蜡油加氢脱硫集总动力学模型研究

doi:10.16085/j.issn.1000-6613.2019-1137

摘要/Abstract

摘要：

以减压蜡油（VGO）加氢脱硫（HDS）小试实验数据为基础，针对VGO HDS反应速率快慢，将原料中硫化物划分为快反应速率、中反应速率、慢反应速率3个集总，建立VGO HDS反应三集总动力学模型，并采用Levenberg-Marguardt算法对模型参数进行了求解。结果表明，该模型平均相对误差仅为5.18%，预测值可靠，外推性良好，模型参数计算结果符合加氢反应规律。通过模型计算，分析了液时空速、反应温度、反应压力对VGO HDS过程的影响，得到了HDS详细的反应规律，可为VGO HDS反应集总动力学研究和实验分析提供参考。

关键词: 减压蜡油, 加氢脱硫, 集总动力学, 加氢反应规律

Abstract:

Based on the experimental data of vacuum gas oil hydrodesulfurization (VGO HDS) , the reactions of the sulfides in raw material were divided into three lumps: fast reaction rate lump, medium reaction rate lump and slow reaction rate lump. The three lumped kinetic models of VGO HDS reactions were then established, and the model parameters were estimated by the Levenberg-Marguardt algorithm. The results showed that the average relative error of the model was only 5.18%. The predicted value of the model was reliable and the extrapolation was good. The model parameters were in accordance with the law of hydrogenation reaction. The effects of liquid hourly space velocity (LHSV), reaction temperature (T) and reaction pressure (P) on VGO HDS process were analyzed by model calculation. Detailed reaction rules of HDS were obtained, which can provide reference for the lumped kinetics and experimental study of VGO HDS reactions.

Key words: vacuum gas oil (VGO), hydrodesulfurization, lumped kinetics, hydrogenation reaction law

中图分类号:

TE624.4

朱永红,霍鹏举,杨天华,李伟,韩磊,杨程. 蜡油加氢脱硫集总动力学模型研究[J]. 化工进展, 2020, 39(4): 1339-1347.

Yonghong ZHU,Pengju HUO,Tianhua YANG,Wei LI,Lei HAN,Cheng YANG. Lumped kinetic models for VGO hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1339-1347.

图/表 11

表1 原料基本性质

项目	数据	性质	数据/K
密度(20℃)/g·mL^-1	0.9289	IBP	548
残炭（质量分数）/%	0.41	10%（体积分数）	608
碳（质量分数）/%	86.178	30%（体积分数）	652
氢（质量分数）/%	11.596	50%（体积分数）	686
硫（质量分数）/%	1.92	70%（体积分数）	717
氮（质量分数）/%	0.254	90%（体积分数）	768
H/C	1.61	EBP	824

图1 实验装置工艺流程

表2 催化剂理化性质

组成	质量分数/%	物化性质	数据
MoO₃	22.14	外观	三叶草
CoO	6.15	比表面积/m²·g^-1	181
SiO₂	4.25	孔体积/cm3·g^-1	0.46
NaO₂	0.04	堆密度/g·mL^-1	0.72
P₂O₅	3.61	平均直径/nm	8.41
Al₂O₃	63.21	平均长度/mm	1.60

图2 VGO HDS三集总反应网络

表3 VGO加氢过程各实验点工艺条件和产物中硫含量结果

T/K	P/MPa	LHSV/h^-1	V(H₂)/V(Oil)	w_S/μg·g^-1
658	6	1.0	500	1429
658	4	1.0	500	1670
658	4	1.5	500	2027
653	4	1.5	500	2503
653	4	1.0	500	2116
653	6	1.0	500	1822
653	6	1.5	500	2311
653	6	2.0	500	3000
658	2	1.0	500	1935
658	4	2.0	500	2808
663	2	1.0	500	1507
663	6	2.0	500	2471

表4 VGO HDS集总动力学模型参数

集总	$x i$	k_i₀/h^-1	E_i/kJ·mol^-1	$a i$	$b i$
F	68.68×10^-2	2.3919×10⁶	73.66	0.1899	0.1000
M	22.71×10^-2	8.5421×10¹¹	144.08	0.2000	1.4999
S	8.61×10^-2	3.4997×10¹³	184.73	0.4000	1.7811

表4 VGO HDS集总动力学模型参数

集总	$x i$	k_i₀/h^-1	E_i/kJ·mol^-1	$a i$	$b i$
F	68.68×10^-2	2.3919×10⁶	73.66	0.1899	0.1000
M	22.71×10^-2	8.5421×10¹¹	144.08	0.2000	1.4999
S	8.61×10^-2	3.4997×10¹³	184.73	0.4000	1.7811

图3 产物中硫含量的实验值与模型计算值比较

图4 VGO HDS集总动力学模型预测的产物中不同集总硫含量随LHSV的变化规律

[T=658K； P=6MPa； V(H2)/V(Oil)=500]

图5 VGO HDS集总动力学模型预测的产物中不同集总硫含量在不同反应温度下随LHSV的变化规律

[P=6MPa; V(H2)/V(Oil)=500]

图6 VGO HDS集总动力学模型预测的产物中不同集总硫含量在不同P下随LHSV的变化规律

[T=658K； V(H2)/V(Oil)=500]

图7 VGO HDS集总动力学模型预测的产物中总硫含量在不同P下随T的变化规律

[LHSV=1.5h-1； V(H2)/V(Oil)=500]

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