微藻水热液化生物油化学性质与表征方法综述

微藻水热液化生物油由于性质较差,不能直接作为车载燃料使用,与现代石油炼制工艺结合是一种新的应用途径。综述了微藻生物油的化学性质,包括化学组成、官能团组成与杂原子化合物组成等信息,比较分析了GC-MS、FTIR、NMR和FT-ICR MS等表征方法的异同,简要回顾了微藻水热液化反应机理和精制方法。重点指出微藻水热液化生物油中含氧、含氮化合物含量较高,并具有较高的芳香度和不饱和度,催化加氢精制能够有效脱除杂原子,并增加烷烃含量。微藻基生物燃料的发展,不仅需要精制工艺的提升,也有赖于表征方法的进步。     

微藻水热液化生物油物理性质与测量方法综述

微藻水热液化生物油由于性质较差,不能直接作为车载燃料使用,而作为原料油与现代石油炼制工艺相结合是一种新的应用途径。本文综述了微藻水热液化生物油的物理性质,包括密度、黏度、酸性、热值与元素组成、沸程、平均分子量等信息,介绍了常用的测量方法与手段。简要回顾了微藻水热液化生物油的精制研究,分析比较了不同精制方法及其效果。重点指出微藻水热液化生物油与重质原油和常减压渣油等劣质原料油相比,具有密度和黏度相近、酸值较高、氮氧元素含量较高、热值较低、重质组分和大分子含量较高等特点,加氢精制能够有效提升微藻水热液化生物油性质,但受反应器结焦、催化剂成本和氢气消耗等因素制约,至今未有突破性成果。     

微藻水热液化制取生物油的研究进展

微藻生产成本低,酯类和甘油含量较高,是制备液体燃料的理想原料。水热液化由于可直接处理湿藻并在适当的温度和压力下将其转化为高品质的石油替代产品而引起了广泛关注。本文探讨了微藻三组分,即蛋白质、脂质和碳水化合物的水热降解途径,并总结了目前微藻水热液化过程的主要影响因素,包括温度、停留时间、溶剂以及催化剂等反应条件或参数对生物油的影响。指出为提高微藻生物油的经济性,应进一步优化反应条件,降低催化剂成本,加强微藻水热定向液化技术的研究,富集液体产品中高附加值成分,实现高附加值化学品的综合利用,尽快实现微藻生物油的应用。     

微拟球藻油脂萃取及脱脂藻水热液化

为提高微藻的综合利用效率,使用不同的溶剂系统分别对干、湿微拟球藻进行油脂萃取,并对脱脂后的藻渣进行水热液化实验,探究溶剂萃取脱脂对微藻水热液化产物的影响。溶剂萃取的结果表明,极性溶剂对油脂的萃取率达到25.0%,但对脂质的萃取缺乏选择,萃取物的脂肪酸甲酯产率仅为29.68%;混合溶剂萃取的脂肪酸甲酯回收率达到57.70%。脱脂后的微拟球藻水热粗油产率为27.7%~34.6%,氮含量为5.29%~6.68%,主要由脂肪酸、脂肪酸酯、脂肪酸酰胺、长链烃类、胺类、含氧化合物和含氮杂环化合物组成。经甲醇萃取后的湿藻水热粗油产率为34.6%,氮含量为5.44%,过程能耗低,表明甲醇萃取湿藻结合水热液化具有一定的应用前景。     

