水蒸气对煤焦油模化物裂解行为及析碳的影响

doi:10.11949/j.issn.0438-1157.20181375

化工学报 ›› 2019, Vol. 70 ›› Issue (8): 2898-2908.DOI: 10.11949/j.issn.0438-1157.20181375

水蒸气对煤焦油模化物裂解行为及析碳的影响

翟建荣¹(),钟梅^1,²(),马凤云¹,胡浩权²

1. 新疆大学化学化工学院，新疆维吾尔自治区煤炭清洁转化与化工过程重点实验室，新疆乌鲁木齐 830046
2. 大连理工大学化工学院，煤化工研究所，精细化工国家重点实验室，辽宁大连 116024

收稿日期:2018-11-19 修回日期:2018-12-14 出版日期:2019-08-05 发布日期:2019-08-05
通讯作者: 钟梅
作者简介:翟建荣（1996—），男，硕士研究生，838903286@qq.com
基金资助:
国家自然科学基金项目(21606187);新疆维吾尔自治区政府联合基金重点项目(U1703252);高等学校学科创新引智计划（111计划）项目(D18022)

Effect of steam atmosphere on cracking behavior and carbon deposition of coal tar model compounds

Jianrong ZHAI¹(),Mei ZHONG^1,²(),Fengyun MA¹,Haoquan HU²

1. Key Laboratory of Coal Clean Conversion & Chemical Engineering Process of Xinjiang Uygur Autonomous Region, College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, Xinjiang, China
2. State Key Laboratory of Fine Chemicals, Institute of Coal Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2018-11-19 Revised:2018-12-14 Online:2019-08-05 Published:2019-08-05
Contact: Mei ZHONG

摘要/Abstract

摘要：

采用机械化学法制备Ni-Ce/Al₂O₃催化剂，在固定床反应器中考察了水蒸气气氛对煤焦油模型化合物甲苯＋芘催化裂解行为的影响。根据产物生成规律提出了芘向萘转化的裂解机理，并以D₂O对其进行了验证。通过XRD、TG-DTG和Raman等表征了析碳的类型与结构特征。结果表明：相较于纯氮气气氛，水的加入可明显提升重质组分芘的裂解率，且随水碳比（S/C）增加呈先增加后降低的趋势，在S/C=0.15时达到最大值98.93%，比S/C=0时增加32.09%。析碳率随S/C比增加一直呈下降趋势，由S/C=0时的10.04%降至S/C=0.26时的5.39%。析碳分析结果表明，S/C=0时，生成的积炭类型主要是β型碳及γ型碳，水蒸气存在时，活性较高的α型碳含量增加，说明水蒸气的持续消碳作用抑制了C_α向C_β与C_γ方向转化。

关键词: 催化剂, 催化（作用）, 固定床, 模型化合物, S/C比, 析碳类型

Abstract:

The Ni-Ce/Al₂O₃ catalyst was synthesized via mechanochemical method. The effects of steam on the cracking behavior of toluene and pyrene as coal tar model compounds were investigated in a fixed bed reactor. Based on the product distribution, the cracking mechanism of the conversion of pyrene to naphthalene was proposed and verified by D₂O as a tracer. The types and structural characteristics of carbon deposition on the spent catalysts were characterized by XRD, TG-DTG and Raman, etc. The results showed that the addition of steam obviously enhanced the cracking rate of pyrene, compared with the pure nitrogen atmosphere, and it increased first and then decreased with the increase of steam-carbon ratio (S/C) and reaching a maximum of 98.93% at S/C=0.15, increased by 32.09% in comparison with S/C=0. A downward trend was that the yield of carbon decomposition decreased from 10.04% to 5.39% with the increase of S/C ratio from 0 to 0.26. In addition, carbon analysis results show that the main type of carbon deposits were β-type and γ-type at S/C=0. On the contrary, in the presence of steam, the activity of higher α-type carbon content increased. Therefore, it indicated that the carbon elimination by steam inhibited the conversion of C_α to C_β and C_γ.

Key words: catalyst, catalysis, fixed-bed, model compound, steam-carbon ratio, carbon type

中图分类号:

O 643.32

翟建荣, 钟梅, 马凤云, 胡浩权. 水蒸气对煤焦油模化物裂解行为及析碳的影响[J]. 化工学报, 2019, 70(8): 2898-2908.

