化工学报 ›› 2023, Vol. 74 ›› Issue (8): 3242-3255.DOI: 10.11949/0438-1157.20230426
收稿日期:
2023-04-28
修回日期:
2023-07-12
出版日期:
2023-08-25
发布日期:
2023-10-18
通讯作者:
张睿智
作者简介:
汪林正(1997—),男,博士研究生,wlz1997@sjtu.edu.cn
基金资助:
Linzheng WANG1(), Yubing LU2, Ruizhi ZHANG1(), Yonghao LUO1
Received:
2023-04-28
Revised:
2023-07-12
Online:
2023-08-25
Published:
2023-10-18
Contact:
Ruizhi ZHANG
摘要:
采用反应分子动力学模拟的方法,选择苯、甲苯和苯乙烯作为代表性VOCs组分,分析其在不同温度下发生热解和氧化的反应特性,获得其总包动力学参数,并应用于VOCs在蓄热氧化装置(RTO)中的CFD模拟。芳烃类VOCs的初始热解步骤主要发生脱氢、脱侧链和开环反应,生成对应支链结构的小分子烃类和苯,而氧化过程则直接生成CO、H2O以及少量的烃类。不同VOCs的热解与氧化反应速率存在显著差异,动力学分析表明,使用一级反应假设适用于描述VOCs热解及氧化初始阶段的反应过程。CFD模拟表明,提高入口温度可以显著提升VOCs的转化效率,而在同等VOCs处理量的前提下,提高VOCs浓度、降低进口总流量,对VOCs转化效率的改善程度与提高入口温度相当,这表明VOCs浓缩技术耦合RTO更为高效节能。
中图分类号:
汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation[J]. CIESC Journal, 2023, 74(8): 3242-3255.
图2 ReaxFF模拟所建立的分子体系示意图(a) 甲苯热解;(b) 甲苯氧化
Fig.2 Schematic of the molecular system for ReaxFF simulation(a) pyrolysis of toluene; (b) oxidation of toluene
图6 VOCs模型化合物在2500 K下热解反应的主要产物(a) 苯;(b) 甲苯;(c) 苯乙烯
Fig.6 Main products from pyrolysis of VOCs model compounds under 2500 K(a) benzene; (b) toluene; (c) styrene
图 7 VOCs模型化合物在2500 K下氧化反应的主要产物(a) 苯;(b) 甲苯;(c) 苯乙烯
Fig. 7 Main products from oxidation of VOCs model compounds under 2500 K(a) benzene; (b) toluene; (c) styrene
No. | Reaction | A/s-1 | Ea/(kJ/mol) | R2 |
---|---|---|---|---|
1 | 5.170 | 482.014 | 0.964 | |
2 | 5.132 | 171.104 | 0.973 | |
3 | 1.589 | 390.233 | 0.988 | |
4 | 1.266 | 183.197 | 0.957 | |
5 | 3.752 | 299.918 | 0.989 | |
6 | 2.061 | 134.870 | 0.961 |
表1 MD模拟VOCs转化反应
Table 1 MD simulation VOCs conversion reaction
No. | Reaction | A/s-1 | Ea/(kJ/mol) | R2 |
---|---|---|---|---|
1 | 5.170 | 482.014 | 0.964 | |
2 | 5.132 | 171.104 | 0.973 | |
3 | 1.589 | 390.233 | 0.988 | |
4 | 1.266 | 183.197 | 0.957 | |
5 | 3.752 | 299.918 | 0.989 | |
6 | 2.061 | 134.870 | 0.961 |
Reaction | ReaxFF | Experiment | ||||||
---|---|---|---|---|---|---|---|---|
Condition | A/s-1 | Ea/(kcal/mol) | Ref. | Condition | A/s-1 | Ea/(kcal/mol) | Ref. | |
toluene pyrolysis | 0.2 g/cm3, 2000—2600 K | 2.8×1017 | 95.71 | [ | shock tube, 10 atm | 1.0×1016 | 97.00 | [ |
0.1 g/cm3, 2200—2600 K | 1.589 | 93.27 | this work | shock tube, 1.5 bar | 2.7×1016 | 97.88 | [ | |
toluene oxidation | 0.2 g/cm3, 2500—3000 K, equivalence ratio: 2 | — | 64.63 | [ | shock tube, 1.95—8.85 atm, 1339—1797 K, toluene: 0.5%—1.5%,O2: 4.48%—13.45% | — | 55.09 | [ |
0.1 g/cm3, 2200—2600 K, O2: 90%(volume ratio) | 1.266 | 43.76 | this work | shock tube, 1.5—5.0 atm, 1400—2000 K, equivalence ratio: 0.5~1.875 | — | 55.24 | [ |
表2 甲苯热解及氧化的MD模拟及实验得出的动力学参数对比
Table 2 Comparison of kinetic parameters of the pyrolysis and oxidation of toluene from MD modeling and experiments
Reaction | ReaxFF | Experiment | ||||||
---|---|---|---|---|---|---|---|---|
Condition | A/s-1 | Ea/(kcal/mol) | Ref. | Condition | A/s-1 | Ea/(kcal/mol) | Ref. | |
toluene pyrolysis | 0.2 g/cm3, 2000—2600 K | 2.8×1017 | 95.71 | [ | shock tube, 10 atm | 1.0×1016 | 97.00 | [ |
0.1 g/cm3, 2200—2600 K | 1.589 | 93.27 | this work | shock tube, 1.5 bar | 2.7×1016 | 97.88 | [ | |
toluene oxidation | 0.2 g/cm3, 2500—3000 K, equivalence ratio: 2 | — | 64.63 | [ | shock tube, 1.95—8.85 atm, 1339—1797 K, toluene: 0.5%—1.5%,O2: 4.48%—13.45% | — | 55.09 | [ |
0.1 g/cm3, 2200—2600 K, O2: 90%(volume ratio) | 1.266 | 43.76 | this work | shock tube, 1.5—5.0 atm, 1400—2000 K, equivalence ratio: 0.5~1.875 | — | 55.24 | [ |
图9 不同入口浓度下总VOCs质量分数与PAHs产物(以萘计)质量分数分布
Fig.9 Mass fraction distribution of total VOCs and PAHs (counting naphthalene) at different inlet concentrations
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