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。     

Box-Behnken响应面法优化粪便直接液化制取生物质油工艺条件的研究

粪便的直接液化是实现粪便无害化、减量化和资源化处理的一种新兴工艺。文章针对人粪便直接液化的工艺条件进行了探讨。以生物质油产率为指标,单因素实验结果显示,反应温度为310℃,停留时间为30min时,生物质油产率最高,为51.77%。利用Box-Benhnken响应曲面优化人粪便直接液化的工艺条件,结果显示,反应温度是影响生物质油产率的关键因素;反应温度为314℃,停留时间为43 min时,生物质油产率最高,为49.59%;生物质油热值最高可达36.59 MJ/kg。研究表明,直接液化过程是C,H元素由人粪便向生物质油中富集的过程。     

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.     

生物质快速热解蒸气的在线催化研究

在固定床上对生物质流化床快速热解产生的蒸气进行了直接催化试验.选用HZSM-5催化剂,探讨了催化温度和催化剂量对催化后产物分布及生物油组分的影响.结果表明:在催化温度为375℃、催化剂量为30 mL时,可获得较高的液相产率(36.4%)、较低的气相产率(20.4%)和焦产率(13.9%).通过分析最佳工况下的生物油组分,发现精制油中含氧量高的有机酸、酯、酮、醛、呋喃等含量明显降低,而含氧量低的小分子酚类及不合氧的烃类含量大幅提高.     

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。     

生物质热解与生物油的特性研究

用木屑、稻壳、玉米秆和棉花秆为原料进行了热解液化试验,生物油的产率分别为63%、53%、57%和56%,生物油的热值均为17~18MJ/kg。生物油成分分析表明,生物油是一种复杂含氧有机化合物与水组成的混合物,包括了几乎所有化学类别的有机物,如醚、酯、醛、酮、酚、醇和有机酸等。生物油粘温特性研究表明,当温度低于85℃时,生物油粘度随着温度升高而减小,符合液体粘温通用关系式;当温度高于85℃时,生物油粘度随着温度升高而上升,生物油中某些化合物开始产生聚合反应。     

微藻直接离子液体脂肪酶制备生物柴油

采用小球藻、甲醇为原料,脂肪酶为催化剂,离子液体为提取剂和反应介质,直接提取酯交换制备生物柴油。考察不同工艺条件对产率的影响,结果表明:甲醇用量和藻粉质量比为8∶1,离子液体[BMIM][DCA]和藻粉质量比为1∶1,脂肪酶用量为藻粉质量的12%,反应温度为50℃,酯交换反应时间为16 h条件下,生物柴油的转化率可达69.6%。采用微藻直接离子液体脂肪酶制备生物柴油无需从微藻粉中提取油脂,因此降低过程成本、缩短工艺,能实现含油微藻到生物柴油的一步转化。     

微波热解工艺参数影响气液产物组成的研究

针对生物质微波热解生物油产率低且含水量高,气体产物较为复杂的特点,通过实验对热解参数、堆积程度、传热介质3个方面进行考察研究。实验结果表明,在热解温度为600℃,预热温度为160℃,填充程度为100%的条件下得生物油最大产率为51.12%,生物炭产率为26.56%,合成气产率为22.32%;生物油以酚类化合物和呋喃类化合物为主,合成气以CO,H2,CH4,CO2,C2～C4小分子气体为主。     

菜籽油超声波法制备生物柴油的研究

以菜籽油和甲醇为反应原料,以KNO3/Al2O3为催化剂,采用超声波法制备生物柴油,考察了超声波频率、醇油物质的量比、催化剂用量等条件对反应的影响。试验结果表明,该反应的最佳条件:超声波频率为30kHz,醇油物质的量比为7∶1,催化剂用量为菜籽油质量的2.0%。在此条件下,生物柴油产率为94%。所得生物柴油的主要性能指标均符合德国的生物柴油标准。     

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.     

Comparative studies of thermochemical liquefaction characteristics of microalgae using different organic solvents

The effect of different organic solvents, such as methanol, ethanol and 1,4-dioxane, on thermochemical liquefaction characteristics of Spirulina (a kind of high-protein microalgae) was systematically studied. The liquefaction experiments were conducted in a 1000 mL autoclave at different temperatures from 573 to 653 K with a fixed solid/liquid ratio. Liquefaction of Spirulina processed in methanol and ethanol favored the conversion rate and bio-oil yield compared with that in 1,4-dioxane solvent. The bio-oil generated in methanol contained higher C and H concentrations but a lower O content, resulting in a higher caloric value (39.83 MJ/kg). The results of FT-IR (Fourier Transform Infrared Spectroscopy) and GC-MS (Gas Chromatography-Mass Spectroscopy) analyses indicated that the compositions of bio-oil products were greatly affected by the type of solvent used for the liquefaction process. The major component of bio-oil produced with methanol was hexadecanoic acid methyl ester (C₁₇H₃₄O₂, 35.53%). However, ethanol favored the formation of hexadecanoic acid ethyl ester (C₁₈H₃₆O₂, 26.27%). When Spirulina were operated with 1,4-dioxane, the bio-oil was dominated by hexadecanenitrile (C₁₆H₃₁N, 22.7%). The presence of methanol and ethanol might promote the formation of esters. Low-boiling-points compounds with phenol ring structure or heterocyclics can be generated when 1,4-dioxane was employed as solvent.     

