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林产化学与工业 ›› 2020, Vol. 40 ›› Issue (2): 83-92.doi: 10.3969/j.issn.0253-2417.2020.02.011

• 研究报告 • 上一篇    下一篇

Pt-Re-MCM-41催化剂的制备、表征及其催化热解玉米芯制呋喃类化合物

李文斌1,郑云武1,*(),李水荣2,卢怡1,郑志锋2   

  1. 1. 林业生物质资源高效利用技术国家地方联合工程研究中心; 西南地区林业生物质资源高效利用国家林业和草原局重点实验室; 西南林业大学 材料科学与工程学院, 云南 昆明 650224
    2. 厦门市现代农业生物质高值化技术重点实验室; 福建省生物质高值化技术工程研究中心; 厦门大学 能源学院, 福建 厦门 361102
  • 收稿日期:2019-09-19 出版日期:2020-04-28 发布日期:2020-04-27
  • 通讯作者: 郑云武 E-mail:zhifeng.zheng@xmu.edu.cn
  • 作者简介:李文斌(1995—),男,甘肃天水人,硕士生,主要从事生物质催化转化制备化学品研究
  • 基金资助:
    国家自然科学基金资助项目(31670599);云南省新能源重大科技专项(2015ZB001);西南林业大学材料科学与工程学院“新境杯”科技创新基金

Preparation, Characterization of Pt-Re-MCM-41 Catalyst and Its Catalytic Conversion of Corncob for Producting Furan Compounds

Wenbin LI1,Yunwu ZHENG1,*(),Shuirong LI2,Yi LU1,Zhifeng ZHENG2   

  1. 1. National Local Joint Engineering Research Center for Efficient Utilization of Forestry Biomass Resources; Key Laboratory for Highly-Efficient Utilization of Forest Biomass Resources in the Southwest China, National Forestry and Grassland Administration; College of Materials Engineering, Southwest Forestry University, Kunming 650224, China
    2. Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass; Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass; College of Energy, Xiamen University, Xiamen 361102, China
  • Received:2019-09-19 Online:2020-04-28 Published:2020-04-27
  • Contact: Yunwu ZHENG E-mail:zhifeng.zheng@xmu.edu.cn

摘要:

以MCM-41为载体,采用分步浸渍法制备了一系列不同金属负载量的Pt-Re-MCM-41催化剂,采用氮气吸附-脱附、X射线衍射(XRD)和NH3程序升温脱附(NH3-TPD)对催化剂的理化性质进行表征,并探讨了Pt-Re-MCM-41对催化转化玉米芯热解产物制备呋喃类化合物的影响,及其重复使用和再生性能。实验结果表明:金属Pt、Re均匀地分散在催化剂表面,且负载后没有改变MCM-41的结构性能,但负载后催化剂的比表面积和孔容减小,平均孔径增大。催化剂体系同时具有弱酸和中强酸,Pt、Re负载后催化剂表面的两种酸含量均增加。二维气相色谱(GC×GC)检测到的化合物的类型和数量比一维气相色谱(GC)更为全面,约为GC的4~5倍。催化剂的加入均抑制了醇类、酸类、含氮类和糖类的产生,促进了酮类、呋喃类和碳氢化合物的生成,但对酯类和酚类的影响不大。Pt-Re-MCM-41催化剂均能提高呋喃类化合物的GC含量,在1.0%Pt-1.0%Re-MCM-41催化下且催化温度为450 ℃时GC含量可达33.12%,与无催化剂相比增加了12.11个百分点,且低催化温度(≤450 ℃)有利于2(5H)-呋喃酮和2-呋喃甲醇的生成,高催化温度(≥500 ℃)有利于糠醛、2-甲基呋喃和3-糠醛的生成。1.0%Pt-1.0%Re-MCM-41催化剂连续使用3次后,焙烧可恢复活性,呋喃类化合物GC含量仍可达32.6%。

关键词: 催化转化, Py-GC×GC-MS, Pt-Re-MCM-41, 呋喃类化合物, 活性

Abstract:

A series of Pt-Re-MCM-41 catalysts with different metal loading were prepared by step impregnation method with MCM-41 as support. The physical and chemical properties of the catalysts were characterized by nitrogen adsorption-desorption, X-ray diffraction (XRD) and NH3 temperature programmed desorption (NH3-TPD). The effect of Pt-Re-MCM-41 on the catalytic conversion of corncob pyrolysis products to furan compounds, including its repeated using and regeneration performance, were discussed. The experimental results showed that Pt and Re were uniformly dispersed on the catalyst surface, and the structure and properties of MCM-41 were not changed after loading, but the surface area, pore volume of the catalyst decreased and the average pore diameter increased after loading. The catalyst system had weak acid and medium strong acid at the same time. After Pt and Re loading, the content of the two acid sites on the catalyst surface increased. The type and number of compounds detected by GC×GC were, about 4-5 times than that detected by GC. The addition of the catalyst inhibited the production of alcohols, acids, nitrogen and sugars, and promoted the formation of ketones, furan and hydrocarbons, but had little effect on esters and phenols. The Pt-Re-MCM-41 catalyst could increase the GC content of furan compounds. The GC content could reach 33.12% with 1.0%Pt-1.0%Re-MCM-41 as catalyst and the catalytic temperature was 450℃ and increased by 12.11 percentage point compared with that without catalyst. Low catalytic temperature (≤ 450℃) was favorable for the formation of 2 (5H) -furanone and 2-furan methanol, and high catalytic temperature (≥ 500℃) was beneficial for furfural, 2-methylfuran and 3-furfural formation. The activity of the 1.0%Pt-1.0%Re-MCM-41 catalyst was reduced after three times, and the activity was basically recovered after calcination. Among them, the furan compound GC antent reached 32.6%.

Key words: catalytic conversion, Py-GC×GC-MS, Pt-Re-MCM-41, furan compounds, activity

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