Production and characterisation of bio-oil from Gold Mohar (Delonix regia) seed through pyrolysis process

Fast pyrolysis of the crushed Delonix regia seed was carried out in a semi-batch reactor at a temperature ranging from 400 to 650°C with an objective to produce bio-oil. The effect of temperature to obtain an optimum condition for maximum bio-oil yield and the composition of pyrolysis product were investigated. The maximum bio-oil yield was found to be 48?wt% at pyrolysis temperature of 600°C. The chemical composition of bio-oil obtained at optimum condition was analysed using Fourier-transformed infrared spectroscopy and Gas chromatography–mass spectrometry. The chemical analysis of the biofuel showed the presence of hydrocarbons in major, aldehydes, ketones, amides, nitriles, etc. The composition and fuel characteristics of the pyrolysis oil obtained in this work show that it may potentially be used as a renewable fuel and chemical feedstock.     

Use of heavy fraction of bio-oil as fuel for hydrogen production in iron-based chemical looping process

Chemical looping hydrogen (CLH) process with renewable energy sources as fuel shows the potential of producing pure hydrogen with inherent capture of CO₂ in a low-cost and sustainable way. The heavy fraction (HF) of bio-oil, derived from the fast pyrolysis of biomass and characterized as an energy carrier with difficulty in upgrading itself to bio-fuel or chemicals, was used in this study to generate H₂. Four low-cost iron-based oxygen carriers including an ilmenite and three iron ores were initially evaluated with respect to their reducibility and the ability to minimize carbon or iron carbide (Fe₃C) formation in a thermogravimetric analyzer (TGA). The reactivity and cyclic performance of the selected best candidate was then assessed in a laboratory scale fixed-bed reactor with HF bio-oil as fuel. The screening test in TGA showed that ilmenite was superior over the three iron ores in terms of promoting CO conversion and minimizing carbon or Fe₃C formation. Ilmenite could maintain its increasing reducibility with the increase of surrounding CO concentration, in contrast with the iron ores that were deactivated seriously by the formed carbon or Fe₃C. Subsequent CLH test with ilmenite and HF bio-oil showed that the reducibility and H₂ production capacity of ilmenite were strongly dependent on the operating temperature. The steam oxidation step at 950 °C yielded H₂ concentration and hydrogen yield exceeding all of those observed at the other investigated temperatures because of the deepest reduction degree of ilmenite at 950 °C. The decrease in the reducibility and H₂ production capacity of ilmenite in the cyclic test could be ascribed to the poorer physical structure of ilmenite with cycles.     

Correlation for estimation of the chemical availability (exergy) from ultimate analysis of pyrolytic oils obtained from fast pyrolysis of biomass

The purpose of this study is to evaluate the chemical exergy (E^CH) of liquid products obtained from fast pyrolysis of biomass. I have calculated the chemical exergy values from a formula in literature and have developed a formula for estimating the chemical exergy of biomass from the higher heating value and their ultimate analysis values. The mean differences between these values range from –0.391% to 0.460%. The formula developed for estimating the chemical exergy of biomass from the higher heating value and their ultimate analyses had a correlation coefficient (R² = 0.9999), and the prediction of this formula is good. The goal is to identify desirable attributes that may serve as the basis for decision-making for future biofuel options. Studies on the pyrolytic oils showed that the oils obtained from chestnut cupulae and maple fruit can be used as a renewable fuel and chemical feedstock.     

市政污泥在超临界甲醇条件下酯化制油研究

利用自行设计的反应釜研究了市政污泥在超临界甲醇条件下的油化行为。主要考察了温度、停留时间、污泥与甲醇的配比、催化剂对污泥油化过程的影响,以期找到最佳反应条件。结果表明:当控制温度在360℃、停留时间为80 min时,制得的生物油产量最高,可达44.7%。当干污泥量为20 g时,污泥与甲醇的固液比越大,其产油率越高。加入催化剂能有效促进污泥油化过程,以碱性催化剂KOH的促进效果最明显。     

生物油非催化热转化过程中受热结焦特性研究进展

生物油在受热条件下极易结焦,结焦是影响生物油规模化利用的重要因素之一,因此深入理解生物油受热结焦特性是实现生物油高效热转化利用的基础。本文从生物油热解过程的关键反应参数（温度、升温速率、气氛、压力、灰分）、生物油化学成分、生物油有机组分间交互作用、自由基反应特性等方面综述了生物油受热结焦特性相关研究进展,总结了反应参数对生物油热解结焦反应网络的影响,梳理了生物油各特征组分单独热解结焦及特征组分间交互作用对结焦特性的影响机制,并基于生物油结焦机理和焦炭的物化特性,总结了通过定向调控生物油结焦反应过程,将焦炭作为燃料和炭材料的潜在利用途径。最后,指出了明晰生物油受热结焦机理还需从生物油组分间交互作用机制和自由基反应机理的角度进一步探究。本文为实现生物油高效热转化利用提供了理论参考和借鉴。     

