木质素热解生物油组成成分与分子尺寸分布特性分析

选用脱碱木质素作为原料,以热裂解气质联用技术(Py-GC/MS)研究木质素在350～600℃下热解产物成分和含量,并利用Joback法、 Lijie法和Tahami法3种基团贡献法计算了生物油各组成成分的临界参数和动力学直径,对木质素热解油产物的分子动力学直径分布特性进行计算.结果显示,愈创木基结构、紫丁香基结构、苯酚类、邻苯二酚类和芳烃类等5种芳香族化合物是350～600℃下木质素热解生物油的主要组成成分,其中愈创木基结构化合物的平均峰面积百分比达到70.7%.随着反应温度从350提高到600℃,分子动力学直径在0.560～0.610 nm区间内的木质素热解油组分含量从14.6%增加至31.3%.木质素热解生物油主要产物的动力学直径在0.560～0.710nm,表明一些孔径尺寸在此范围内的分子筛如SSZ-20、 ZSM-5和Beta可作为木质素裂解制备高品质芳烃燃料的催化剂.     

脱水Ni-Fe类水滑石的制备及其作为环保型催化剂用于生物质糠醛的高选择性缩醛化反应

合成了含硝酸根离子的脱水Ni-Fe类水滑石（Ni-Fe HTLCs）并将其应用于室温下的糠醛缩醛化反应。脱水Ni-Fe HTLCs对糠醛缩醛化反应显示出高选择性并基本实现糠醛的完全转化。作为耐水的路易斯酸和脱水剂,脱水Ni-Fe HTLCs被证明是适用于糠醛缩醛化反应的高效双功能催化剂。通过研究发现,脱除Ni-Fe HTLCs中水分导致颗粒收缩并增强层板间硝酸根离子间的电荷互斥,Ni-Fe HTLCs中弱酸性位点在糠醛缩醛化中发挥重要作用,脱水可改变酸性位点结构并增强其活性。脱水Ni-Fe HTLCs可吸收缩醛化反应中产生的大部分水分,但吸水后Ni-Fe HTLCs的结构并不能完全恢复,这可能是由扩散进入HTLCs层板间的有机分子导致。     

减压蒸馏生物油与乙醇在ZSM-5/MCM-41上共催化裂化

采用减压蒸馏生物油为原料,与无水乙醇2:3(质量比)混合,在固定床中ZSM-5/MCM-41分子筛上共催化裂化,考查了反应温度和质量空速(WHSV)对裂化产物的影响。对ZSM-5/MCM-41进行了NH₃-TPD、BET、N₂吸附-脱附等表征,对裂化气体产物通过气相色谱仪分析,减压蒸馏生物油和精制生物油采用气相色谱-质谱联用仪进行定量分析。结果表明,反应温度500 ℃、WHSV 3.75 h^-1为反应优化工况。此反应条件下,精制生物油酸类物质从减压蒸馏生物油中的25.6%降至反应后的0.1%,效果显著,且精制生物油产率为46.8%,气体产物中CO₂和CO的浓度共9.5%。     

Fe、Mo助剂对Ni基催化剂加氢脱氧性能的影响

制备了一系列NiM/γ-Al<,2>O<,3>(M=Fe,Mo)负载型催化剂,通过BET、TPR、XRD、XPS、H<,2>-TPD和NH<,3>-TPD等对催化剂的物化性质进行了表征.并以乙酸为模型化合物,研究了Fe、Mo助剂对C-C键和C-O键的断裂、加氢脱氧活性和产物选择性的影响.结果表明:Fe、Mo助剂的加入可...     

