微波响应型CMF@CoS2/MoS2催化剂的制备及其用于木质素蒸气的催化重整

doi:10.6023/A24030079

摘要/Abstract

本研究以Anderson型多金属氧酸盐 (NH₄)₃[CoMo₆O₂₄H₆]•6H₂O为前驱体, 采用一步水热法制备微波响应型CMF@CoS₂/MoS₂催化剂. 当微波频率为2.45 GHz时, 催化剂拥有良好的微波吸收性能(介电损耗正切角值0.23), 证明了其拥有优异的微波响应能力. 木质素蒸气微波辅助催化解聚(MACD)实验表明, CMF@CoS₂/MoS₂显著提高了单酚产率(59.30%)和苯酚选择性(24.69%). 多物理场耦合分析表明, CMF@CoS₂/MoS₂由于其优异的微波吸收性, 能够通过“热点效应”增强局部反应温度, 使木质素蒸气(570 ℃)吸附于高温CoS₂/MoS₂活性组分(910 ℃)表面进一步促进其催化重整. 本工作开发的新型微波响应型CMF@CoS₂/MoS₂催化剂为从木质素炼制高价值酚类平台化合物提供了新的途径.

关键词: 木质素, 微波, 单酚, 苯酚, 催化剂

To take the place of non-renewable resources derived from traditional petrochemical energy conversing of lignin into high-value platform chemicals has become one of the future research hotspots. Among many conversion technologies, microwave-assisted catalytic depolymerization technology is widely used in the catalytic reforming of lignin due to its advantages of block heating rate, low energy consumption, high product selectivity, etc.. The selection of catalysts plays a crucial role in the reforming of lignin. In this work, microwave-responsive CMF@CoS₂/MoS₂ catalyst was prepared by a one-step hydrothermal method using Anderson-type polymetallic oxides (NH₄)₃[CoMo₆O₂₄H₆]•6H₂O as precursors. The morphological features and microwave absorption properties of CMF@CoS₂/MoS₂ catalysts were characterized through scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscope (TEM) and 3656A vector network analyzer. The results showed that CMF@CoS₂/MoS₂ is composed of nanoflowers deposited on the CMF 3D skeleton. And CMF@CoS₂/MoS₂ has excellent microwave absorption properties (dielectric loss angle tangent of 0.23). The catalytic reforming of lignin vapor was carried out using a designed dynamic vapor flow reaction system, and the results showed that the CMF@CoS₂/MoS₂ catalyst possessed highly efficient catalytic reforming ability. The monophenol yield (59.30%) and phenol selectivity (24.69%) of the lignin depolymerization product were increased under the reaction conditions of 400 s, 1000 W, and 600 mL/min N₂. Finite element analysis of the microwave-assisted catalytic depolymerization (MACD) of lignin reveals that the CMF@CoS₂/MoS₂ is capable of generating a “hotspot” effect under microwave irradiation to raise the local temperature of the 3D skeleton to 910 ℃ due to its excellent microwave absorption properties, which is a good example of the MACD of lignin. The heat exchange of lignin vapor with a lower temperature (570 ℃), captured during depolymerization, further promotes the catalytic reforming of lignin vapor. This is key to the efficient catalytic reforming of lignin vapor over the CMF@CoS₂/MoS₂ catalyst. In conclusion, this work provides a promising method for the efficient production of phenols from lignin over bifunctional CMF@CoS₂/MoS₂ catalyst with “wave-absorbing heat transfer” and “catalytic conversion”.

Key words: lignin, microwave, monophenols, phenol, catalyst

引用此文

付祎帅, 王文亮, 苗晖, 陈育彤, 崔洋怡, 王紫薇, 潘佳文, 肖国伟. 微波响应型CMF@CoS₂/MoS₂催化剂的制备及其用于木质素蒸气的催化重整[J]. 化学学报, 2024, 82(6): 596-603.

Yishuai Fu, Wenliang Wang, Hui Miao, Yutong Chen, Yangyi Cui, Ziwei Wang, Jiawen Pan, Guowei Xiao. Fabrication of Microwave-responsive CMF@CoS₂/MoS₂ Catalyst and Highly Efficient Reforming of Lignin Vapor by Microwave Irradiation[J]. Acta Chimica Sinica, 2024, 82(6): 596-603.

