the hygroscopic property of formic acid, resulting in overall decrease of cell performance and long-term stability. Optimizing operating conditions, the use of 60% PtRu/C with only 1 mg/cm² on plain carbon paper can be one of the good choice to achieve both sustainable power performance and higher utilization of anode catalysts keeping cell resistance.     

可资源化烷基化废酸裂解装置若干问题分析与探讨

介绍了烷基化废酸裂解工艺过程。探讨了实际生产过程中裂解温度、助燃空气温度、燃料气用量、硫磺用量、空气过剩量等烷基化废酸裂解装置的各种影响因素。重点提出了降低燃料气能耗以使装置变亏为盈的措施。     

Performance of the direct formic acid fuel cell with electrochemically modified palladium-antimony anode catalyst

Previous work has shown that palladium catalysts are quite active for formic acid electrooxidation, but the catalysts need to be periodically regenerated to remove a CO impurity from the surface. The objective of this paper is to determine whether antimony additions could suppress the CO formation under fuel cell conditions. We find that antimony doubles the rate of reaction in an electrochemical cell, but the increase is less in real fuel cell conditions. The current that is produced at 0.6 V is approximately 14% greater for the fuel cell containing antimony additions than the palladium anode catalyst. In a constant-current test, we find that the fuel cell assembled with palladium-antimony anode catalyst produces 18% more voltage than the palladium anode catalyst after 9 h of operation. These results show that the antimony additions that significantly improve oxidation in the electrochemical cell have a much lesser impact in the formic acid fuel cell - they do not suppress CO formation in the fuel cell as anticipated.     

Effects of fatty acid derivatives on the ignition quality and cold flow of diesel fuel

The biodiesel that is considered as a possible substitute or extender of conventional automotive diesel fuel is commonly composed of fatty acid methyl esters that are prepared from the glycerides in vegetable oils by transesterification with methanol. This form of biodiesel is compatible with diesel fuel but offers no improvement in its ignition quality. This work describes the results of a series of experiments aimed at assessing other common fatty acid derivatives that could provide the desired biofuel component and, at the same time, improve the performance of the fuel. It was found that tertiary fatty amines and amides are significantly more effective than methyl esters in enhancing the ignition quality of the finished diesel fuel without having any negative effect on its cold flow properties.     

Mo oxide modified catalysts for direct methanol, formaldehyde and formic acid fuel cells

Pt black and PtRu black fuel cell anodes have been modified with Mo oxide and evaluated in direct methanol, formaldehyde and formic acid fuel cells. Mo oxide deposition by reductive electrodeposition from sodium molybdate or by spraying of the fuel cell anode with aqueous sodium molybdate resulted in similar performance gains in formaldehyde cells. At current densities below ca. 20 mA cm⁻², cell voltages were 350–450 mV higher when the Pt catalyst was modified with Mo oxide, but these performance gains decreased sharply at higher current densities. For PtRu, voltage gains of up to 125 mV were observed. Modification of Pt and PtRu back catalysts with Mo oxide also significantly improved their activities in direct formic acid cells, but performances in direct methanol fuel cells were decreased.     

Denicking of fatty acid pitch

Unsaturated fatty acids are usually hydrogenated with a nickel catalyst. As a side reaction, nickel dissolves in the fatty acids and forms nickel soaps. On refining the crude fatty acid feedstock by distillation, these nickel soaps are enriched in the bottom fraction (pitch) to a concentration range of 2,500–5,500 ppm. With a heat value comparable to heavy fuel oil, the pitch has been used as fuel. However, due to new environmental restrictions, the nickel concentration must be considerably reduced to limit gas emission of nickel. In this study, solvent extraction was investigated as a separation method for denickling of this valuable oleochemical by-product. At a temperature of 80°C, the nickel content in the pitch was reduced from 2,900 ppm to 4 ppm in three extraction steps by means of 1 wt% citric acid in water. Based on experimental results, a preliminary process flowsheet is presented consisting of extraction, stripping, acid washing and electrolysis. An economic analysis, performed on the extraction process and a process based on direct combustion followed by electrostatic precipitation revealed that direct combustion is economically more advantageous. However, the compatibility of the extraction alternative can be considerably improved by process optimization. The type and concentration of the stripping and acid washing agents, phase ratios, temperature, ionic strength and the equilibrium pH of the aqueous and acid phases are important process parameters that should be considered in the optimization process.     