Jianrong ZHAI, Mei ZHONG, Fengyun MA, Haoquan HU. Effect of steam atmosphere on cracking behavior and carbon deposition of coal tar model compounds[J]. CIESC Journal, 2019, 70(8): 2898-2908.

图/表 17

图1 催化剂评价装置

Fig.1 Schematic diagram of catalytic evaluation device

表1 不同水量对模型化合物催化裂解性能的影响

Table 1 Effect of water flow on catalytic cracking performance of model compounds

水/碳比	模型化合物	液体产率/%	气产率/%	析碳率/%	芘裂解率/%	芘生成率/ (mg/g)
0	甲苯	87.46	2.53	10.01	—	0.46
0	甲苯＋芘	87.53	2.43	10.04	66.84	—
0.08	甲苯	75.75	17.39	7.65	—	0.40
0.08	甲苯＋芘	74.61	19.39	6.68	86.91	—
0.12	甲苯	75.11	18.91	6.98	—	0.34
0.12	甲苯＋芘	74.02	20.31	6.61	88.19	—
0.13	甲苯	70.23	24.10	6.76	—	0.31
0.13	甲苯＋芘	69.94	24.75	6.32	94.68	—
0.15	甲苯	65.60	29.10	6.52	—	0.26
0.15	甲苯＋芘	66.43	28,63	6.07	98.93	—
0.26	甲苯	54.33	41.55	5.71	—	0.20
0.26	甲苯＋芘	55.45	40.65	5.39	96.41	—

图2 S/C比对甲苯+芘裂解性能的影响

Fig.2 Effect of S/C ratio on cracking performance of toluene and pyrene

图3 S/C比对各气体组分产率的影响

Fig.3 Effect of S/C on yield of gas component

图4 裂解反应液体产物 GC-MS 图

Fig.4 GC-MS results of liquid product from cracking reaction

表2 裂解反应液体产物GC-MS图的定性分析

Table 2 Qualitative analysis of GC-MS spectrum of liquid product from cracking reaction

峰	名称	峰	名称
1	对二甲苯	7	3-甲基联二苯
2	邻二甲苯	8	2,2’-二甲基联苯
3	间二甲苯	9	3,3’-二甲基联苯
4	萘	10	顺式-1,2二苯乙烯
5	2-乙烯基萘	11	菲
6	二苯基甲烷	12	芘

图5 不同S/C比下萘含量的变化趋势

Fig.5 Variation of naphthalene content under different S/C ratio

图6 产物中萘和菲的同位素分析

Fig.6 Isotopic analysis of naphthalene and phenanthrene in products

图7 催化剂表面发生的裂解反应

Fig.7 Cracking reaction on surface of catalyst

图8 评价实验后催化剂的XRD谱图

Fig.8 XRD patterns of spent catalysts

图9 反应后催化剂的TG和DTG图

Fig.9 TG and DTG profiles of spent catalysts

图10 反应后催化剂的Raman谱图和I D/I G值

Fig.10 Raman spectra of spent catalysts and value of I D/I G

表3 反应后催化剂的Raman高斯拟合分析

Table 3 Raman Gauss fitting analysis of catalyst after reaction

水/碳比	峰面积
水/碳比	D峰	G峰	总面积
0	202137	122233	324370
0.08	147727	82603	230330
0.12	148508	80892	229400
0.13	87057	50340	137400
0.15	59651	32537	92188
0.26	44518	24489	69007

图11 反应后催化剂的TPH图

Fig.11 TPH profiles of spent catalysts

图12 反应后催化剂的TEM图

Fig.12 TEM profiles of spent catalysts

图13 试样的N2吸附-脱附和孔径分布曲线

Fig.13 N2 adsorption-desorption isotherms and pore size distributions of catalysts

表4 催化剂的孔结构特征

Table 4 Pore characteristics of catalysts

水/碳比	比表面积/(m²/g)	平均孔径/nm	平均孔容/(cm³/g)
新鲜	139	8.19	0.37
0	21	11.15	0.07
0.12	90	4.85	0.12
0.26	126	4.65	0.15

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水蒸气对煤焦油模化物裂解行为及析碳的影响

Effect of steam atmosphere on cracking behavior and carbon deposition of coal tar model compounds

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