磁性固体酸S2O82-/ZrO2-Al2O3-Fe3O4的制备及催化液化生物质的研究

doi:10.3969/j.issn.0253-2417.2017.03.006

摘要/Abstract

摘要： 利用沉淀-浸渍法制备了磁性固体酸催化剂S₂O₈^2-/ZrO₂-Al₂O₃-Fe₃O₄，将其应用于乙醇介质中能源植物柳枝稷的催化液化，并采用X射线衍射（XRD）、BET比表面积测定、NH₃程序升温脱附（NH₃-TPD）、傅里叶红外光谱（FT-IR）和振动样品磁强计（VSM）等测试方法对催化剂的物化性质和结构进行了表征，考察了Al/Zr物质的量比、煅烧温度等制备条件对其催化性能的影响，并研究了反应温度、反应时间、催化剂用量等对柳枝稷液化反应的影响。结果表明：当n（Al）：n（Zr）为1：1，煅烧温度为650 ℃时，制备的催化剂催化活性最高，在260 ℃、催化剂用量4%（以原料质量计）、反应时间2.5 h时，可以获得较好的液化效果，生物油产率达到56%。GC-MS分析表明产物生物油的主要成分为酯类、醇类及烃类物质。催化剂重复使用3次后，回收率达到87.5%，生物油产率仅下降12%。

关键词: 磁性固体酸, 催化液化, 酸性, 柳枝稷

Abstract: Magnetic solid acid catalyst S₂O₈^2-/ZrO₂-Al₂O₃-Fe₃O₄ was prepared by coprecipitation and impregnation methods and used to catalyze the liquefaction of Panicum virgatum L.(switchgrass)in ethanol. The physicochemical properties and structure of the catalyst were characterized by X-ray diffraction (XRD), Brunauer-Emmet-Teller method (BET), temperature programmed desorption of NH₃ (NH₃-TPD), Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometer (VSM). The influences of Al/Zr molar ratio and calcination temperature on the catalytic performance were investigated. Moreover, the effects of reaction conditions such as reaction temperature, reaction time, as well as mass of catalyst on liquefaction of switchgrass were studied. The experimental results indicated that the catalyst with a Al/Zr molar ratio of 1/1 calcined at 650℃ showed the best activity. An optimum bio-fuel yield of 56% was obtained under the reaction temperature of 260℃, catalyst amount of 4% and 2.5 h of reaction time. The chemical composition of the liquefaction production was identified by GC-MS, in which esters, alcohols and hydrocarbons were the dominate. After 3 times of reuse, the recovery rate of the catalyst still reached 87.5%, and the bio-fuel yield decreased by 12%.

Key words: magnetic solid acid, catalytic liquefaction, acidity, switchgrass

中图分类号:

TQ351

武海棠, 郑冀鲁, 梁名伟, 张军华. 磁性固体酸S₂O₈^2-/ZrO₂-Al₂O₃-Fe₃O₄的制备及催化液化生物质的研究[J]. 林产化学与工业, 2017, 37(3): 45-52.

WU Haitang, ZHENG Jilu, LIANG Mingwei, ZHANG Junhua. Preparation of Magnetic Solid Acid Catalyst S₂O₈^2-/ZrO₂-Al₂O₃-Fe₃O₄ and Its Application for Catalytic Liquefaction of Switchgrass[J]. Chemistry and Industry of Forest Products, 2017, 37(3): 45-52.

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磁性固体酸S₂O₈^2-/ZrO₂-Al₂O₃-Fe₃O₄的制备及催化液化生物质的研究

Preparation of Magnetic Solid Acid Catalyst S₂O₈^2-/ZrO₂-Al₂O₃-Fe₃O₄ and Its Application for Catalytic Liquefaction of Switchgrass

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