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图/表 11

图1. (a) MF、CMF和CMF@CoS2/MoS2的实物图; (b) CMF放置于蒲公英上的实物图; (c) CMF@CoS2/MoS2按压回弹实验

Figure 1. (a) Actual picture of MF, CMF and CMF@CoS2/MoS2; (b) actual picture of CMF placed on a dandelion; (c) elasticity test of CMF@CoS2/MoS2 under pressure

图2. (a, d)不同放大倍数下MF的扫描电镜图像; (b, e)不同放大倍数下CMF的扫描电镜图像; (c, f) CMF@CoS2/MoS2的扫描电镜图像; (g) CMF@CoS2/MoS2的扫描电镜图像以及相应的Co, Mo和S元素图谱

Figure 2. (a, d) SEM images of MF at different magnifications; (b, e) SEM images of CMF at different magnifications; (c, f) SEM images of CMF@CoS2/MoS2; (g) SEM image and the corresponding elemental mapping images of Co, Mo, and S for CMF@CoS2/MoS2

图3. (a) CMF@CoS2/MoS2纳米花的透射电子显微镜图像; (b) CMF@CoS2/MoS2的HRTEM图像; (c) CMF@CoS2/MoS2和CMF@MoS2的X射线衍射图像

Figure 3. (a) TEM image of CMF@CoS2/MoS2 nanoflower; (b) HRTEM image of CMF@CoS2/MoS2; (c) XRD patterns of CMF@CoS2/MoS2 and CMF@MoS2

图4. (a) 催化剂复介电常数实部; (b) 催化剂复介电常数虚部; (c) 催化剂介电损耗正切系数; (d) 催化剂介电损耗正切系数的理论值和实际值

Figure 4. (a) Catalyst complex dielectric constant real part; (b) catalyst complex dielectric constant imaginary part; (c) catalyst dielectric loss tangent factor; (d) theoretical and practical values of catalyst dielectric loss tangent factors

图5. (a) MAD和MACD反应的产物分布; (b) 生物油的总离子色谱图; (c) 生物油的组分分布; (d) 生物油的酚类选择性

Figure 5. (a) Product distribution of MAD and MACD reactions; (b) total ion chromatogram of bio-oil; (c) component distribution of bio-oil; (d) phenolic selectivity of bio-oil

图6. CMF@CoS2/MoS2 在MACD中的催化重整循环性能

Figure 6. The cyclic stability of catalytic reforming with CMF@CoS2/MoS2 in MACD

图7. 不同微波功率下的温度场和电场分布. 反应条件: 反应时间: 400 s; 氮气流速: 600 mL/min

Figure 7. Distribution of temperature field and electric field with different microwave power. Reaction conditions: reaction time: 400 s; nitrogen flow rate: 600 mL/min

图8. (a) CMF@CoS2/MoS2特定条件的有限元模型; (b) CMF@CoS2/MoS2加热速率的有限元模拟

Figure 8. (a) Finite element model for CMF@CoS2/MoS2 set-up conditions; (b) finite element simulation of CMF@CoS2/MoS2 heating rate (a) Finite element model for CMF@CoS2/MoS2 set-up conditions; (b) finite element simulation of CMF@CoS2/MoS2 heating rate

图9. 微波辅助动态气相流动反应系统

Figure 9. Microwave-assisted dynamic vapor flow reaction system

参数名称	参数值
相对磁导率μ_r	1
相对介电常数(CMF@CoS₂/MoS₂) ε_r	5.00-1.17*j
相对介电常数(CoS₂/MoS₂) ε_r	2.39-0.73*j
相对介电常数(CMF) ε_r	5.01-0.98*j
相对介电常数(木质素(脱碱)) ε_r	3.08-0.13*j
电导率σ/(S•m^-1)	0
比热率	1.24
密度/(kg•m^-3)	12

表1. CMF@CoS2/MoS2的物理参数

Table 1. Physical parameters of CMF@CoS2/MoS2

图10. (a)微波反应器的几何模型; (b) CMF@CoS2/MoS2 的几何模型 (a)微波反应器的几何模型; (b) CMF@CoS2/MoS2 的几何模型

Figure 10. (a) Geometrical model of the microwave reactor; (b) geometrical model of the CMF@CoS2/MoS2 (Cheng, B.)

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微波响应型CMF@CoS₂/MoS₂催化剂的制备及其用于木质素蒸气的催化重整

Fabrication of Microwave-responsive CMF@CoS₂/MoS₂ Catalyst and Highly Efficient Reforming of Lignin Vapor by Microwave Irradiation

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