新型换热表面硫酸腐蚀特性的数值预测

低温腐蚀是造成换热设备失效并降低其经济性的重要原因。基于汽液平衡理论和多组分扩散影响数值模拟了不同换热管管壁表面及翅片表面酸露点温度和酸蒸气、水蒸气冷凝沉积速率等影响低温腐蚀的相关因素,数值预测了换热表面局部酸露点温度,为换热器精细设计提供指导。结果表明,燃料类型、飞灰颗粒和翅片结构均会对换热表面酸露点温度造成不同程度影响。燃料类型决定烟气成分和燃烧温度,对酸露点温度影响较大;烟气中飞灰颗粒的存在会降低酸露点温度;翅片结构能够改变周围烟气速度,影响酸露点温度和壁面上酸蒸气、水蒸气冷凝沉积速率。基于以上数值研究提出丁胞和矩形纵向涡复合H型翅片结构可降低壁面上烟气酸露点温度,降低酸蒸气、水蒸气冷凝沉积速率。     

以单体酸为原料制备生物柴油

研究了以单体酸为原料制备生物柴油的方法,反应以对甲苯磺酸为催化剂,单体酸与甲醇进行酯化反应获得脂肪酸甲酯。分别考察了酯化反应条件如甲醇与脂肪酸的摩尔比、反应时间、催化剂浓度以及反应温度对酯化率的影响。通过正交实验得到最佳酯化反应参数：醇酸摩尔比3∶1,反应时间3 h,对甲苯磺酸用量6%,反应温度60 ℃,该条件下单体酸酯化率达98.25%。实验制得的单体酸甲酯生物柴油的主要性能指标符合ASTM质量标准,并与0^#柴油性质接近。     

生物质生产乙酰丙酸研究进展

乙酰丙酸具有高反应活性和广泛的用途,是重要的平台化合物,可由生物质转化而来。本文综述了生物质生产乙酰丙酸的研究进展,包括催化方法和纯化方法。     

Phosphoric acid doped polybenzimidazole membranes: Physiochemical characterization and fuel cell applications

A polymer electrolyte membrane fuel cell operational at temperatures around 150–200 °C is desirable for fast electrode kinetics and high tolerance to fuel impurities. For this purpose polybenzimidazole (PBI) membranes have been prepared and H₃PO₄-doped in a doping range from 300 to 1600 mol %. Physiochemical properties of the membrane electrolyte have been investigated by measurements of water uptake, acid doping level, electric conductivity, mechanical strength and water drag coefficient. Electrical conductivity is found to be insensitive to humidity but dependent on the acid doping level. At 160 °C a conductivity as high as 0.13 S cm^–1 is obtained for membranes of high doping levels. Mechanical strength measurements show, however, that a high acid doping level results in poor mechanical properties. At operational temperatures up to 190 °C, fuel cells based on this polymer membrane have been tested with both hydrogen and hydrogen containing carbon monoxide.     

Characterization of gas flow configurations for phosphoric acid fuel cells

The cell performance and polarization distribution in the horizontal plane of a phosphoric acid fuel cell (PAFC) were studied for thirteen different types of gas flow. In all cases, the potentials of the anode and cathode in the fuel outlet area shifted to positive directions. At 90% utilization of fuel, the potential shift and the cell voltage changed significantly from one type to another. Experimental results show that the cell voltage increased, and the potential shift decreased in the following order; CROSS-FLOW < RETURN-FLOW = CO-FLOW < COUNTER-FLOW < type E2. The extent of the change between various types depended on the following three conditions. (1) The fuel gas has an opportunity to be used twice in the horizontal plane of a cell. (2) The fuel gas flow is in parallel with the air flow. (3) The fuel gas flow is opposite to the air flow. These are requirements for obtaining good and stable performance of a fuel cell. The CROSS-FLOW case has none of these three conditions, the RETURN-FLOW case has the first condition, the CO-FLOW case has the second, the COUNTER-FLOW case has the second and the third conditions, and the best gas flow type (type E2) has all.     

