甲醇水蒸气重整本征动力学和模拟研究

doi:10.12422/j.issn.1006-396X.2025.05.009

摘要/Abstract

摘要：

为解决Aspen化工模拟中自带催化剂数据库的局限性，提出一种PL（Power Law）型双速率动力学模型，将动力学模型导入Aspen Plus进行制氢多过程模拟，考察了在模拟过程中引入催化剂对反应的影响，旨在实现更真实的化工过程模拟。结果表明，该双速率动力学模型可以反映真实的制氢状况；提高温度和降低液时空速，均有利于提高甲醇转化率，但同时增大CO的选择性；水碳物质的量比（水碳比）对反应的影响较小，考虑能源消耗选择水碳比1.0~1.4为宜；当反应温度为280 ℃、进料流速为1.5 mL/min时，经甲醇水蒸气重整、水汽变换和CO催化氧化后，产物中CO的体积分数仅为6.89 μL/L，产物可用于质子交换膜燃料电池(PEMFC)的应用中。

关键词: 甲醇水蒸气重整, 本征动力学, Aspen Plus, 制氢, 过程模拟

Abstract:

In order to resolve the limitation of the built-in catalyst database in Aspen simulations,a dual-rate kinetic model based on the Power Law (PL) formulation is proposed.The kinetic model is integrated into Aspen Plus for multi-process simulation of hydrogen production.By incorporating the influence of catalysts on the reactions during the simulation,a more realistic chemical process simulation is achieved.The dual-rate kinetic model accurately reflects actual hydrogen production conditions: increasing temperature and reducing liquid hourly space velocity (LHSV) both enhance methanol conversion and simultaneously increase CO selectivity.The steam-to-carbon molar ratio has a minor impact on the reaction.By considering energy consumption,the optimal range of the steam-to-carbon molar ratio is 1.0~1.4.Under the condition in which the reaction temperature is 280 °C and the feed flow rate is 1.5 mL/min,the multi-process simulation results demonstrate that the CO concentration in the product is reduced to only 6.89 μL/L after methanol steam reforming, water-vapor shift,and CO selective oxidation.This CO concentration meets the requirements for proton exchange membrane fuel cells(PEMFC).

Key words: Methanol steam reforming, Intrinsic kinetic, Aspen Plus, Hydrogen production, Progress simulation

中图分类号:

TQ013.2

李谡民, 董世城, 宋仁升, 王斌, 高伟, 潘立卫. 甲醇水蒸气重整本征动力学和模拟研究[J]. 石油化工高等学校学报, 2025, 38(5): 69-80.

Sumin LI, Shicheng DONG, Rensheng SONG, Bin WANG, Wei GAO, Liwei PAN. Intrinsic Kinetic and Simulation Study of Methanol Steam Reforming[J]. Journal of Petrochemical Universities, 2025, 38(5): 69-80.

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链接本文: https://journal.lnpu.edu.cn/syhg/CN/10.12422/j.issn.1006-396X.2025.05.009

https://journal.lnpu.edu.cn/syhg/CN/Y2025/V38/I5/69

图/表 21

图1 催化剂粒径对甲醇转化率的影响

Fig.1 The influence of catalyst particle size on methanol conversions

图2 液时空速对外扩散的影响

Fig.2 The influence of liquid hourly space velocity on external diffusion

表1 MSR动力学实验数据

Table 1 Experimental data on the kinetics of MSR

序号	A	B/h^-1	C/℃	$F C O 2$ /（mol·h^-1）	F_CO/（mol·h^-1）	$X C H 3 O H$ /%
1	1.0	0.6	220	7.95×10^-3	3.62×10^-4	69.32
2	1.0	1.8	240	1.67×10^-2	2.70×10^-4	47.10
3	1.0	3.0	260	3.00×10^-2	3.68×10^-4	50.63
4	1.0	4.2	280	4.29×10^-2	1.10×10^-3	52.36
5	1.0	5.4	300	6.00×10^-2	3.59×10^-3	58.87
6	1.2	1.8	220	1.47×10^-2	2.21×10^-4	41.62
7	1.2	3.0	240	2.14×10^-2	2.60×10^-4	38.72
8	1.2	4.2	260	3.41×10^-2	7.37×10^-4	44.45
9	1.2	5.4	280	5.28×10^-2	1.40×10^-3	53.84
10	1.2	0.6	300	8.56×10^-3	2.10×10^-3	95.19
11	1.4	3.0	220	1.68×10^-2	1.09×10^-4	32.31
12	1.4	4.2	240	2.53×10^-2	2.67×10^-4	34.82
13	1.4	5.4	260	4.03×10^-2	9.11×10^-4	43.69
14	1.4	0.6	280	8.41×10^-3	1.38×10^-3	93.24
15	1.4	1.8	300	2.39×10^-2	3.91×10^-3	88.53
16	1.6	4.2	220	1.78×10^-2	6.14×10^-5	25.82
17	1.6	5.4	240	8.33×10^-2	2.33×10^-4	29.02
18	1.6	0.6	260	7.82×10^-3	6.33×10^-4	90.58
19	1.6	1.8	280	2.35×10^-2	1.16×10^-3	83.40
20	1.6	3.0	300	3.62×10^-2	2.63×10^-3	78.69
21	1.8	5.4	220	1.62×10^-2	8.90×10^-5	19.39
22	1.8	0.6	240	7.83×10^-3	2.34×10^-4	86.51
23	1.8	1.8	260	1.85×10^-2	5.97×10^-4	68.41
24	1.8	3.0	280	3.10×10^-2	9.68×10^-4	68.62
25	1.8	4.2	300	5.07×10^-2	1.71×10^-3	80.35

