CaO对小球藻多糖热解产物分布的影响
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摘要
利用小型固定床反应器,考察CaO对小球藻多糖热解三相产物分布的影响规律,利用气相色谱(GC)、X射线衍射(XRD)、红外光谱(FT-IR)、气相色谱/质谱联用(GC/MS)等测试手段,综合分析CaO与多糖混合热解脱氧的反应路径。结果表明,与多糖热解相比,25%CaO与75%多糖混合热解生物油有机相的含氧量降低7.32%,呋喃类产物明显减少:含氧气体产量整体下降,其中CO2降低14.87%:固体焦炭的含氧量增加23.11%。CaO与多糖混合热解脱氧主要存在2种反应路径:1)CaO可固定多糖热解过程的部分羰基(C==O)产物;2)生成Ca(OH)2来降低热解液相产物的含水率。
The effect of CaO on the distribution characteristics of three phases products from pyrolysis of Chlorella polysaccharide was studied by means of a small fixed-bed reactor. Reaction path of CaO deoxidation were analyzed comprehensively by GC,XRD,FT-IR and GC-MS. The results show that compared with the direct pyrolysis of Chlorella polysaccharide,the oxygen content of organic components decrease by 7.32% and the furan products reduce obviously;The release of CO_2 decreases by 14.87% and oxygen-containing gas yield overall decline;Furthermore,the oxygen content of solid coke increase by 23.11% when the mass ratio of CaO and polysaccharide was 1/3. FT-IR results indicate that there are two reaction paths in the deoxidation reaction of polysaccharides with CaO:one is to play an important role in the fixation of carbonyl(C==O)from pyrolysis of chlorella polysaccharide,and the other is to reduce the moisture of liquid products by generating Ca(OH)2.
The effect of CaO on the distribution characteristics of three phases products from pyrolysis of Chlorella polysaccharide was studied by means of a small fixed-bed reactor. Reaction path of CaO deoxidation were analyzed comprehensively by GC,XRD,FT-IR and GC-MS. The results show that compared with the direct pyrolysis of Chlorella polysaccharide,the oxygen content of organic components decrease by 7.32% and the furan products reduce obviously;The release of CO_2 decreases by 14.87% and oxygen-containing gas yield overall decline;Furthermore,the oxygen content of solid coke increase by 23.11% when the mass ratio of CaO and polysaccharide was 1/3. FT-IR results indicate that there are two reaction paths in the deoxidation reaction of polysaccharides with CaO:one is to play an important role in the fixation of carbonyl(C==O)from pyrolysis of chlorella polysaccharide,and the other is to reduce the moisture of liquid products by generating Ca(OH)2.
引文
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[2] Marcilla A,CataláL,García-Quesada J C,et al. A review of thermochemical conversion of microalgae[J].Renewable and Sustainable Energy Reviews,2013,27:11—19.
[3] Milano J,Ong H C,Masjuki H H,et al. Microalgae biofuels as an alternative to fossil fuel for power generation[J]. Renewable and Sustainable Energy Reviews,2016,58:180—197.
[4]杨文衍,曾燕,罗嘉,等.微拟球藻热解及其催化热解制备生物油研究[J].燃料化学学报,2011,39(9):664—669.[4] Yang Wenyan,Zeng Yan,Luo Jia,et al. Production of bio-oil by direct and catalytic pyrolysis of Nannochloropsis sp[J]. Journal of Fuel Chemistry and Technology,2011,39(9):664—669.
[5] Guo Qingjie,Wu Man,Wang Kai,et al. Catalytic hydride oxygenation of algae bio-oil over bimetallic Ni-Cu/ZrO catalysts[J]. Industrial&Engineering Chemistry Research,2015,54(3):890—899.
[6]杨林,张秀丽,杨雅,等. CaO表面更新对微拟球藻催化热解制备生物油的影响[J].化工学报,2014,65(11):4340—4346.[6] Yang Lin,Zhang Xiuli,Yang Ya,et al. Production of bio-oil by catalytic pyrolysis of Nannochloropsis sp. over renewed surface CaO catalysts[J]. Journal of Chemical Industry and Engineering(China), 2014, 65(11):4340—4346.
[7] Liu Shiyu, Xie Qinglong, Zhang Bo, et al. Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5as the catalyst[J]. Bioresource Technology,2016,204:164—170.
[8] Veses A,Aznar M,Martinez I,et al. Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts[J]. Bioresource Technology, 2014, 162:250—258.
[9]林郁郁. CaO伴随生物质热裂解制油在线脱氧的实验研究[D].上海:上海交通大学,2011.[9] Lin Yuyu. Experimental investigation on biomass fast pyrolysis in the presence of CaO for in-situ deoxygenation of bio-oil[D]. Shanghai:Shanghai Jiaotong University,2011.
[10] Wang Shuang, Wang Qian, Jiang Xiumin, et al.Compositional analysis of bio-oil derived from pyrolysis of seaweed[J]. Energy Conversion and Management,2013,68:273—280.
[11] Anastasakis K, Ross A B, Jones J M. Pyrolysis behaviour of the main carbohydrates of brown macroalgae[J]. Fuel,2011,90(2):598—607.
[12] Lu Qiang,Xiong Wanming,Li Wenzhi,et al. Catalytic pyrolysis of cellulose with sulfated metal oxides:A promising method for obtaining high yield of light furan compounds[J]. Bioresource Technology, 2009, 100(20):4871—4876.
[13] Shafizadeh F,Lai Y Z. Thermal degradation of 1,6-anhydro-β-D-glucopyranose[J]. The Journal of Organic Chemistry,1972,37(2):278—284.
[14] Sanders E B,Goldsmith A I,Seeman J I,et al. A model that distinguishes the pyrolysis of D-glucose,D-fructose, and sucrose from that of cellulose.Application to the understanding of cigarette smoke formation[J]. Journal of Analytical and Applied Pyrolysis,2003,66:29—50.
[15]唐强,于凤文,吕红云,等.金属离子对生物质热裂解的影响[J].化工进展,2010,29(Sup1):48—51.[15] Tang Qiang,Yu Fengwen,Lyu Hongyun,et al. Effect of metal ions on pyrolysis of biomass[J]. Chemical Industry and Engineering Progress,2010,29(Sup1):48—51.
[16]唐艳军,李友明,宋晶,等.纳米/微米碳酸钙的结构表征和热分解行为[J].物理化学学报,2007,23(5):717—722.[16] Tang Yanjun,Li Youming,Song Jing,et al. Structural characterization and decomposition behavior of microsized and nanosized CaCO3[J]. Acta PhysicoChemica Sinica,2007,23(5):717—722.
[17]金达莱,岳林海,徐铸德.球形碳酸钙复合物的红外,拉曼光谱分析研究[J].无机化学学报,2004,20(6):715—720.[17] Jin Dalai,Yue Linhai,Xu Zhude. Infared and Raman analysis of spherical CaCO3composite[J]. Chinese Journal of Inorganic Chemistry,2004,20(6):715—720.
[18] Lu H,Khan A,Smirniotis P G. Relationship between structural properties and CO2capture performance of CaO-based sorbents obtained from different organometallic precursors[J]. Industrial&Engineering Chemistry Research,2008,47(16):6216—6220.
[19] Yang Xulai,Zhang Jian,Zhu Xifeng. Decomposition and calcinations characteristics of calcium-enriched biooil[J]. Energy&Fuels,2008,22(4):2598—2603.