李文斌, 郑云武, 李水荣, 卢怡, 朱泳峰, 王继大, 郑志锋. 玉米芯热解催化转化制备呋喃类化合物工艺优化[J]. 农业工程学报, 2019, 35(17): 256-262. DOI: 10.11975/j.issn.1002-6819.2019.17.031
    引用本文: 李文斌, 郑云武, 李水荣, 卢怡, 朱泳峰, 王继大, 郑志锋. 玉米芯热解催化转化制备呋喃类化合物工艺优化[J]. 农业工程学报, 2019, 35(17): 256-262. DOI: 10.11975/j.issn.1002-6819.2019.17.031
    Li Wenbin, Zheng Yunwu, Li Shuirong, Lu Yi, Zhu Yongfeng, Wang Jida, Zheng Zhifeng. Optimization of process for preparation of furan compounds by pyrolysis catalytic conversion of corncob[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2019, 35(17): 256-262. DOI: 10.11975/j.issn.1002-6819.2019.17.031
    Citation: Li Wenbin, Zheng Yunwu, Li Shuirong, Lu Yi, Zhu Yongfeng, Wang Jida, Zheng Zhifeng. Optimization of process for preparation of furan compounds by pyrolysis catalytic conversion of corncob[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2019, 35(17): 256-262. DOI: 10.11975/j.issn.1002-6819.2019.17.031

    玉米芯热解催化转化制备呋喃类化合物工艺优化

    Optimization of process for preparation of furan compounds by pyrolysis catalytic conversion of corncob

    • 摘要: 为探索木质生物质气固非均相催化热解制备呋喃类化合物新途径,该文以玉米芯为原料,采用MCM-41、活性炭(AC)、Al2O3、HZSM-5(Si/Al=38,46,80)、TiO2和ZrO2为催化剂,在玉米芯催化热解催化剂筛选的基础上,采用响应曲面法对MCM-41、AC和TiO2催化热解玉米芯工艺条件进行优化,研究催化剂对热解产物组成和呋喃产率的影响。结果表明,较高比表面积的MCM-41?AC和TiO2催化剂可明显促进呋喃类化合物的生成,呋喃类产率可分别达到31.43%、28.78%和30.44%,而HZSM-5系列催化剂最低;单个因素影响顺序为催化剂>催化热解温度>原料与催化剂质量比;催化剂类型和催化热解温度具有明显的交互作用;当催化热解温度为550 ℃、玉米芯与催化剂质量比为1∶1,采用活性炭为催化剂时,呋喃类化合物产率最高可达35.30%。研究结果可以为基于气固催化反应的木质生物质催化热解制呋喃类化学品提供依据。

       

      Abstract: Abstract: Catalytic upgrading of biomass pyrolysis products was an important way for converting biomass to high-value chemicals. Catalytic pyrolysis process produced a higher-oxygenated containing bio-oil over 100 compounds. Furan compounds (furans) were important green platform chemicals in organic synthesis. In order to find a new route for production of furans from catalytic pyrolysis of lignocellulosic biomass by gas-solid heterogeneous catalyst, catalytic conversion of biomass into furan yield and selectivity with catalytic pyrolysis vapor upgrading over different types of catalysts (Al2O3, MCM-41, AC (Activated Carbon), HZSM-5 (Si/Al=38, 46, 80), TiO2 and ZrO2) were investigated. Simultaneously, the response surface methodology was used to determine the optimum process conditions of catalytic pyrolysis of corncob by using MCM-41, AC and TiO2 as catalysts. The results showed that MCM-41 and AC catalysts had the largest specific surface area, followed by HZSM-5, while Al2O3, ZrO2 and TiO2 had the opposite results. In addition, all the catalyst belonged to mesoporous catalysts with the average pore size of 3-16 nm. The main components of corncob with non-catalytic pyrolysis were aldehydes and ketones (17.62%), furans (22.55%) and aromatic compounds (25.18%). Moreover, 4-hydroxy-3-methylacetophenone, 2,3-dihydro-benzofuran and catechol had the highest contents, which were 8.65%, 13.1% and 4.01% respectively. All catalysts inhibited the formation of acid compounds, especially, when AC and HZSM-5(80) were added, the acidic compounds disappeared. The formation of aldehydes and ketones was not significant with the presence of ZrO2, and was inhibited by other types of catalysts. And, HZSM-5 (38), HZSM-5 (46) and AC enhanced the formation of aromatic hydrocarbon, which increased by 1.82%, 14.12% and 12.64% respectively. However, other catalysts were facilitating the formation of furans, which increased by 7.89% (TiO2), 8.88 %( MCM-41), 6.23 %( AC) and 4.95 %( ZrO2), respectively compared with non-catalytic pyrolysis. The maximum yield of furfural of 3.46% was obtained (catalyst is AC) under the conditions of catalytic pyrolysis temperature of 500 ℃ and mass ratio of corncob to catalyst of 2:1. Both TiO2 and HZSM-5 catalysts promoted the formation of furfural, but the effect was not significant. The other catalysts inhibited the formation of furfural. The influence of HZSM-5 catalyst on 2 (5H) -furanone was small, while the other catalysts promoted the production of 2 (5H) -furanone, the maximum yield was obtained with the presence of MCM-41, which increased by 5.45%. And the addition of catalyst inhibited the formation of -benzofuran-2,3-dihydrogen and 5-hydroxymethylfurfural. All the catalysts promoted the production of 5-methyl-2(3H) -furanone except for Al2O3. A highly fitting regression equation was obtained by using the response surface methodology to optimize the preparation process of furans compounds produced by catalytic pyrolysis of corncob, which could effectively predict the yield of furans. The order of effect parameters on the yield of furans was as follows: catalyst > catalytic pyrolysis temperature > mass ratio of corncob to catalyst. The yield of furans could reach 35.30% at the optimum process conditions of catalytic pyrolysis temperature of 550℃ and the mass ratio of corncob to catalyst of 1:1 by using AC catalyst. It would provide a basis for the catalytic pyrolysis of lignocellulosic biomass for production of high value-added chemicals by using heterogeneous catalysts at gas-solid catalytic reaction conditions. And it would provide a new pathway for furans production.

       

    /

    返回文章
    返回