杜氏盐藻在亚/超临界水中液化制生物油

在高温高压反应釜中进行亚/超临界水直接液化杜氏盐藻制生物油过程的研究。对杜氏盐藻的藻粉和藻渣两种原料的主要成分进行了分析。考察了反应温度、反应时间、催化剂、料液比、反应压力等对盐藻粉和盐藻渣液化行为的影响。在此基础上通过正交试验表明:反应温度360℃,反应时间60min,催化剂K_2CO_3加入量2.5%是适合的条件。在上述条件下微藻在超临界水中的液化率为89.37%,产油率为29.04%。通过FT-IR、GC-MS等手段分析了生物油的特性和组分,表明生物油是组成复杂的酸性有机混合物。     

壳类生物质与煤共液化的研究

以核桃壳和褐煤为研究对象,系统考察了核桃壳/煤质量配比、原料/四氢萘溶剂质量比、反应温度、反应时间及催化剂对共液化效果的影响。结果表明,当核桃壳/煤质量配比为50/50,原料/四氢萘溶剂比例为1/10,反应温度300℃和反应时间为31min时,可获得较好的共液化效果。碳酸钠与硫铁催化剂对核桃壳与煤的共液化均具有明显的催化作用,转化率和油产率可获大幅提高。核桃壳与煤的共液化存在明显协同作用,且这种作用在催化剂条件下更明显。     

正交试验探讨脂肪酸超临界酯化制备生物柴油

探讨脂肪酸在超临界甲醇中酯化反应的规律及最佳条件。以橡胶籽油脂肪酸为原料,在间歇式高温高压反应釜中通过酯化反应制备生物柴油,分别考察了酯化反应条件如反应温度、反应时间、甲醇与脂肪酸的体积比对酯化率的影响。应用正交试验方法得出酯化反应的较适宜条件为：反应温度290℃,反应时间30min,甲醇与脂肪酸的体积比为4：1。在此反应条件下转化率可达99．2％。橡胶籽油生物柴油成分主要有亚油酸甲酯、油酸甲酯、亚麻酸甲酯,还有少量的硬脂酸甲酯、棕榈酸甲酯。     

稻草在离子液体([Emim]Br)中的热解研究

为研究离子液体对植物纤维素热解行为的影响,以稻草为原料,在离子液体溴化3-甲基-1-乙基咪唑([Emim]Br)中进行热解反应,考察了反应温度、离子液体与稻草的质量比及反应时间对生物油产率的影响,得到热解较佳工艺条件:热解反应温度为230℃,离子液体与稻草的质量比为2∶1,热解反应时间为45 min,生物油得率达到38.1%。对热解得到的生物油进行GC-MS分析,呋喃类和苯酚类物质的含量较高,分别占17.17%和21.98%。     

花椒籽油生物柴油制备工艺研究

以花椒籽油为原料,对KOH催化其与甲醇发生酯交换反应制备生物柴油进行研究.采用物理萃取法降低花椒籽油中游离脂肪酸的含量,三次萃取后酸值达到2 mgKOH/g以下.研究了花椒籽油和甲醇在氢氧化钾催化下的酯交换反应.进行了不同醇油摩尔比、催化剂用量、反应时间、反应温度等反应条件下对产率的影响,得到最佳反应条件为醇油物质的量之比为12∶1,催化剂添加量为油脂质量的1.2％,反应温度为60 ～65℃,反应时间为45 min.     

塑料和木屑的共液化以及催化液化实验研究

在温度为613～693K、压力为20～30MPa的条件下,以去离子水为溶剂在1L间歇式高压反应釜中对塑料和木屑进行共液化研究,实验考察了反应时间、溶剂填充率、温度、催化剂对液化行为的影响。结果表明:木屑的加入能降低塑料液化对高温的要求,共液化能获得较高的液化油收率。在未添加催化剂的情况下,共液化反应在653K的温度下油收率达最大值24.0%,转化率达83.5%,油的热值为44.6MJ/kg。催化剂的使用能降低反应所需要的温度并获得较高的液化油收率以及转化率。研究发现,HZSM-5分子筛的催化作用最为明显。     