煤基喷气燃料研究现状及展望

为促进我国喷气燃料的发展,介绍了JP-900、煤基全合成喷气燃料和煤直接液化喷气燃料3种煤基喷气燃料的研究历程和制备方法,对比分析了煤基喷气燃料和传统石油基喷气燃料的理化性能和使用性能,最后对煤基喷气燃料的发展提出了相关建议。JP-900的氮含量和硫含量都很少,具有较高的闪点和较低的冰点,密度高,极性化合物含量很少,其热稳定性和燃烧性能均优于石油基的航空燃料。煤基全合成喷气燃料的热稳定性、润滑性、材料相容性等指标相似或更优于传统石油基喷气燃料Jet A-1。煤直接液化油的组成特点与JP-900相似,具有高密度、高闪点、低冰点和富含环烷烃等特点,但其中的杂原子化合物会显著影响其燃料性能。除煤基全合成喷气燃料外,其他2种煤基喷气燃料还没有投入商业应用。未来应进一步增加煤液化产能,建立健全煤基喷气燃料的试验方法,建立煤基喷气燃料的产品标准,以实现煤基喷气燃料的大规模工业化生产和商业应用。     

微拟球藻油脂萃取及脱脂藻水热液化

为提高微藻的综合利用效率,使用不同的溶剂系统分别对干、湿微拟球藻进行油脂萃取,并对脱脂后的藻渣进行水热液化实验,探究溶剂萃取脱脂对微藻水热液化产物的影响。溶剂萃取的结果表明,极性溶剂对油脂的萃取率达到25.0%,但对脂质的萃取缺乏选择,萃取物的脂肪酸甲酯产率仅为29.68%;混合溶剂萃取的脂肪酸甲酯回收率达到57.70%。脱脂后的微拟球藻水热粗油产率为27.7%～34.6%,氮含量为5.29%～6.68%,主要由脂肪酸、脂肪酸酯、脂肪酸酰胺、长链烃类、胺类、含氧化合物和含氮杂环化合物组成。经甲醇萃取后的湿藻水热粗油产率为34.6%,氮含量为5.44%,过程能耗低,表明甲醇萃取湿藻结合水热液化具有一定的应用前景。     

微藻制备生物油的研究进展

微藻是最有潜力的生物燃料原料之一。综述了微藻生物油制备的研究进展,包括微藻油脂抽提法、微藻热解液化法以及超临界液化、微波热解液化、热化学催化液化等几种新型热解液化技术。介绍了现有技术的特点、优势,指出了今后研究的主要方向。     

生物质液化技术的研究进展

生物质液化包括生物化学法生产燃料乙醇和热化学法生产生物油,热化学法又可分为快速热解液化和加压液化。着重介绍了目前达到工业示范规模的各种快速热解液化工艺,如旋转锥反应器、携带床反应器、循环流化床反应器、涡旋反应器、真空热解磨反应器等,以及处于实验室阶段的等离子体液化工艺。指出循环流化床工艺具有很高的加热和传热速率,且处理量可以达到较高的规模,是目前利用最多、液体产率最高的工艺。建议加强纤维素生物酶法糖化发酵生产燃料乙醇工艺的开发以及热化学法生物油精制新工艺的开发。     

煤直接液化粗油提质加工工艺研究现状

分析对比了煤直接液化油的汽油和柴油馏分与石油基汽油和柴油馏分杂原子含量和族组分的差异,指出煤直接液化油中氮和芳烃含量高,需要经过苛刻的加工改质,才能作为车用内燃机燃料使用。介绍了煤液化粗油提质加工的研究现状,讨论了油品加氢催化剂和不同馏分产物的加氢提质工艺,展望了该工艺的发展趋势。     

木质纤维素生物质水热液化的研究进展

对木质纤维素生物质的模型化合物(纤维素、半纤维素和木质素)的水热液化机理进行了剖析。纤维素和半纤维素降解路径主要是水解成单糖并进一步生成酸类、醛类、酮类等。木质素结构较复杂,液化产物中含有大量苯系化合物,具体木质纤维素生物质的水热液化反应更为复杂,不同的木质纤维素生物质原料水热液化产生的生物油含量不同;分析了原料种类、催化剂、反应温度、反应压力、对水热液化过程以及产品组成和收率的影响;对生物质水热液化制备生物油的研究进行了展望,认为发展木质纤维素生物质水热条件下降解的数学模型,开发新型反应器、研制催化剂,是今后生物质水热液化工程实验的发展方向。     