表1 MSR动力学实验数据

Table 1 Experimental data on the kinetics of MSR

序号	A	B/h^-1	C/℃	$F C O 2$ /（mol·h^-1）	F_CO/（mol·h^-1）	$X C H 3 O H$ /%
1	1.0	0.6	220	7.95×10^-3	3.62×10^-4	69.32
2	1.0	1.8	240	1.67×10^-2	2.70×10^-4	47.10
3	1.0	3.0	260	3.00×10^-2	3.68×10^-4	50.63
4	1.0	4.2	280	4.29×10^-2	1.10×10^-3	52.36
5	1.0	5.4	300	6.00×10^-2	3.59×10^-3	58.87
6	1.2	1.8	220	1.47×10^-2	2.21×10^-4	41.62
7	1.2	3.0	240	2.14×10^-2	2.60×10^-4	38.72
8	1.2	4.2	260	3.41×10^-2	7.37×10^-4	44.45
9	1.2	5.4	280	5.28×10^-2	1.40×10^-3	53.84
10	1.2	0.6	300	8.56×10^-3	2.10×10^-3	95.19
11	1.4	3.0	220	1.68×10^-2	1.09×10^-4	32.31
12	1.4	4.2	240	2.53×10^-2	2.67×10^-4	34.82
13	1.4	5.4	260	4.03×10^-2	9.11×10^-4	43.69
14	1.4	0.6	280	8.41×10^-3	1.38×10^-3	93.24
15	1.4	1.8	300	2.39×10^-2	3.91×10^-3	88.53
16	1.6	4.2	220	1.78×10^-2	6.14×10^-5	25.82
17	1.6	5.4	240	8.33×10^-2	2.33×10^-4	29.02
18	1.6	0.6	260	7.82×10^-3	6.33×10^-4	90.58
19	1.6	1.8	280	2.35×10^-2	1.16×10^-3	83.40
20	1.6	3.0	300	3.62×10^-2	2.63×10^-3	78.69
21	1.8	5.4	220	1.62×10^-2	8.90×10^-5	19.39
22	1.8	0.6	240	7.83×10^-3	2.34×10^-4	86.51
23	1.8	1.8	260	1.85×10^-2	5.97×10^-4	68.41
24	1.8	3.0	280	3.10×10^-2	9.68×10^-4	68.62
25	1.8	4.2	300	5.07×10^-2	1.71×10^-3	80.35

图3 甲醇水蒸气重整制氢多过程流程图

Fig.3 Multi-process flow diagram for hydrogen production by methanol steam reforming

表2 各反应器中发生的主要反应

Table 2 The main reactions that occur in each reactor

反应器	反应式	Δ_rH_{298 K}/(kJ·mol^-1)	反应温度/℃
重整反应器	CH₃OH+H₂O→3H₂+CO₂	49.4	150~350
重整反应器	CO+H₂O→CO₂+H₂	-41.2	150~350
水汽变换反应器	CO+H₂O→CO₂+H₂	-41.2	150~250
CO氧化反应器	2CO+O₂→2CO₂	-565.9	150~300
CO氧化反应器	2H₂+O₂→2H₂O	-483.6	150~300

表3 甲醇水蒸气重整本征动力学的模型参数1

Table 3 Intrinsic kinetic parameter 1 of methanol steam reforming

参数	k_SR/[mol·(s·g·kPa^0.418)^-1]	k_RWGS/[mol·(s·g·kPa^0.531)^-1]	E_SR/(J·mol^-1)	E_RWGS/(J·mol^-1)
数值	47.62	76.22	58 013	87 204

