MOF型Ca0.7Nd0.3CoO3对木质素热解的催化性能研究

doi:10.3969/j.issn.1006-396X.2022.05.006

石油化工高等学校学报 ›› 2022, Vol. 35 ›› Issue (5): 54-63.DOI: 10.3969/j.issn.1006-396X.2022.05.006

MOF型Ca_0.7Nd_0.3CoO₃对木质素热解的催化性能研究

王海英¹^,²(), 王程昊³, 张文成²(), 王晓鹏⁴, 陈彦广¹, 张雷¹, 韩洪晶¹()

^1.东北石油大学化学化工学院，黑龙江大庆 163318
^2.中国石油大庆化工研究中心，黑龙江大庆 163714
^3.中国石油大庆石化分公司，黑龙江大庆 163714
^4.中国石油集团安全环保技术研究院有限公司，北京 102206

收稿日期:2022-08-25 修回日期:2022-10-14 出版日期:2022-10-25 发布日期:2022-11-22
通讯作者: 张文成,韩洪晶
作者简介:王海英（1990⁃），女，博士，讲师，从事催化材料合成及催化转化技术方面的研究；E⁃mail：wanghaiying1990@126.com。
基金资助:
国家自然科学青年基金项目(21908021);黑龙江省中央支持地方高水平人才项目(2020GSP17);中国石油科技创新基金项目(2021DQ02?0701);东北石油大学引导性创新基金项目(2021YDL?03);东北石油大学新能源新领域培育项目(XNYXLY202102);东北石油大学人才引进科研启动经费资助项目(2021KQ07)

Study on the Catalytic Performance of Metal⁃Organic Framework⁃Type Ca_0.7Nd_0.3CoO₃ on Pyrolysis of Lignin

Haiying Wang¹^,²(), Chenghao Wang³, Wencheng Zhang²(), Xiaopeng Wang⁴, Yanguang Chen¹, Lei Zhang¹, Hongjing Han¹()

^1.School of Chemistry and Chemical Engineering，Northeast Petroleum University，Daqing Heilongjiang 163318，China
^2.PetroChina Daqing Petrochemical Research Center，Daqing Heilongjiang 163714，China
^3.PetroChina Daqing Petro?Chemical Corporation，Daqing Heilongjiang 163714，China
^4.CNPC Safety and Environmental Technology Research Institute Co. ，LTD. ，Beijing 102206，China

Received:2022-08-25 Revised:2022-10-14 Published:2022-10-25 Online:2022-11-22
Contact: Wencheng Zhang, Hongjing Han

摘要/Abstract

摘要：

催化热解是木质素资源化利用的一种有效途径。采用溶剂热法合成三元金属?有机框架（MOF）前驱体，通过焙烧调控制得钙钛矿Ca_1?_x Nd _x CoO₃（CNC?x），考察了其催化甘蔗渣木质素（BL）热解性能和再生性能，分析了气液相产物组成分布规律。结果表明，800 ℃焙烧制得的CNC?0.3表现出良好的催化BL热解性能，在温度为200~500 ℃时，热解活化能由64.24 kJ/mol降低至58.92 kJ/mol；与BL热解相比，气相产物收率降低，固相产物收率增加，液相产物收率由15.11%提高至17.94%；液相产物主要包括苯酚类、愈创木酚类、紫丁香酚类、苯醚类等芳香基含氧化合物，芳香基含氧化合物的总选择性比纯BL热解时提高了11.0%；经过5次循环再生，CNC?0.3仍具有良好的结构和催化稳定性。

关键词: 金属?有机框架（MOF）, 钙钛矿, 甘蔗渣木质素, 热解, 芳香基含氧化合物

Abstract:

Catalytic pyrolysis is an effective way to use lignin resource.A ternary metal?organic framework (MOF) precursor was synthesized by using the solvothermal method, and then the perovskite Ca_1-_x Nd _x CoO₃ (CNC?x) was prepared by controllable calcination.The performance of the perovskite for catalyzing bagasse lignin (BL) pyrolysis and regeneration was investigated,and the distribution law of the compositions of gaseous and liquid phase products was analyzed. The results show that CNC?0.3 calcined at 800 ℃ shows excellent performance in catalyzing BL pyrolysis.Under a temperature of 200~500 ℃,the pyrolysis activation energy is reduced from 64.24 kJ/mol to 58.92 kJ/mol.Compared with BL pyrolysis,the yield of gaseous phase products decreases,while that of solid phase products increases.The yield of liquid phase products is increased from 15.11% to 17.94%,and the liquid phase products are mainly aromatic oxygenated chemicals including phenols,guaiacols,syringols,and phenyl ethers.The total selectivity of aromatic oxygenated chemicals is 11.0% higher than that under pyrolysis.After five times of regeneration,CNC?0.3 still shows satisfactory structural and catalytic stability.

Key words: Metal organic framework (MOF), Perovskite, Bassage lignin, Pyrolysis, Aromatic oxygenates

中图分类号:

TQ351

王海英, 王程昊, 张文成, 王晓鹏, 陈彦广, 张雷, 韩洪晶. MOF型Ca_0.7Nd_0.3CoO₃对木质素热解的催化性能研究[J]. 石油化工高等学校学报, 2022, 35(5): 54-63.

