【作者】 刘绍鹏；

【导师】 宗志敏；

【作者基本信息】 中国矿业大学 ， 化学工艺， 2011， 博士

【摘要】 生物质液化油的利用包括燃料利用和非燃料利用。然而由于生物质液化油的组成的复杂性,目前的研究主要偏重于燃料利用。本论文以稻壳液化油为主要原料,把稻壳液化油经过水分离与离心分离后所得的两部分即水溶性和水不溶性稻壳液化油作为分析样本,对两种稻壳液化油利用石油醚等多种极性不同的有机溶剂按照极性由小到大的顺序进行分级萃取,利用GC/MS技术分析萃取物的主要成分。结果表明:稻壳液化油中的化合物在溶剂氯仿、乙醚和乙酸乙酯中的溶解性质比较好,其萃取率均在15%以上。稻壳液化油的成分十分复杂,主要含有酚、酮、醛、酯、酸和烷烃,大部分化合物都含有氧元素以及含氧官能团,如羟基和甲氧基等。由于稻壳液化油含有羧酸类化合物,导致稻壳液化油呈酸性。同时还发现少量的蒽类、菲类多环化合物和酰胺类化合物。用同种有机溶剂萃取水溶和水不溶两部分稻壳液化油,所检测到的物质有很大差异,同时用不同有机溶剂分级萃取同种稻壳液化油得到的萃取物中所含的化合物的种类也不尽相同。在水不溶性稻壳液化油的苯萃取物中,烷烃的相对含量很高,达到了57.0%,而在其它溶剂的萃取物中却含有很少甚至不含有烷烃。用石油醚和二硫化碳萃取出稻壳液化油中一定量的4-羟基3-甲氧基苯甲醛,该化合物有高附加值。次氯酸钠对老化组分的氧化产物中发现非芳香族化合物含量较多,说明稻壳液化油的老化主要与非芳香族化合物有关。考察了不同种类的有机溶剂/无机盐双水相体系的分相能力,表明了NaH2PO4/乙醇体系对稻壳热解液具有较好的分相效果以及萃取分离效果;实验研究中,同时优化了该双水相体系的操作条件,选取质量百分比为38.5%的NaH2PO4和15.4%的乙醇构成的双水相体系对稻壳液化油进行初步改性。处理后的稻壳液化油再利用催化酯化技术对其进行改性处理,催化酯化后采用常压蒸馏,得到60 oC-85 oC馏分、85 oC-95 oC馏分和残留组分,利用气相色谱质谱联用仪(GC/MS)分析各馏分的组成;同时对经过双水相萃取处理后的和未经处理的稻壳液化油催化酯化的效果进行了对比。利用柱层析分离技术对蒸馏后的稻壳液化油双水相萃取物进行分离,分离馏分采用GC/MS分析其组成。通过测定模型化合物的分配系数,研究了模型化合物双水相萃取的分配行为。实验表明:双水相萃取体系使得稻壳液化油中水含量降低了34.8%,达到了较好的改性效果。催化酯化提质有效地提高了双水相处理和未处理的稻壳液化油的pH值;酯化后的双水相萃取稻壳液化油和稻壳液化油原油常压蒸馏过程中,主要馏分都在60 oC-85 oC之间,产率分别为63.0%和67.7%;两种酯化后的稻壳液化油各馏分检测到的组分相似,以烷烃类化合物以及酚、酮和醛等含氧化合物为主;同时发现双水相萃取的稻壳液化油酯化产物中检测到酯类化合物的种类远多于稻壳液化油酯化产物中酯类化合物的种类。通过对双水相萃取稻壳液化油下相的分离与分析,表明双水相体系可用于稻壳液化油中左旋葡聚糖的提取。模型化合物双水相萃取的分配行为的研究,为稻壳液化油在双水相萃取的分配行为提供了理论基础。考察了稻壳液化油中的组分和氨反应的机理,发现纯羟基丙酮与氨反应可以得到3,5-二甲基-2-恶唑啉-4-甲醇,在乙酸参与和酸性条件下生成嘧啶、吡嗪。优化了羟基丙酮与氨在微波环境下的反应条件,反应温度、时间和氨浓度分别为90oC、10 min和15%。该论文有图78幅,表29个,参考文献207篇。更多还原