10 kt/a丁二醇废硫酸裂解制酸工艺设计

介绍了炔醛法BDO生产装置配套的10 kt/a废硫酸裂解制酸装置的工艺流程、工艺参数和主要设备,并对裂解温度、燃料气选择、废硫酸组分、裂解炉炉气剩余氧气含量等制酸工艺的影响因素进行了分析,提出了设计优化思路.该BDO废硫酸裂解制酸装置自投入运行以来,运行情况良好,BDO废硫酸处理量达到1250 kg/h,从根本上解决了...     

Effect of calixpyrrole on electrochemical properties of Pt electrocatalyst in phosphoric acid electrolyte

In high-temperature proton exchange membrane fuel cells and phosphoric acid fuel cells, concentrated phosphoric acid is used as a proton-conducting medium. However, the use of phosphoric acid causes an adsorption problem onto Pt catalyst, which is known to impede the oxygen reduction reaction. To solve the problem, calixpyrrole is introduced as an electrode additive to block the adsorption of phosphate ion onto Pt catalyst. The introduction of calixpyrrole which can strongly interact with phosphate ion results in the enlargement of the available surface area of Pt catalyst and, accordingly, the enhancement of catalyst utilization in electrode. Among calix[n]pyrrole class, calix[4]pyrrole is synthesized and used as the electrode additive in this study.     

Heat transfer in a phosphoric acid fuel cell stack

The electricity production in PAFC (Phosphoric Acid Fuel Cell) is accompanied by approximately equal amount of heat generation. For the best performance and efficient operation of the fuel cell stack, temperature distribution in the fuel cell stack should be controlled. Because the temperature gradient, both in the direction of stacking and in the cell plate, affects the cell performance, endurance, eletrolyte loss, and corrosion. In this study, a 30-plate phosphoric acid fuel cell stack was analyzed and modelled by using electrochemical equations and heat and mass transfer equations. To obtain more realistic profiles, local values of temperature and current density were used in the calculation. Obtained results agreed well with experimentally measured values : the temperature deviation from the measured values was less than 1.5°C.     

Electrolytes for methanol-air fuel cells. I. The performance of methanol electro-oxidation catalysts in sulphuric acid and phosphoric acid electrolytes

Phosphoric acid and sulphuric acid have been compared as potential electrolytes for methanol-air fuel cells. The performances of typical electro-oxidation catalysts were measured in both electrolytes over a range of concentrations. With all catalysts the activity falls with increasing acid concentration. While this is to some extent due to the decrease in water activity at higher concentrations it seems that with both acids there is significant poisoning of the catalyst. The results can be explained for both electrolytes by assuming that adsorption of undissociated acid poisons the catalyst surfaces and that the reaction rate on the poisoned surfaces is proportional to the water activity.     

杂多酸催化剂催化氧化脱硫研究进展

介绍了杂多酸催化剂在燃料油氧化脱硫中的应用研究进展。详细叙述了过渡金属、碱金属和稀土金属杂多酸催化剂、杂多酸季铵盐催化剂、杂多酸离子液体催化剂和以碳材料、二氧化钛、二氧化硅、高分子材料等为载体的负载型杂多酸催化剂,阐述了各种杂多酸催化剂的特点及脱硫效果,指出综合应用杂多酸催化剂特性开发活性高、耗氧少、重复使用性强的优良新型杂多酸催化剂是催化氧化深度脱硫的重要研究方向。