预处理生物质的热解实验研究  

Experimental study on pyrolysis of pretreated biomass

作　　者：周亚运[1] 肖军[1] 吕潇[1] 沈来宏[1] 

机构地区：[1]东南大学能源热转换及其过程测控教育部重点实验室,南京210096

出　　处：《东南大学学报（自然科学版）》2016年第2期317-325,共9页Journal of Southeast University：Natural Science Edition

基　　金：国家重点基础研究发展计划(973计划)资助项目(2013CB228106);国家自然科学基金资助项目(51576047)

摘　　要：通过分步添加Ca（OH）2与甲酸获得甲酸钙的方法对生物质进行预处理,在管式炉上开展了预处理生物质热解实验,研究了甲酸钙预处理对4种生物质热解特性的影响.样品的红外分析显示,甲酸钙预处理影响了纤维素和半纤维素的结构,一定程度上破坏了乙酰基侧链,而对木质素苯环结构影响较小,且出现了明显的羧酸根官能团振动.热解实验结果表明：木屑的生物油产率高于3种秸秆类生物质（玉米秆、稻秸、麦秆）,最大生物油产率达到0.496 g/g.甲酸钙预处理使得生物质的半焦和气体产率增加,而生物油产率下降.GC-MS分析显示,木屑生物油酸类含量低于秸秆类生物质,而酚类物质含量较高,其中麦秆生物油酸类含量最高,酸度最强.甲酸钙预处理明显减少了生物油中乙酸和左旋葡聚糖的含量,增加了羟基丙酮与环戊烯酮等酮类物质;而且甲酸钙预处理显著降低了生物油的酸性,且对秸秆类生物质的改善作用更加明显,其中木屑生物油p H值从4.1~4.3增加到5.6~5.8,麦秆生物油从2.4~2.7增加到5.0~5.3.Biomass was pretreated using calcium formate obtained by adding Ca（ OH）_2 and formic acid in steps. The pyrolysis experiments of pretreated biomass were carried out in the tube furnace,and the effects of calcium formate pretreatment on the pyrolysis characteristics of four kinds of biomass were investigated. Infrared analysis shows that the structure stabilities of cellulose and hemicellulose are reduced,and the acetyl side chain of hemicellulose is destroyed in a certain degree,while the benzene ring of lignin has been little affected after calcium formate pretreatment. Furthermore,there exists an obvious carboxylate functional group vibration in the pretreated biomass. The pyrolysis experimental results showthat the bio-oil yield of sawdust is higher than those of the corn straw,the rice straw,and the wheat straw,and the maximum is 0. 496 g / g. The calcium formate pretreatment increases the yields of char and gas of biomass,but reduces the bio-oil yield. The results of GC-MS showthat the acidic content of sawdust bio-oil is less than those of bio-oil from agriculture straws,whereas the phenolic content of sawdust bio-oil is higher. Among the agriculture straws,the acidic content of wheat strawbio-oil is the highest,and the acidity is the strongest. The calcium formate pretreatment significantly reduces the relative contents of acetic acid and levoglucosan in bio-oil while increases the contents of hydroxyl acetone and cyclopentenones. The pretreatment is prone to decrease the acidity of bio-oil,and the improvement on agriculture straws is more significant,where the p H value of the bio-oil derived from pretreated sawdust is increased from 4. 1-4. 3 to 5. 6-5. 8,while that for wheat strawis increased from 2. 4-2. 7 to 5. 0-5. 3.

关 键 词：生物质 热解 预处理 甲酸钙 

分 类 号：TK6[动力工程及工程热物理—生物能]