Optimization of Propane Dehydrogenation Process Conditions over Pt⁃Based Catalyst Based on Response Surface Methodology

doi:10.12422/j.issn.1006-396X.2025.02.009

Abstract

Abstract:

The propane dehydrogenation reaction is thermodynamically unfavorable, tnecessitating kinetic control through optimized process conditions. Single?factor experiments and multi?factor Response Surface Methodology (RSM) were employed to analyze and optimize propane dehydrogenation conditions over a PtSnK/Al?O? catalyst, followed by experimental verification. First, single?factor experiments determined the range of values for the factors to be studied in the response surface methodology. Then, a Box?Behnken design with three factors (reaction temperature, space velocity, and hydrogen?hydrocarbon ratio) was used to optimize the reaction conditions of propane dehydrogenation by multifactor response surface methodology with propylene selectivity as the response value, and finally, the optimized process conditions were experimentally verified. Results indicated that the optimal reaction temperature, VHSV, and H?/C?H? molar ratio were 605 ℃, 2 200 h?1, and 0.6, respectively. The theoretical propylene selectivity prediction under these conditions was 93.01%. The order of influence weight from largest to smallest was reaction temperature > H?/C?H? molar ratio > VHSV. Experimental verification yielded a propylene selectivity of 93.00% and propane conversion of 32.00%. Experimental determination of propylene selectivity is consistent with RSM predictions, confirming the model's reliability and credibility.

Key words: Catalysts, Propane dehydrogenation, Process conditions, Selectivity, Response surface methodology

摘要：

丙烷脱氢反应在热力学上处于不利状态，因此需要通过优化工艺条件来实现动力学控制。利用单因素实验和多因素响应面法分析优化PtSnK/Al₂O₃催化剂上丙烷脱氢工艺条件，并进行了实验验证。通过单因素实验为响应面法筛选出考察因素取值范围；采用反应温度、体积空速、氢烃比（氢气与丙烷的物质的量比）3个因素的Box?Behnken设计，以丙烯选择性为响应值，对丙烷脱氢反应条件进行了多因素响应面法分析优化；对优化后的工艺条件进行了实验验证。结果表明，优化的反应温度为605 ℃，体积空速为2 200 h^-1，氢烃比为0.6，该工艺条件下丙烯选择性的理论预测值为93.01%；各因素影响的权重从大到小的顺序为反应温度>氢烃比>体积空速；优化后丙烯选择性的实验测定值为93.00%，丙烷转化率为32.00%，丙烯选择性的实验测定值与通过多因素响应面法预测的结果一致，说明模型可靠、可信。

关键词: 催化剂, 丙烷脱氢, 工艺条件, 选择性, 响应面法

CLC Number:

TQ032

Xilin PIAO, Hai WAN, Haotian CHI, Haijuan ZHANG. Optimization of Propane Dehydrogenation Process Conditions over Pt⁃Based Catalyst Based on Response Surface Methodology[J]. Journal of Petrochemical Universities, 2025, 38(2): 72-80.

朴茜琳, 万海, 迟昊天, 张海娟. 基于响应面法的Pt基催化剂上丙烷脱氢工艺条件优化[J]. 石油化工高等学校学报, 2025, 38(2): 72-80.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2025.02.009

https://journal.lnpu.edu.cn/syhg/EN/Y2025/V38/I2/72

Figures/Tables 11

Fig.1 Schematic diagram of the catalyst impregnation process

Fig.2 Dark field TEM and particle size distribution of the active phase Pt in the catalyst of PtSnK/Al2O3 catalysts

Fig.3 Effect of reaction temperature on the conversion rate of propane dehydrogenation and the selectivity for propylene, and the distribution of reaction products at different temperatures

Fig.4 Effect of space velocity on the conversion rate of propane and the selectivity for propylene, and the distribution of reaction products at different volumetric airspeed conditions

Fig.5 Effect of hydrogen-to-hydrocarbon ratio on the conversion rate of propane and the selectivity for propylene， and the distribution of reaction products at different hydrogen to hydrocarbon ratios

Table 1 Three-factor, three-level response surface methodology experimental design

因素	水平
因素	-1	0	1
A/℃	600	620	640
B/h^-1	1 000	2 000	3 000
C	0.5	1.0	1.5

Table 2 Box-Behnken response surface experiment results

序号	A/℃	B/h^-1	C	D/%	序号	A/℃	B/h^-1	C	D/%
1	640	3 000	1.0	84.70	10	600	2 000	1.5	92.60
2	620	2 000	1.0	91.33	11	640	2 000	0.5	84.60
3	620	2 000	1.0	91.43	12	600	3 000	1.0	93.70
4	620	2 000	1.0	91.64	13	620	1 000	0.5	91.42
5	620	1 000	1.5	90.40	14	640	1 000	1.0	84.00
6	600	2 000	0.5	93.40	15	620	2 000	1.0	91.70
7	620	3 000	0.5	92.30	16	620	2 000	1.0	91.53
8	600	1 000	1.0	92.70	17	640	2 000	1.5	84.00
9	620	3 000	1.5	91.20

Table 3 Analysis of variance results of Box-Behnken response surface experiment

实验条件	差平方和	均方	影响程度（F）	失拟程度（P）	显著性
Model模型	188.610	20.960	878.32	<0.000 1	极显著
A	154.000	154.000	6 454.37	<0.000 1	极显著
B	1.430	1.430	59.85	0.000 1	极显著
C	1.550	1.550	64.91	<0.000 1	极显著
残差	0.170	0.024
失拟相	0.076	0.025	1.12	0.441 3	不显著
纯误差	0.091	0.023
总相关	188.780

Fig.6 Residual normal plot and distribution diagram of theoretical predicted values and experimental measured values

Fig.7 3D response surface plot and contour plot of propylene selectivity influenced by reaction temperature, volumetric space velocity, and hydrogen to hydrocarbon ratio

Fig.8 Propane dehydrogenation conversion and propylene selectivity under optimal process conditions

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