固体酸催化下玉米芯在近临界甲醇-环己烷中的液化研究

doi:10.3969/j.issn.0253-2417.2017.06.010

林产化学与工业 ›› 2017, Vol. 37 ›› Issue (6): 73-80.doi: 10.3969/j.issn.0253-2417.2017.06.010

固体酸催化下玉米芯在近临界甲醇-环己烷中的液化研究

潘青青^1,2, 张军^1,2, 吴真^1,2, 李迅^1,2, 张瑜^1,2, 王飞^1,2

1. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037;
2. 南京林业大学化学工程学院;江苏省生物质绿色燃料与化学品重点实验室, 江苏南京 210037

收稿日期:2017-07-24 出版日期:2017-12-25 发布日期:2018-01-05
通讯作者: 王飞,教授,博士,博士生导师,主要研究领域为生物质能源与生物质化学品;E-mail:hgwf@njfu.edu.cn E-mail:hgwf@njfu.edu.cn
作者简介:潘青青(1992-),女,江苏扬州人,硕士生,主要从事木质纤维生物质催化转化制备液体燃料的研究
基金资助:
国家重点研发计划（2016YFD0600801）

Liquefaction of Corncob with Solid Acid as Catalyst in Near-critical Methanol-cyclohexane

PAN Qingqing^1,2, ZHANG Jun^1,2, WU Zhen^1,2, LI Xun^1,2, ZHANG Yu^1,2, WANG Fei^1,2

1. Jiangsu Co-innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China;
2. College of Chemical Engineering, Nanjing Forestry University;Jiangsu Key Lab. of Biomass-based Green Fuels and Chemicals, Nanjing 210037, China

Received:2017-07-24 Online:2017-12-25 Published:2018-01-05

摘要/Abstract

摘要： 通过共沉淀法和浸渍法制备了SO₄^2-/TiO₂-ZrO₂固体酸催化剂，并采用傅里叶红外光谱（FT-IR）、X射线能谱（EDX）和氮气吸附-脱附分析等手段对催化剂进行表征，考察了溶剂配比、反应温度、反应停留时间和催化剂用量对玉米芯在近临界甲醇-环己烷中液化转化率的影响，并利用FT-IR和气相色谱-质谱联用仪（GC-MS）对玉米芯液化产物进行了分析。结果表明：SO₄^2-成功地负载到TiO₂-ZrO₂上，且SO₄^2-/TiO₂-ZrO₂属于介孔材料；玉米芯的最佳催化液化条件为V（甲醇）：V（环己烷）=2：1，反应温度250℃，反应停留时间1.5 h，催化剂用量（以玉米芯质量计）4%，玉米芯与溶剂的固液比为1：15（g：mL），此条件下液化转化率为76.67%。FT-IR和GC-MS分析表明玉米芯液化产物主要成分为酚类和酯类化合物。

关键词: 近临界, 甲醇-环己烷, 玉米芯, 催化液化

Abstract: SO₄^2-/TiO₂-ZrO₂ solid acid catalyst was prepared by co-precipitation and impregnation. The catalysts were characterized by Fourier transform infrared spectrometer(FT-IR), energy dispersive X-ray spectrometer(EDS) and nitrogen physisorption. The effects of solvent ratio, reaction temperature, reaction time and catalyst dosage on corncob conversion were investigated. The chemical compositions of liquefaction production with and without catalysts were determined by FT-IR and gas chromatography/mass spectrometry(GC-MS). The results indicated that SO₄^2- was successfully loaded on the TiO₂-ZrO₂ and SO₄^2-/TiO₂-ZrO₂ was a mesoporous material. The optimal conditions of liquefaction were 1 g corncob with 4% SO₄^2-/TiO₂-ZrO₂ at 250℃ for 1.5 h when the volume ratio of methanol to cyclohexane was 2 and the solid-liquid ratio of corncob and solution was 1:15(g:mL), under which the liquefied rate reached the maximum of 76.67%. The main components of the liquefaction product were phenols and ester compounds.

Key words: near-critical, methanol-cyclohexane, corncob, catalytic liquefaction

中图分类号:

TQ35

潘青青, 张军, 吴真, 李迅, 张瑜, 王飞. 固体酸催化下玉米芯在近临界甲醇-环己烷中的液化研究[J]. 林产化学与工业, 2017, 37(6): 73-80.

PAN Qingqing, ZHANG Jun, WU Zhen, LI Xun, ZHANG Yu, WANG Fei. Liquefaction of Corncob with Solid Acid as Catalyst in Near-critical Methanol-cyclohexane[J]. Chemistry and Industry of Forest Products, 2017, 37(6): 73-80.

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固体酸催化下玉米芯在近临界甲醇-环己烷中的液化研究

Liquefaction of Corncob with Solid Acid as Catalyst in Near-critical Methanol-cyclohexane

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