固定床生物油气化反应数学模拟

生物油气化对提高生物质能利用和保护环境具有重要意义。生物油气化选择乙酸、丙酮、丙三醇、苯酚、糠醛组成的混合物作为生物油模型物,在固定床圆柱形管式反应器进行气化模拟,用吉布斯自由能最小化法对其水蒸气催化重整制氢过程进行热力学分析。应用热动力学方程和质量平衡原理推算反应器模型,估算了反应热力学参数,通过Aspen Plus中的Gibbs反应器模拟生物油在不同温度下产物的平衡组成,计算出化学平衡体系的摩尔定压热容,利用Runge-Kutta法结合Matlab软件进行求解得出催化剂床层气化转化率;考察了反应温度对平衡时气体产物的影响。在固定床圆柱形管式反应器进行气化模拟实验,得出不同反应温度时反应产物气体产率和生物油气化反应较佳反应温度,通过比较得出实验结果与模拟计算值较一致。     

利用随机近似热探针方法的生物油热物性研究

提出了基于蒙特卡洛随机近似的热探针方法,该方法以热探针微分方程的精确解为基础,可同时进行热导率、比热容等热物性的测量.对水、甘油、硅油、酒精的测量结果显示,该方法热导率测量的最大相对误差仅为0.7%,比热容相对误差绝对值的平均值为2.6%,最大相对误差为3.8%.利用该方法对快速裂解所生产的生物油的热导率和比热容进行了测量,给出了温度、有机助剂对生物油热导率和比热容的影响,并对结果进行了分析.     

Hydroprocessing of Bio-Oils and Oxygenates to Hydrocarbons. Understanding the Reaction Routes

To produce diesel fuel from renewable organic material such as vegetable oils, it has for a number of years been known that triglycerides can be hydrogenated into linear alkanes in a refinery hydrotreating unit over conventional sulfided hydrodesulfurization catalysts. A number of new reactions occur in the hydrotreater, when a biological component is introduced, and experiments were conducted to obtain a more detailed understanding of these mechanisms. The reaction pathways were studied both in model compound tests and in real feed tests with mixtures of straight-run gas oil and rapeseed oil. In both sets of experiments, the hydrogenation of the oxygen containing compounds was observed to proceed either via a hydrodeoxygenation (HDO) route or via a decarboxylation route. The detailed pathway of the HDO route was further illuminated by studying the hydroprocessing of methyl laurate into n-dodecane. The observed reaction intermediates did not support a simple stepwise hydrogenation of the aldehyde formed after hydrogenation of the connecting oxygen in the ester. Instead, it is proposed that the aldehyde formed is enolized before further hydrogenation. The existence of an enol intermediate was further corroborated by the observation that a ketone lacking α-hydrogen (that cannot be directly enolized) had a much lower reactivity than a corresponding ketone with α-hydrogen. In real feed tests, the complete conversion of rapeseed oil into linear alkanes at mild hydrotreating conditions was demonstrated. From the gas and liquid yields, the relative rates of HDO and decarboxylation were calculated in good agreement with the observed distribution of the n-C₁₇/n-C₁₈ and n-C₂₁/n-C₂₂ formed. The hydrogen consumption associated with each route is deduced, and it was shown that hydrogen consumed in the water-gas-shift and methanization reactions may add significant hydrogen consumption to the decarboxylation route. The products formed exhibited high cetane values and low densities. The challenges of introducing triglycerides in conventional hydrotreating units are discussed. It is concluded that hydrotreating offers a robust and flexible process for converting a wide variety of alternative feedstocks into a green diesel fuel that is directly compatible with existing fuel infrastructure and engine technology.     

HZSM-5/MCM-41对小球藻催化热解的影响

以HZSM-5/MCM-41为催化剂,在管式炉内对小球藻进行了催化热解研究。考察了HZSM-5/MCM-41复合催化剂中MCM-41的添加比例对小球藻热解产物影响,并采用GC-MS和元素分析对所制取生物油进行了表征。结果表明:与HZSM-5催化剂相比,90%HZSM-5与10%MCM-41混合后生物油中3,7,11,15-四甲基-2-十六烯的选择性最好。羧酸类和含氮物质分别降低12.85%、43.97%,脂肪烃和芳烃的质量分数之和达到50.34%,且不存在硬脂酰胺和油酸腈等物质。根据元素分析可知,10%的MCM-41的引入使生物油含氧量降低23.52%,O/C原子比明显降低,H/C原子比得到提高,热值达到32.995 MJ·k-1,且油品组成与生物柴油接近。热重实验表明,分子筛催化剂失活主要是由于积炭的产生,HZSM-5/MCM-41具有良好的稳定性。随着催化剂用量的增加,生物油热值增加,同时含水量也增多,HZSM-5/MCM-41与小球藻质量比例为1:5时,生物油产率最高。     

生物油低温加氢脱氧的研究

采用Pt系负载型催化剂,在高压反应釜内进行了生物质快速裂解油(生物油)的低温加氢脱氧研究。考察了催化剂的种类(Pt/C和Pt/γ-Al_2O_3)、反应温度(180～240℃)和反应时间(20～80 min)对生物油加氢脱氧效果及产物收率的影响。实验结果表明,采用Pt/γ-Al_2O_3催化剂,在优化的反应条件(即反应温度220℃、反应时间60 min)下,生物油的脱氧率可达50%以上。产物分析结果表明,由于氧的脱除,提质油热值增加到33.45 MJ/kg,而羧基的转化使其pH提高到3.25;且产物实现了油水分离。该方法的特点是焦炭收率低(低于2%),因此催化剂的寿命长。