Pd[P(C_6H_5)_3]_4均相催化精制生物油的试验研究

采用四三苯基瞵合钯为催化剂,对均相催化精制生物油进行试验研究,探讨了反应条件的影响和精制前后各组分的变化及其变化机理.实验表明:反应温度130～140℃、反应时间12h、反应压力5MPa、催化剂与生物油的比值0.002为较佳反应条件;经过此条件精制后,酸、醛和碳碳双键含量(%面积)分别比原始生物油减少90%、88%和48%,酯含量(%面积)增加86%,酮、苯酚、聚糖和呋喃含量几乎不变.     

Hydrothermal catalytic liquefaction mechanisms of agal biomass to bio-oil

The liquefaction mechanisms of the algal biomass to bio-oil were investigated by using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy, respectively. It was found that NaOH was a satisfactory catalyst and contributed to helping the liquefaction of algal biomass. The bio-oil from algal biomass was composed of many compounds, including carbohydrates, alcohol, hydroxybenzene, carboxylic acid, alkene, ester, and others. The mechanism of hydrothermal catalytic liquefaction was discussed. It was found that, comparing with the husk bio-fuel, the algal bio-oil as a promising alternative fuel was more close to the traditional diesel fuel in physicochemical properties. The novel research outcomes contribute to improving the yield of bio-oil from microalgae, reducing the cost of the bio-oil and accelerating the commercial application of the algal bio-oil in the near future.     

亚超临界水中蓝藻的热化学液化

分别考察了反应温度、反应时间和反应物料液比对蓝藻在亚超临界水中的热化学液化效果的影响,结果表明,在反应温度为380℃,反应时间为40 min,反应物料液比为1:20时,液化效果最好,总转化率和油产率分别达到94.5％和41.3％.生物油的GCMS、元素和热值分析表明,生物油的主要成分是芳香族、吡咯和吡啶衍生物等物质,生...     

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.     

Production of crude bio-oil via direct liquefaction of spent K-Cups

Spent K-Cups were liquefied into crude bio-oil in a water-ethanol co-solvent mixture and reaction conditions were optimized using response surface methodology (RSM) with a central composite design (CCD). The effects of three independent variables on the yield of crude bio-oil were examined, including the reaction temperature (varied from 255 °C to 350 °C), reaction time (varied from 0 min to 25 min) and solvent/feedstock mass ratio (varied from 2:1 to 12:1). The optimum reaction conditions identified were 276 °C, 3 min, and solvent/feedstock mass ratio of 11:1, giving a mass fraction yield of crude bio-oil of 60.0%. The overall carbon recovery at the optimum conditions was 93% in mass fraction. The effects of catalyst addition (NaOH and H₂SO₄) on the yield of crude bio-oil were also investigated under the optimized reaction conditions. The results revealed that the presence of NaOH promoted the decomposition of feedstock and significantly enhanced the bio-oil production and liquefaction efficiency, whereas the addition of H₂SO₄ resulted in a negative impact on the liquefaction process, decreasing the yield of crude bio-oil.     

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.     

Bio-oil extraction and physicochemical characterization of Caesalpinia pulcherrima plant seed oil

Dwarf Poinciana (Caesalpinia pulcherrima) seeds are studied for first time for the extraction of bio-oil. The dried and crushed seeds are optimized for maximum yield of bio-oil with a series of polar and nonpolar solvents and recovered by a simple distillation process. Methanol is found to yield the maximum bio-oil. The fatty acid analysis of bio-oil reveals the prevalence of linoleic acid (54.67%), followed by palmitic acid (16.9%), stearic acid (12.5%), and oleic acid (10.32%). Basic fuel properties like specific gravity, viscosity, refractive index, iodine value, saponification value, fire point, flash point, pour point, and calorific value are studied.     

Optimization study of sub/supercritical water liquefication of lignite: Fast liquefaction for high bio-oil yield

Sub/supercritical water liquefication (SCWL) is a water-based thermochemical technology as well as an environmentally friendly treatment by converting wet feedstock into bioenergy. In the present study, a systematic investigation of SCWL of lignite was carried out covering a temperature range between 320 and 440 °C when residence time increased from 5 min to 40 min. The highest bio-oil oil yield of 34.3% with solid residue of 52.7% was obtained at 440 °C for 5 min. Phenol derivatives, carboxylic acids, long chain hydrocarbons, ketones, and naphthalene were the main bio-oil composition through FTIR and GC-MS analysis. Gas yields and their exact compositions were also determined and CO₂ was the dominate gas product but the percentage of CH₄ became significant at severe SCWL conditions. A conclusion was drawn that fast liquefaction (e.g. 5 min) at relative higher temperature (e.g. 400 °C) which avoid excessive gasification and repolymerization reactions was an optimization strategy for high yield bio-oil production from SCWL of lignite.