杨木屑多组分溶剂液化工艺的研究

利用热化学液化方法对生物质杨木屑液化工艺进行研究,以液化温度、液化时间、催化剂量为影响因素,液化率为指标,采用正交试验优化木屑液化的工艺条件。在此基础上,利用最佳工艺条件下制备的液化油替代聚醚多元醇制备聚氨酯发泡材料。结果表明:3个因素的影响大小关系为:催化剂量液化时间液化温度。最佳条件为液化剂聚乙二醇∶乙二醇∶丙三醇为3∶1∶1,固液比1∶5,催化剂量为液体总量的3%,反应时间60min,反应温度160℃,杨木屑液化率为93.8%。液化产物的酸值范围43.48~67.32 mg KOH/g,羟值范围155.68~235.62 mg KOH/g。利用最佳工艺条件下所得杨木屑液化油替代聚醚多元醇制备聚氨酯发泡材料的性能较好。     

猪体水热液化工艺参数优化及生物油特性分析

以猪体为原料,以高位热值、C元素回收率、N元素残留率作为生物油质量指标,采用响应面法研究反应温度（220~300 ℃）、反应时间（40~80 min）、固含量（10%~30%）对猪体水热转化生物油产率与质量的影响。研究结果表明：反应条件均会影响水热反应的进行且温度影响最显著,分别在不同反应条件下得到单一指标最优的生物油;生物油的最大产率为76.94%（278 ℃、64 min、29%固含量）,最大HHV值为38.63 MJ/kg（290 ℃、47 min、30%固含量）,最大C元素回收率为93.16%（260 ℃、60 min、10%固含量）,最低N元素残留率为15.52%（220 ℃、40 min、12%固含量）。生物油的元素分析结果表明水热液化可有效降低生物油中N、O元素含量,提高生物油品质。傅里叶变换红外光谱分析与热重分析结果表明,生物油的化学成分复杂且以分子量较大、碳链较长的有机物为主。     

利用微藻热化学液化制备生物油的研究进展

微藻是制备生物质液体燃料的良好材料,利用微藻热化学液化制备生物油在环保和能源供应方向都具有非常重要的意义。目前国内外研究者主要采用快速热解液化和直接液化两种热化学转化技术进行以微藻为原料制备生物油的研究。快速热解生产过程在常压下进行,工艺简单、成本低、反应迅速、燃料油收率高、装置容易大型化,是目前最具开发潜力的生物质液化技术之一。但快速热解需要对原料进行干燥和粉碎等预处理,微藻含水率极高,会消耗大量的能量,使快速热解技术在以微藻为原料制备生物油方面受到限制。直接液化技术反应温度较快速热解低,原料无需烘干和粉碎等高耗能预处理过程,且能产生更优质的生物油,将会是微藻热化学液化制备生物油发展的主流方向,极具工业化前景。国内外研究者还尝试利用超临界液化、共液化、热化学催化液化、微波裂解液化等多种新型液化工艺进行微藻热化学液化制备生物油的实验研究。今后的主要研究方向应是将热化学液化原理研究、生产工艺开发、反应器研发、反应条件优化、产品精制等有机地结合起来,进行深入研究。同时应努力节约成本、降低能耗。     

硫酸氢钠催化生物柴油合成反应的研究

以固体酸硫酸氢钠(NaHSO4·H20)为催化剂,以菜籽油和甲醇为反应物进行酯交换反应制备脂肪酸甲酯(生物柴油).采用正交实验考察了各因素对生物柴油产率的影响,得出最佳反应条件:反应温度为90℃,反应时间为12h,醇油物质的量比为40:1,催化剂用量为菜籽油质量的6%.极差顺序为温度、反应时间、醇油物质的量比、催化剂用量.     

