Intrinsic Kinetic and Simulation Study of Methanol Steam Reforming

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

Abstract

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

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

CLC Number:

TQ013.2

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.

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.

0
/ / Recommend

Add to citation manager EndNote|Ris|BibTeX

URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2025.05.009

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

Figures/Tables 21

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

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

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

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

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

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

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

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

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

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

Fig.5 Flow diagram of methanol steam reforming process

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

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

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

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

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

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

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	-

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

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

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

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

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

References 23

[1]	赵玉晴，蒋文明，刘杨.氢能产业发展现状及未来展望［J］.安全健康和环境，2023，23（1）：1-12.
	ZHAO Y Q，JIANG W M，LIU Y.Development status and future prospects of hydrogen energy industry［J］.Safety Health & Environment，2023，23（1）：1-12.
[2]	LORENZUT B，MONTINI T，DE ROGATIS L，et al.Hydrogen production through alcohol steam reforming on Cu/ZnO-based catalysts［J］.Applied Catalysis B-Environmental，2011，101（3-4）：397-408.
[3]	韩笑，张兴华，闫华光，等.全球氢能产业政策现状与前景展望［J］.电力信息与通信技术，2021，19（12）：27-34.
	HAN X，ZHANG X H，YAN H G，et al.Current situation and prospect of global hydrogen energy industry policy［J］.Electric Power Information and Communication Technology，2021，19（12）：27-34.
[4]	ROSLI R E，SULONG A B，DAUD W R W，et al.A review of high-temperature proton exchange membrane fuel cell（HT-PEMFC） system［J］.International Journal of Hydrogen Energy，2017，42（14）：9293-9314.
[5]	OLAH G A.Towards oil independence through renewable methanol chemistry［J］.Angewandte Chemie International Edition，2013，52（1）：104-107.
[6]	刘玉娟，许骥，佟宇飞，等.氧化铈纳米材料合成方法的研究进展［J］.辽宁石油化工大学学报，2017，37（5）：8-12.
	LIU Y J，XU J，TONG Y F，et al.Progress in research of the synthesis methods of nanometer ceria［J］.Journal of Liaoning Shihua University，2017，37（5）：8-12.
[7]	YAQOOB L，NOOR T，IQBAL N.Recent progress in development of efficient electrocatalyst for methanol oxidation reaction in direct methanol fuel cell［J］.International Journal of Energy Research，2021，45（5）：6550-6583.
[8]	JIANG W，MA X X，ZHANG D K，et al.Highly efficient catalysts for hydrogen generation through methanol steam reforming：A critical analysis of modification strategies，deactivation，mechanisms and kinetics［J］.Journal of Industrial and Engineering Chemistry，2024，130：54-72.
[9]	ZHANG Y D，GUO S P，TIAN Z Y，et al.Experimental investigation of steam reforming of methanol over La₂CuO₄/CuZnAl-oxides nanocatalysts［J］.Applied Energy，2019，254：113022.
[10]	JING J，LI L M，CHU W，et al.Microwave-assisted synthesis of high performance copper-based catalysts for hydrogen production from methanol decomposition［J］.International Journal of Hydrogen Energy，2018，43（27）：12059-12068.
[11]	WEI Y H，LI S Y，JING J，et al.Synthesis of Cu–Co catalysts for methanol decomposition to hydrogen production via deposition–precipitation with urea method［J］.Catalysis Letters，2019，149（10）：2671-2682.
[12]	SUN Q Y，MEN Y，WANG J G，et al.Support effect of Ag/ZnO catalysts for partial oxidation of methanol［J］.Inorganic Chemistry Communications，2018，92：51-54.
[13]	杨昕毓，孙舒，石岩，等.水热时间对CuO/CeO₂催化甲醇水蒸气重整制氢的影响［J］.石油化工高等学校学报，2025，36（2）：63-69.
	YANG X Y，SUN S，SHI Y，et al.Effects of hydrothermal reaction time on the performance of CuO/CeO₂ catalyst for hydrogen production from steam reforming methanol［J］.Journal of Petrochemical Universities，2025，36（2）：63-69.
[14]	KIM J H，JANG Y S，KIM D H.Multiple steady states in the oxidative steam reforming of methanol［J］.Chemical Engineering Journal，2018，338：752-763.
[15]	SUN Z，ZHANG X H，LI H F，et al.Chemical looping oxidative steam reforming of methanol：A new pathway for auto-thermal conversion［J］.Applied Catalysis B-Environmental，2020，269：118758.
[16]	JIANG Y L，HUANG Q，WANG F A，et al.Simulation study on hydrogen production from methanol partial oxidation steam reforming over a Cu/ZnO/A1₂O₃ catalyst［J］.Journal of Fuel Chemistry and Technology，2001（3）：207-213.
[17]	SÁ S，SOUSA J M，MENDES A.Steam reforming of methanol over a CuO/ZnO/Al₂O₃ catalyst，part I：Kinetic modelling［J］.Chemical Engineering Science，2011，66（20）：4913-4921.
[18]	AMPHLETT J C，CREBER K A M，DAVIS J M，et al.Hydrogen production by steam reforming of methanol for polymer electrolyte fuel cells［J］.International Journal of Hydrogen Energy，1994，19（2）：131-137.
[19]	PEPPLEY B A，AMPHLETT J C，KEARNS L M，et al.Methanolsteam reforming on Cu/ZnO/Al₂O₃ part 1：The reaction network［J］.Applied Catalysis A：General，1999，179（1-2）：21-29.
[20]	刘金东.Cu/ZnO/CeO₂催化CO₂加氢制甲醇动力学研究及Aspen流程模拟［D］.泉州：华侨大学，2022.
[21]	ZHANG F X，SHI Y S，YANG L J，et al.Kinetics for hydrogen production by methanol steam reforming in fluidized bed reactor［J］.Science Bulletin，2016，61（5）：401-405.
[22]	ÖZCAN O，AKIN A N.Methanol steam reforming kinetics using a commercial CuO/ZnO/Al₂O₃ catalyst：Simulation of a reformer integrated with HT-PEMFC system［J］.International Journal of Hydrogen Energy，2023，48（60）：22777-22790.
[23]	DZURYK S，REZAEI E.Intensification of the reverse water gas shift reaction by water-permeable packed-bed membrane reactors［J］.Industrial & Engineering Chemistry Research，2020，59（42）：18907-18920.