表4 甲醇水蒸气重整本征动力学的模型参数2

Table 4 Intrinsic kinetic parameter 2 of methanol steam reforming

参数	a	b	c	d	e	f	g	h
数值	0.684	0.067	-0.114	-0.219	0.491	0.443	-0.109	-0.294

表5 模型参数的统计检验结果

Table 5 The statistical test results of the model parameters

方程	M	M_P	R²	F	F_0.05
SR	25	6	0.979 1	138	2.49
RWGS	25	6	0.971 0	83	2.49

图4 模型实验值与预测值间的相对残差

Fig.4 The relative residuals between the experimental values and the model-predicted values

图5 甲醇水蒸气重整模拟流程图

Fig.5 Flow diagram of methanol steam reforming process

图6 反应温度和液时空速对甲醇转化率影响的2D和3D图

Fig.6 2D and 3D graphs of the influence of reaction temperature and liquid highly space velocity on the CH3OH conversion

图7 反应温度和液时空速对CO选择性影响的2D和3D图

Fig.7 2D and 3D graphs of the influence of reaction temperature and liquid highly space velocity on the CO selectivity

图8 反应温度和水碳比对甲醇转化率影响的2D和3D图

Fig.8 2D and 3D graphs of the influence of reaction temperature and water-to-carbon molar ratio on the conversion of CH3OH

图9 反应温度和水碳比对CO选择性影响的2D和3D图

Fig.9 2D and 3D graphs of the influence of reaction temperature and water-to-carbon molar ratio on the CO selectivity

表6 不同水碳比下流程的模拟数据

Table 6 Simulation data of the process under different water-to-carbon ratios

水碳比	加热器热负荷/W	反应器热负荷/W	总热负荷/W	$X C H 3 O H$ /%	S_CO/%	H₂产量/（mol·h^-1）
1.0	1.221 0	0.635 6	1.856 6	90.08	7.51	0.105 4
1.2	1.392 8	0.614 5	1.907 3	91.91	7.39	0.100 3
1.4	1.360 6	0.595 2	1.955 8	93.34	7.38	0.095 5
1.6	1.435 3	0.578 1	2.013 4	94.50	7.41	0.090 9
1.8	1.507 3	0.562 9	2.070 2	95.47	7.48	0.086 7
2.0	1.597 0	0.549 7	2.146 7	96.28	7.56	0.082 8

表6 不同水碳比下流程的模拟数据

Table 6 Simulation data of the process under different water-to-carbon ratios

水碳比	加热器热负荷/W	反应器热负荷/W	总热负荷/W	$X C H 3 O H$ /%	S_CO/%	H₂产量/（mol·h^-1）
1.0	1.221 0	0.635 6	1.856 6	90.08	7.51	0.105 4
1.2	1.392 8	0.614 5	1.907 3	91.91	7.39	0.100 3
1.4	1.360 6	0.595 2	1.955 8	93.34	7.38	0.095 5
1.6	1.435 3	0.578 1	2.013 4	94.50	7.41	0.090 9
1.8	1.507 3	0.562 9	2.070 2	95.47	7.48	0.086 7
2.0	1.597 0	0.549 7	2.146 7	96.28	7.56	0.082 8

表7 初始反应条件

Table 7 The establishment of the initial reaction conditions

反应条件	初始设定值	灵敏度分析范围
进料流速/（mL·min^-1）	3.0	0.1~5.0
甲醇反应温度/℃	280	200~300
WGS1温度/℃	180	-
WGS2温度/℃	150	-
CO氧化温度/℃	200	-
反应压力/kPa	101.325	-
水碳比（反应进料）	1.4	-
碳氧物质的量比（PROX）	1.5	-

图10 反应温度对气体产物摩尔流率的影响

Fig.10 The influence of reaction temperature on the molar flow rate of gas products

图11 反应温度对甲醇转化率及产物CO体积分数的影响

Fig.11 The influence of reaction temperature on the methanol conversion and the volume fraction of product CO

图12 总进料流速对气体产物摩尔流率的影响

Fig.12 The influence of the total feed flow rate on the molar flow rate of the gas products

图13 总进料流速对甲醇转化率及产物CO体积分数的影响

Fig.13 The influence of the total feed flow rate on methanol conversion and volume fraction of product CO

图14 各产物气体占比的实验值与模拟值的比较

Fig.14 Comparison of the experimental and simulated values for the proportions of each product

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