Hydrothermal liquefaction of macroalgae: Influence of zeolites based catalyst on products

Hydrothermal liquefaction (HTL) of Ulva prolifera macroalgae (UP) was carried out in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different weight percentage (10–20 wt%) at 260–300 °C for 15–45 min. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite, and Mordenite in the conversion of Ulva prolifera showed that is affected by properties of zeolites. Maximum bio-oil yield for non-catalytic liquefaction was 16.6 wt% at 280 °C for 15 min. The bio-oil yield increased to 29.3 wt% with ZSM-5 catalyst (15.0 wt%) at 280 °C. The chemical components and functional groups present in the bio-oils are identified by GC-MS, FT-IR, ¹H-NMR, and elemental analysis techniques. Higher heating value (HHV) of bio-oil (32.2–34.8 MJ/kg) obtained when catalyst was used compared to the non-catalytic reaction (21.2 MJ/kg). The higher de-oxygenation occurred in the case of ZSM-5 catalytic liquefaction reaction compared to the other catalyst such as Y-zeolite and mordenite. The maximum percentage of the aromatic proton was observed in bio-oil of ZSM-5 (29.7%) catalyzed reaction and minimum (1.4%) was observed in the non-catalyst reaction bio-oil. The use of zeolites catalyst during the liquefaction, the oxygen content in the bio-oil reduced to 17.7%. Aqueous phase analysis exposed that presence of valuables nutrients.     

Liquefaction of palm kernel shell in sub- and supercritical water for bio-oil production

The heavy palm oil industry in Malaysia has generated various oil palm biomass residues. These residues can be converted into liquids (bio-oil) for replacing fossil-based fuels and chemicals. Studies on the conversion of these residues to bio-oil via pyrolysis technology are widely available in the literature. However, thermochemical liquefaction of oil palm biomass for bio-oil production is rarely studied and reported. In this study, palm kernel shell (PKS) was hydrothermally liquefied under subcritical and supercritical conditions to produce bio-oil. Effects of reaction temperature, pressure and biomass-to-water ratio on the characteristics of bio-oil were investigated. The bio-oils were analyzed for their chemical compositions (by GC–MS and FT-IR) and higher heating values (HHV). It was found that phenolic compounds were the main constituents of bio-oils derived from PKS for all reaction conditions investigated. Based on the chemical composition of the bio-oil, a general reaction pathway of hydrothermal liquefaction of PKS was postulated. The HHV of the bio-oils ranged from 10.5 to 16.1 MJ/kg, which were comparable to the findings reported in the literature.     

Improving the quality of fast pyrolysis bio-oil by reduced pressure distillation

In the present study, reduced pressure distillation was performed to obtain distilled bio-oil from fast pyrolysis bio-oil. The experiments were completed at temperature 80 °C with a residual pressure of 15 mmHg. The distilled bio-oil yields of 61 wt% from reduced pressure distillation of fast pyrolysis bio-oil were obtained. The oxygen contents of the distilled bio-oil is 9.2 wt% and the distilled bio-oil has lower content of oxygen than the fast pyrolysis bio-oil. For this reason, compared with the fast pyrolysis bio-oil, the distilled bio-oil has higher heating value, lower corrosivity and better stability. The heating value of distilled bio-oil is 34.2 MJ/kg, which is about 2 times of that of fast pyrolysis bio-oil. It is found that the distilled bio-oil stored at 60 °C results in a weight loss of about 0.3% for mild steel and the distilled bio-oil’s viscosity hardly increases during storage. These properties of distilled bio-oil make it more suitable for fuel oil use or as a source of chemicals than fast pyrolysis bio-oil.     

Utilization possibilities of Albizia amara as a source of biomass energy for bio-oil in pyrolysis process

Pyrolysis is one of the potential routes to harmless energy and useful chemicals from biomass. The pyrolysis of Albizia amara was studied for determining the main characteristics and quantities of liquid products. Particular investigated process variables were temperature from 350 to 550°C, particle size from 0.6 to 1.25 mm, and heating rate from 10 to 30 °C/min. The maximum bio-oil yield of 48.5 wt% at the pyrolysis temperature of 450°C was obtained at the particle size of 1.0 mm and at the heating rate of 30 °C/min. The bio-oil product was analyzed for physical, elemental, and chemical composition using Fourier transform infrared spectroscopy and gas chromatography spectroscopy. The bio-oil contains mostly phenols, alkanes, alkenes, saturated fatty acids and their derivatives. According to the experimental results, the pyrolysis bio-oil can be used as low-grade fuel having heating value of 18.63 MJ/kg and feedstock for chemical industries.     