生物原油炼制： 副产物内循环及水热自催化

利用高温高压条件模拟石油生成的生物质水热液化技术可用于制备生物原油,以替代日益枯竭的石油资源,然而副产物处置问题制约了其可持续发展。解决该问题的方法首先是通过水热定向催化调控减少副产物,然后集成各种技术将副产物尽可能原位资源化。基于此并依据生物炼制的思想,本文对一种集成几种水热技术炼制生物原油的模式进行了讨论。依据生物质水热液化副产物的特性,通过对固体产物水热合成制备催化剂、水相产物回用产生有机酸、气体产物分离或彻底氧化后水热还原生产有机酸等,可实现副产物内循环并强化自催化生成生物原油。指出该模式符合绿色化工的理念,对于加快规模化生产可替代石油的生物原油、缓解能源危机具有重要的参考意义。     

反应条件对玉米秸秆水热液化产物分布及特性的影响

利用间歇式生物质水热液化反应釜,通过正交试验设计考察不同反应条件对玉米秸秆水热液化(HTL)的影响,过程参数包括反应温度(250～350℃),反应时间(0～60 min)和含固量(5％～15％).从元素组成、官能团分布、主要化学成分以及结构形貌等对玉米秸秆水热液化产物的特性进行了分析.研究结果表明:玉米秸秆水热液化的较...     

滇池藻水热液化成油特性研究

以滇池藻为原料研究水热液化条件对其液化反应的影响,并分析反应温度对水热液化产物分布及生物油特性的影响。结果表明：在反应温度300℃、反应时间60 min、原料含固率20%条件下生物油产率最高为14.82%,生物油能量回收率最高为54.11%,碳、氢元素回收率分别为49.65%、24.83%,其热值为35.79 MJ/kg。GC-MS分析结果显示：生物油含烃类22.4%,有机酸类34.3%,氮氧化合物21.1%,酯类5.47%。反应温度对生物油组分中含氮氧杂环化合物、酯类、有机酸类、烃类以及酚类化合物GC含量变化有很大影响。反应温度为380℃时转化率最高为83.87%,生物油H/C最高,N/C最低,比值分别为1.39和0.05,热值为36.76 MJ/kg。     

重油分子结构组成的分析方法研究进展

综述了近年来重油分子结构的研究方法,分别介绍了烃类化合物、胶质和沥青质及氧、氮、硫杂原子化合物结构组成的分析方法,并分析比较了不同分析方法的优缺点。质谱法、钌离子催化氧化法、裂解色谱法等在研究重油分子结构中不断有新的突破,各种分析手段的结合为重油分子结构组成提供更加准确、丰富的信息。     

Multifunctional heteroatom zeolites: construction and applications

Multifunctional heteroatom zeolites have drawn broad attentions due to the possible synergistic effects in the catalytic reactions. Remarkable achievements have been made on the synthesis, characterization and catalytic applications of multifunctional heteroatom zeolite, while a review on this important topic is still missing. Herein, current research status of multifunctional heteroatom zeolites is briefly summarized, aiming to boost further researches. First, the synthesis strategies toward heteroatom zeolites are introduced, including the direct synthesis and postsynthesis routes; then, the spectroscopic techniques to identify the existing states of heteroatom sites and the corresponding physiochemical properties are shown and compared; finally, the catalytic applications of multifunctional heteroatom zeolites in various chemical reactions, especially in one-step tandem reactions, are discussed.     

