分散型催化剂在煤/重油共炼体系中的加氢抑焦作用

doi:10.11949/0438-1157.20240047

化工学报 ›› 2024, Vol. 75 ›› Issue (7): 2556-2564.DOI: 10.11949/0438-1157.20240047

• 催化、动力学与反应器 • 上一篇下一篇

分散型催化剂在煤/重油共炼体系中的加氢抑焦作用

杨露¹(), 刘聪聪², 孟彤彤¹, 张博远¹, 杨腾飞¹(), 邓文安³, 王晓斌¹()

^1.山东理工大学化学化工学院，山东淄博 255000
^2.淄博市产品质量检验研究院，山东淄博 255000
^3.中国石油大学（华东）化学化工学院，山东青岛 266580

收稿日期:2024-01-10 修回日期:2024-05-20 出版日期:2024-07-25 发布日期:2024-08-09
通讯作者: 杨腾飞,王晓斌
作者简介:杨露（1998—），女，硕士研究生，350641167@qq.com
基金资助:
国家自然科学基金项目(21776166);山东省泰山学者专项(tsqn202211141)

Hydrogenation and coke-suppression performance of dispersed catalyst in coal/heavy oil co-processing reactions

Lu YANG¹(), Congcong LIU², Tongtong MENG¹, Boyuan ZHANG¹, Tengfei YANG¹(), Wen’an DENG³, Xiaobin WANG¹()

^1.School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255000, Shandong, China
^2.Product Quality Inspection Research Institute, Zibo 255000, Shandong, China
^3.College of Chemical Engineering, China University of Petroleum, Qingdao 266580, Shandong, China

Received:2024-01-10 Revised:2024-05-20 Online:2024-07-25 Published:2024-08-09
Contact: Tengfei YANG, Xiaobin WANG

摘要/Abstract

摘要：

采用马瑞常渣与印尼褐煤进行煤/重油加氢共炼反应，研究了马瑞常渣脱除沥青质和催化剂加量对共炼体系加氢转化深度的影响。利用XRD、XPS、TEM、TG、¹³C NMR和SEM对共炼反应后固体残渣进行表征。结果表明，沥青质的存在会促进生焦过程并显著降低共炼体系中煤的转化效率，达到同等转化深度时脱沥青油体系中所需催化剂加量大幅度降低。对于沥青质含量较高的马瑞常渣体系，催化剂反应后固体残渣中有机碳质组分芳香度降低，含氧组分比重下降，且残余有机碳也更易发生热解，表明催化剂对反应体系中碳质组分优异的氢解作用。固体残渣的微观形貌分析则显示出催化剂对生焦过程的良好抑制效果，有助于提高反应体系的加氢转化深度。

关键词: 分散, 催化剂, 加氢, 沥青质, 生焦

Abstract:

The influence of asphaltene removal and catalyst dosage on the hydro conversion efficiency of the coal/heavy oil co-processing system using MRAR and Indonesian lignite were investigated. The solid residues after co-processing reaction were characterized by XRD, XPS, TEM, TG, ¹³C NMR and SEM. The results show that the presence of asphaltene will promote the coking process and significantly reduce the conversion efficiency of coal in the co-processing system. When reaching the same conversion depth, the amount of catalyst required in the deasphalted oil system will be greatly reduced. For the MRAR systems with a relative high asphaltene content, the application of catalyst resulted in a decreased aromaticity of organic carbon components in the solid residues and a reduced proportion of oxygen-containing components. Additionally, residual organic carbon components were more prone to pyrolysis, indicating an excellent hydrogenolysis effect of the catalyst on the carbon components during the reaction process. Microscopic morphology analysis of the solid residues showed that the catalysts exhibited a favorable role in inhibiting coke formation, which helps to improve the hydrogenation conversion depth of the reaction system.

Key words: dispersion, catalyst, hydrogenation, asphaltene, coke formation

中图分类号:

TQ 529

杨露, 刘聪聪, 孟彤彤, 张博远, 杨腾飞, 邓文安, 王晓斌. 分散型催化剂在煤/重油共炼体系中的加氢抑焦作用[J]. 化工学报, 2024, 75(7): 2556-2564.

Lu YANG, Congcong LIU, Tongtong MENG, Boyuan ZHANG, Tengfei YANG, Wen’an DENG, Xiaobin WANG. Hydrogenation and coke-suppression performance of dispersed catalyst in coal/heavy oil co-processing reactions[J]. CIESC Journal, 2024, 75(7): 2556-2564.