Haiying Wang, Chenghao Wang, Wencheng Zhang, Xiaopeng Wang, Yanguang Chen, Lei Zhang, Hongjing Han. Study on the Catalytic Performance of Metal⁃Organic Framework⁃Type Ca_0.7Nd_0.3CoO₃ on Pyrolysis of Lignin[J]. Journal of Petrochemical Universities, 2022, 35(5): 54-63.

图/表 16

图1 Ca1?x Nd x CoO3（x=0.1、0.3、0.5、0.7、0.9）的XRD谱图

Fig.1 XRD patterns of Ca1?x Nd x CoO3(x=0.1,0.3,0.5,0.7,0.9)

图2 不同焙烧温度下制得的CNC?0.3的XRD谱图

Fig.2 XRD patterns of CNC?0.3 calcined at different temperatures

图3 不同焙烧温度下制得的CNC?0.3的SEM照片

Fig.3 SEM images of CNC?0.3 calcined at different temperatures

表1 BL的元素分析结果

Table 1 The resuls of elemental composition of BL %

w（C）	w（O）^a	w（H）	w（N）	w（S）
61.55	30.15	6.32	0.79	1.19

图4 BL的FT?IR谱图

Fig.4 FT?IR spectrum of BL

图5 BL的SEM照片和粒度分布曲线

Fig.5 SEM images and particle size distribution of BL

图6 BL热解和CNC?0.3催化BL热解过程的TG曲线

Fig.6 TG curves of BL pyrolysis and BL pyrolysis catalyzed by CNC?0.3

图7 BL热解和CNC?0.3催化BL热解过程的动力学拟合曲线

Fig.7 Kinetic fitting curves of BL pyrolysis and BL pyrolysis catalyzed by CNC?0.3

表2 BL热解和CNC?0.3催化BL热解过程的动力学参数

Table 2 Kinetic parameters of BL pyrolysis and BL pyrolysis catalyzed by CNC?0.3

热解体系	反应级数n	动力学方程	E/(kJ $⋅$ mol^-1)	A/s^-1	R²
BL	2	$d α d t = 730.5 e - 64 236 8.314 T (1 - α) 2$	64.24	730.5	0.991
BL+CNC⁃0.3	2	$d α d t = 482.7 e - 58 923 8.314 T (1 - α) 2$	58.92	482.7	0.990

表2 BL热解和CNC?0.3催化BL热解过程的动力学参数

Table 2 Kinetic parameters of BL pyrolysis and BL pyrolysis catalyzed by CNC?0.3

热解体系	反应级数n	动力学方程	E/(kJ $⋅$ mol^-1)	A/s^-1	R²
BL	2	$d α d t = 730.5 e - 64 236 8.314 T (1 - α) 2$	64.24	730.5	0.991
BL+CNC⁃0.3	2	$d α d t = 482.7 e - 58 923 8.314 T (1 - α) 2$	58.92	482.7	0.990

图8 BL热解和CNC?0.3催化BL热解所得气液固相产物的收率

Fig.8 Yields of gaseous, liquid and solid products obtained from BL pyrolysis and BL pyrolysis catalyzed by CNC?0.3

图9 BL热解和CNC?0.3催化BL热解所得气相产物和液相产物选择性

Fig.9 Selectivity of gaseous products and liquid products obtained from BL pyrolysis and BL pyrolysis catalyzed by CNC?0.3

图10 新鲜、反应5次后和再生5次后CNC?0.3的XRD谱图

Fig.10 XRD patterns of fresh CNC?0.3,spent CNC?0.3 after 5 cycles,and regenerated CNC?0.3 after 5 cycles

图11 BL热解产生的焦、新鲜CNC?0.3、反应5次后、再生5次后CNC?0.3的SEM照片

Fig.11 SEM image of char obtained from BL pyrolysis, fresh CNC?0.3,spent CNC?0.3 after 5 cycles,and regenerated CNC?0.3 after 5 cycles

图12 CNC?0.3再生不同次数后催化BL热解所得液相产物的收率

Fig.12 The yield of liquid products obtained from BL pyrolysis catalyzed by CNC?0.3 after different times of regeneration

表3 CNC?0.3再生不同次数后催化BL热解所得液相产物中各类化合物的选择性

Table 3 The selectivity of defferent species of compounds in the liquid products obtained from BL pyrolysis catalyzed by CNC?0.3 after different times of regeneration

再生次数	液相产物中的选择性/%
再生次数	苯酚类	愈创木酚类	紫丁香酚类	苯醚类	其他类
0	22.52	27.81	21.67	3.19	24.81
1	23.26	28.35	20.83	3.67	23.89
2	23.04	27.38	22.37	3.52	23.69
3	22.94	27.25	22.15	3.13	24.53
4	21.82	29.37	21.04	3.95	23.82
5	21.32	26.84	23.55	2.85	25.44

图13 新鲜和再生5次后CNC?0.3的XPS谱图

Fig.13 XPS spectra of fresh CNC?0.3,regenerated CNC?0.3 after 5 cycles

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MOF型Ca_0.7Nd_0.3CoO₃对木质素热解的催化性能研究

Study on the Catalytic Performance of Metal⁃Organic Framework⁃Type Ca_0.7Nd_0.3CoO₃ on Pyrolysis of Lignin

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