Hydrothermal processing of microalgae using alkali and organic acids

Aquatic organisms such as microalgae have been identified as a potential source of third generation biofuels due to their fast growth rate, ability to sequester CO₂ and their potential for producing lipids. Conversion by hydrothermal liquefaction is ideally suited to high moisture content feedstocks such as microalgae and involves the processing of biomass in hot compressed water with or without the presence of a catalyst. This study aims to investigate the conditions for producing high quality, low molecular weight bio-crude from microalgae and cyanobacteria containing low lipid contents including Chlorella vulgaris and Spirulina. Liquefaction experiments have been performed in a high pressure batch reactor at 300 °C and 350 °C. The influence of process variables such as temperature and catalyst type has been studied. Catalysts employed include the alkali, potassium hydroxide and sodium carbonate and the organic acids, acetic acid and formic acid. Liquefaction yields have been determined and the bio-crude has been analysed for CHNOS content and calorific value. The bio-crude has been analysed by GC/MS to examine composition and thermal gravimetric analysis (TGA) to estimate its boiling point range. The aqueous fraction has been analysed for typical cations and anions by ion exchange chromatography and for total organic carbon (TOC). The yields of bio-crude are higher using an organic acid catalyst, have a lower boiling point and improved flow properties. The bio-crude contains a carbon content of typically 70-75% and an oxygen content of 10-16%. The nitrogen content in the bio-crude typically ranges from 4% to 6%. The higher heating values (HHV) range from 33.4 to 39.9 MJ kg⁻¹. Analysis by GC/MS indicates that the bio-crude contains aromatic hydrocarbons, nitrogen heterocycles and long chain fatty acids and alcohols. A nitrogen balance indicates that a large proportion of the fuel nitrogen (up to 50%) is transferred to the aqueous phase in the form of ammonium. The remainder is distributed between the bio-crude and the gaseous phase the latter containing HCN, NH₃ and N₂O depending upon catalyst conditions. The addition of organic acids results in a reduction of nitrogen in the aqueous phase and a corresponding increase of NH₃ and HCN in the gas phase. The addition of organic acids has a beneficial effect on the yield and boiling point distribution of the bio-crude produced.     

Liquid Chromatographic fractionation of oil-sand and crude oil asphaltenes

Asphaltenes extracted from Alberta oil sands (Athabasca, Cold Lake, and Peace River) and crude oils (Taber South and Fenn-Big Valley) were fractionated by sequential elution solvent chromatography (SESC) involving 10 organic solvents on a silica column. Athabasca asphaltenes and SESC fractions were further studied by elemental analysis, i.r., u.v., and n.m.r. spectroscopy. Incomplete extraction of maltenes from the oil-sand bitumens increased the yields of the first two SESC fractions, the saturates and aromatics, of oil-sand asphaltenes relative to the crude oil asphaltenes. About 55 wt% of the asphaltenes elute in fractions 3–5. Two distinct molecular types are present in the asphaltenes; namely, lower functionality species with lower heteroatom content and the higher functionality species with higher heteroatom content. Compounds eluting in fractions 3–10 are predominantly polynuclear aromatics with alkyl substituants and probably bridged by cycloalkanes. The extent of bridging as well as the location, number and type of heteroatoms determines the fraction in which each compound appears. Complexity of compounds eluting increases with time: earlier fractions are composed of smaller-size polynuclear aromatic centers and contain heteroatoms in predominantly ring locations, whereas later fractions contain a larger proportion of complex species and more functional heteroatom groups.     

A comparison of wet-extracted coconut oils prepared under hot and cold conditions

Virgin coconut oil was prepared by four wet extraction methods which included hot extraction by boiling coconut milk, and three cold extraction methods by centrifugation, fermentation, and chilling followed by thawing of coconut milk. The chemical characteristics related to both saponifiable and unsaponifiable fractions of oils were evaluated. Quality parameters such as peroxide value, iodine value, saponification value, acid value, and moisture content of the four oils remain within the acceptable range for edible purposes. Hot conditions incorporate a richer phenolic profile, a higher α-tocopherol content, and a higher β-carotene content in coconut oil. Epimerization and hydrolysis of the phenolic compounds occur depending on the extraction conditions. The longest shelf-life of the coconut oil prepared under hot conditions may be due to the relatively lower contents of moisture, free acids, peroxides, and higher contents of phenolic compounds, α-tocopherol, and β-carotene in hot-extracted coconut oil. Contrary to popular belief, hot and wet extraction conditions may produce higher quality coconut oil compared to cold extraction conditions.