【Abstract】 Fuel and non-fuel employments are important two parts in biomass liquefied oil usage. However, there are few reports on non-fuel employment of biomass liquefied oil due to the complexion of it.In this paper, oil from rice husk liquefacation was separated by water under centrifugalization into two part, as water soluble part and water insoluble part, respectively. They were fatherly extracted with organic solvent, such as petroleum ether, carbon disulfide, chloroform, diethyl ether and acetic ether by step, the extract from which was analyzed by GC/MS. The result has shown the better solubility of rice husk liquefied oil in chloroform, diethyl ether and acetic ether, in which the extract ratio reaches more than 15%. It has shown us a complex component of rice husk liquefied oil, which mainly contains phenols, ketones, aldehydes, esters, acids and alkanes. Most compounds carry oxygen, such as hydroxyl and methoxyl. Carboxylic acids gift the oil acidity. Anthracene, humble and acylamino were also detected from these extracts. Different compounds exist in these two parts of rice husk liquefied oil, and those extracts by different solvents. Especially, alkanes from insoluble part are detected in benzene, which has reached as high as 57%. 4-hydroxyl, 3-methoxyl- benzaidehyde, a useful compound in rice husk liquefied oil, can be extracted with some solvents such as PE and carbon disulfide. It is detected that there are more non-aromatics in the product of aging rice husk liquefied oil that oxidized by sodium hypochlorite, which means the non-aromatics take important role in the aging reaction of the rice husk liquefied oil.The phase separating ability of different organic solvent / salt aqueous two-phase systems (ATPS), which testified that sodium dihydrogen phosphate / ethanol ATPS had good effects on phase separation and extraction to rice husk liquefied oil. The operating conditions of the ATPS was optimized, in which system the condition was 38.5% (w/w) sodium dihydrogen phosphate and 15.4% (w/w) ethanol, and was arranged to upgrade the rice husk liquefied oil. The rice husk liquefied oil in the upper layer of ATPS was upgraded by catalytic esterification, after which the average distillation of esterification oil, 60 oC-85 oC, 85 oC-95 oC and residue fraction were investigated. The distillation fractions were analyzed by GC/MS. The effects of the rice husk liquefied oil upgraded by aqueous two-phase extraction and esterification with the rice husk liquefied oil upgraded just by esterfication were compared. Column chromatography was arranged to extract the rice husk liquefied oil distillated after upgraded by ATPS, and the extraction fraction were analyzed by GC/MS. By measuring the distribution coefficient of main components in rice husk liquefied oil, the present author studied the distribution behavior of model compounds in ATPS. Experimental results show that:The water content of rice husk liquefied oil was upgraded by ATPS decreased by 34.8%. Catalytic esterification can raise the pH of these two esterification oils. The content of 60-85 oC fractions of esterification from the rice husk liquefied oil treated by ATPS and the crude rice husk liquefied oil are 63% and 67.7%, respectively. The detected compositions of the distillation fractions from these two upgraded esterification oil are similar, which contain hydrocarbons, phenolic compounds, ketones and aldehydes. Meanwhile, it is found that esters in which was treated ATPS were far more than those in rice husk liquefied oil, after esterification. Through the separation and analysis of phase from the rice husk liquefied oil upgraded by ATPS, the study shows that ATPS can be used to extract L-glucan from rice husk liquefied oil. The study of the distribution behavior of ATPS model compounds can provide a theoretical basis for the distribution behavior of rice husk liquefied oil extraction in ATPS.The mechanism of the reaction between rice husk liquefied oil and ammonia was studied. It is discovered that 3,5-dimethyl-2-oxazoline-4-methanol can be obtained by the reaction between pure hydroxyl acetone and ammonia, while with acetic acid in acidic condition, pyridines and pyrazines are obtained. The optimized temperature, time and the concentration of ammonia for the reaction between hydroxyl acetone and ammonia in micro wave are 90oC, 10min and 15%, respectively.更多还原