微藻生物质可再生能源的开发利用

藻类具有生物量大、生长周期短、易培养以及含有较高的脂类等特点，是制备生物质液体燃料的良好材料。微藻热解所得的生物质燃油热值高达33MJ/kg，是木材或农作物秸秆的1．6倍。通过调节微藻的培养条件和脂类含量，可获得高品质、高热值的生物质燃油。     

Bio-oil production via fast pyrolysis of shrub residues in a fluidized-bed reactor

In this article, the shrub residues as raw materials were produced to fast pyrolysis oil (called bio-oil) in a 5-kg/h fluidized-bed reactor. The optimum conditions were obtained at 500°C, flow rate of fluidizing gas of 4 m³/h, and feed rate of 3 kg/h. The liquid yield was up to 60% at the optimum conditions. The bio-oil was easy to divide into two phases: oil phase and aqueous phase. The high heat value of the oil phase was up to 18.55 MJ/kg, but the high heat value of the aqueous phase was only 0.72 MJ/kg. The oil phase and aqueous phase both have lower pH values. The oxygen content was up to 50%, while the sulfur and nitrogen content were very low. Owing to the higher oxygen content and lower pH value in liquid products, it must be further upgraded to bio-oil before application.     

Sub- and supercritical liquefaction of rice straw in the presence of ethanol–water and 2-propanol–water mixture

The critical liquefaction of rice straw to bio-oil with sub- and supercritical mixtures (ethanol–water and 2-propanol–water mixture) was studied in a 1000 ml autoclave at 533–623 K, 6–18 MPa, respectively. The results showed that the maximum yield of bio-oil was 39.7% for the 2-propanol:water volume ratio of 5:5 at 573 K, while the higher heating value (HHV) of bio-oil increased with the reaction temperature and solvent volume ratio. The formation of low-boiling-point materials was reduced by a mixture. Using a mixture could inhibit the formation of residue and then promote the conversion of rice straw with the ratio of 1:9–5:5. The bio-oil was analyzed by GC/MS and Elemental Analyzer, while the morphological changes of residue were observed by a scanning electron microscope (SEM).     

In situ hydrodeoxygenation upgrading of pine sawdust bio-oil to hydrocarbon biofuel using Pd/C catalyst

Hydrodeoxygenation (HDO) is effective for upgrading bio-oil to biofuel. However, the upgrading cost increased due to the high consumption of external hydrogen. In this paper, the hydrogen generated from cheap water using zinc hydrolysis for in situ bio-oil HDO was reported. The effect of different temperatures (200 °C, 250 °C and 300 °C) on bio-oil HDO over Pd/C catalyst was investigated in a batch reactor. The results show that 250 °C yielded biofuel with the highest heating value at 30.17 MJ/kg and the highest hydrocarbons content at 24.09%. Physicochemical properties including heating value, total acid number and chemical compositions of the produced biofuels improved significantly in comparison with that of the original bio-oil.     

Oily Products from Mosses and Algae via Pyrolysis

In this study, the fuel properties of mosses and algae, and the effect of pyrolysis temperature on the yield of bio-oil from moss and alga samples, were investigated. The yield of bio-oil from pyrolysis of the samples increased with temperature. The yields were increased up to 750 K in order to reach the plateau values at 775 K. The maximum yields were 39.1, 34.3, 33.6, 37.0, 35.4, 48.2 and 55.3% of the sample for Polytrichum commune, Dicranum scoparium, Thuidium tamarascinum, Sphagnum palustre, Drepanocladus revolvens, Cladophora fracta and Chlorella protothecoides, respectively. The bio-oil yield for Chlorella protothecoides (a microalga sample) rose from 5.7 to 55.3% as the temperature rose from 525 to 775 K, and then gradually decreased to 51.8% and was obtained at 875 K with a heating rate of 10 K/s. Formulas can be developed to calculate higher heating value (HHV) of different moss and alga samples. The calculated HHV using these new correlations showed mean differences ranging from ?2.3% to +0.06%. The equation developed in this study showed good agreement with experimental results on moss and algae samples. The HHVs for bio-oils from mosses 21.5–24.8 MJ/kg and the HHVs for bio-oils from algae and microalga 32.5 and 39.7 MJ/kg, respectively, were obtained at temperature ranging from 775 to 825 K. In general, algae bio-oils are of higher quality than bio-oils from mosses. In general, microalgae bio-oils are higher quality than bio-oil from wood.