图/表 13

表1 印尼褐煤与马瑞常渣的基本性质

Table 1 Main properties of Indonesia lignite and MRAR

性质	褐煤	常渣
挥发分含量/%（质量分数，daf）	58.4	/
固定碳含量/%（质量分数，daf）	41.6	/
灰分含量/%（质量分数，ad）	4.5	—
密度（20℃）/（g·cm^-3）	1.475	0.998
黏度（100℃）/（mm²·s^-1）	/	294.3
硫含量/%（质量分数）	0.61	2.38
氮含量/%（质量分数）	0.66	0.62
氢/碳摩尔比	0.912	1.526
初馏点~360℃馏分/%（质量分数）	/	1.8
360~480℃馏分/%（质量分数）	/	85.5
>480℃馏分/%（质量分数）	/	12.7
正庚烷沥青质含量/%（质量分数）	/	10.2
甲苯不溶物含量/%（质量分数）	/	—

图1 马瑞常渣脱沥青前后作溶剂进行煤/重油加氢共炼反应的转化率变化

Fig.1 Changes in the conversion efficiency with MRAR or MRARd as solvent for co-processing of coal and heavy oil

图2 不同催化剂加量下共炼体系反应后固体残渣收率及马瑞常渣单独反应的生焦量变化

Fig.2 Variations of the solid residue yield in co-processing system and the coke yield in reacted MRAR alone with different catalyst dosage

图3 马瑞常渣脱沥青前后反应后固体残渣的Ni 2p XPS谱图

Fig.3 Ni 2p XPS spectra of solid residues after reactions with MRAR or MRARd

图4 马瑞常渣脱沥青前后固体残渣的TEM图和元素mapping图

Fig.4 TEM images and corresponding element maps of solid residues after reactions with MRAR or MRARd

图5 不同催化剂加量下反应后固体残渣的H/C原子比

Fig.5 H/C atomic ratio of solid residues with different catalyst dosage

图6 不同催化剂加量下反应后固体残渣的XRD谱图及无定形碳区域的分峰拟合

Fig.6 XRD patterns and the peak-fittings for amorphous carbon regions of solid residues with different catalyst dosage

图7 不同催化剂加量下反应后固体残渣的13C NMR谱图及分峰拟合

Fig.7 13C NMR spectra and the peak-fittings for solid residues with different catalyst dosage

表2 固体残渣中不同类型有机碳的相对含量

Table 2 Relative proportions of different organic carbons in solid residues

固体残渣样品	相对含量/%
固体残渣样品	芳香碳	烷基碳	羰/羧基碳	桥联碳	质子化芳香碳	氧连芳香碳	烷基侧链芳香碳	甲（氧）基碳	亚/次甲基碳	氧连烷基碳
SR0	71.6	28.4	17.8	10.9	26.2	6.3	10.4	15.6	12.8	8.8
SR500	62.5	37.5	13.9	9.5	22.7	5.8	10.6	16.4	21.1	8.2
SR1500	62.3	37.7	13.2	9.0	24.6	5.3	10.2	18.1	19.6	7.4

图8 不同催化剂加量下反应后固体残渣的TG和DTG曲线

Fig.8 TG and DTG curves of solid residues with different catalyst dosage

图9 不同催化剂加量下反应后固体残渣热解的Arrhenius图

Fig.9 Arrhenius plots for pyrolysis of solid residues with different catalyst dosage

表3 固体残渣最高热解温度处的热解动力学参数

Table 3 Pyrolysis kinetic parameters for solid residues at the maximum pyrolysis temperature

固体残渣样品	最高热解温度T_m/℃	活化能E_a/ (kJ·mol^-1)	指前因子A/s^-1	拟合度R²
SR0	479.5	49.9	18.89	0.992
SR500	468.2	41.8	5.14	0.998
SR1500	455.3	36.1	2.83	0.997

图10 不同催化剂加量下的固体残渣的SEM图（5000倍）

Fig.10 SEM images of solid residues with different catalyst dosage (magnification of 5000)

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分散型催化剂在煤/重油共炼体系中的加氢抑焦作用

Hydrogenation and coke-suppression performance of dispersed catalyst in coal/heavy oil co-processing reactions

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