Bio-oil from Jackfruit Peel Waste

Fossil fuels such as petroleum, charcoal, and natural gas sources are the main energy sources at present, but considering their natural limitation in availability and the fact that they are not renewable, there exists a growing need of developing bio-fuel production. Biomass has received considerable attention as a sustainable feedstock that can replace diminishing fossil fuels for the production of energy, especially for the transportation sector. JackfruitwasteisabundantinIndonesiamake itpotentiallyas one of thegreenrefineryfeedstockforthe manufacture ofbio-fuel.As intermediate of bio-fuel,jackfruitpeelsisprocessed intobio-oil. Pyrolysis, a thermochemical conversion process under oxygen-absent condition is an attractive way to convert biomass into bio- oil.In this study, the pyrolysis experiments were carried out ina fixed-bedreactor at a range of temperature of400-600 °C, heating rate range between 10-50 °C/min, and a range of nitrogen flow between 2-4litre/min. The aims of this work were to explore the effects of pyrolysis conditions and to identify the optimum condition for obtaining the highest bio-oil yield.The effect of nitrogen flow rate and heating rate on the yield of bio-oil were insignificant. The most important parameter in the bio-oil production was the temperature of the pyrolysis process.The yield of bio-oil initially increased with temperature (up to 550 °C) then further increase of temperature resulting in the decreased of bio-oil yield. Results showed that the highest bio-oil yield (52.6%)wasobtainedat 550 °C with nitrogen flow rate of 4L/min and heating rate of 50 °C/min. The thermal degradation of jackfruit peel was also studied using thermogravimetric analysis (TGA). Gas chromatography (GC-MS) was used to identify the organic fraction of bio-oil. The water content in the bio-oil product was determined by volumetric Karl-Fischer titration. The physicochemical properties of bio-oil produced from pyrolysis of jackfruit peels such as gross calorific value, pH, kinematic viscosity, density, sulfur content, ash content, pour point and flash point were determined and compared to ASTM standard of bio-oil (ASTM 7544).     

Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts: Model reaction for upgrading of bio-oil

A series of Cu-Mg-Al hydrotalcites derived oxides with a (Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio (from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 °C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.     

Fractional pyrolysis of Cyanobacteria from water blooms over HZSM-5 for high quality bio-oil production

Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.     

生物质快速热解油水相溶液超声乳化特性

使用生物油水相溶液与0# 柴油乳化,筛选了四种常用乳化剂和一种助乳化剂进行复配乳化实验,考察了复配乳化剂型号、乳化剂用量、超声作用时间对乳化效果的影响。结果表明,六种乳化液超过30d不破乳,与0# 柴油相比,密度和热值相差不大,含水量3%以下,黏度增大约40%,pH值降低一半。因素分析法表明,水相溶液与柴油质量比和不同的水相溶液对乳化效果影响较大。探讨了乳化机理,认为生物油水相溶液中水、醛、酸、酮等极性组分化合物稳定地被乳化剂包裹在W/O型乳化液液滴中,生物油水相溶液中少量的乙酸乙酯、芳香类化合物等则增溶于非离子乳化剂胶束中。热力学分析表明,超声乳化作用比静置作用具有更大的熵增,乳化液更趋于稳定平衡状态。     

煤与生物油的成浆性能研究

利用不同煤种的煤和生物油制备了不同浓度的生物油煤浆,考察了生物油煤浆的成浆浓度、表观黏度、流变特性和稳定性。结果表明,生物油煤浆是具有一定屈服应力的非牛顿流体,其流变特性可用宾汉姆方程来描述;生物油煤浆的屈服应力和表观黏度都随着固体浓度的增加而增大;随着剪切速率的增加,生物油煤浆的表观黏度减小;四种煤中,无烟煤的成浆浓度最高,可达42%,其含碳量高达49%,相当于同种煤制成的74%的水煤浆含量。烟煤次之,褐煤最低;生物油与煤粉之间能够形成絮凝性的大分子网络结构,使得生物油煤浆存在屈服应力并能够保持良好的静态稳定性,4.0~5.0 d天没有软沉淀产生,数月没有硬沉淀产生。     

生物油蒸馏残渣理化性质及热失重研究

利用傅里叶变换红外光谱仪、激光共焦显微拉曼光谱仪和TGA Q500热分析仪对生物油蒸馏残渣及其在不同温度处理后的热解焦炭理化性质进行表征,并对其热失重特性进行分析。结果表明,生物油蒸馏残渣主要是由脂肪族、芳香族和低聚糖类等有机化合物组成;在氮气氛围下热解主要分为三个阶段:30-145℃为小分子物质挥发析出阶段145-550℃为大分子物质裂解和氧化阶段,550-750℃为焦炭产生阶段;热处理过程中各类物质逐步有序热解析出,同时固体产物石墨化程度随着热处理终止温度的升高而升高。