超临界甲烷在活性炭与典型金属有机框架材料上的吸附平衡

郭栋; 李姗姗; 王虎; 郑青榕

doi:10.1016/S1872-5813(23)60364-0

超临界甲烷在活性炭与典型金属有机框架材料上的吸附平衡

doi: 10.1016/S1872-5813(23)60364-0

集美大学轮机工程学院福建省船舶与海洋工程重点实验室, 福建厦门 361021

基金项目: 国家自然科学基金(51979121)，福建省自然科学基金重点项目(2020J02041)和厦门市科技计划项目（3502Z20226011）资助

详细信息

作者简介:
郭栋（1999—），硕士研究生，研究方向：从事燃气（氢气、甲烷）吸附储存技术研究。E-mail:guod1201@163.com

通讯作者:
E-mail: qrzheng816@sina.com, zhengqr@jmu.edu.cn

中图分类号: O647.32
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出版历程
- 收稿日期: 2023-02-18
- 修回日期: 2023-04-08
- 录用日期: 2023-04-11
- 网络出版日期: 2023-05-06

Adsorption equilibrium of methane on activated carbon and typical metal organic frameworks

Provincial Key Laboratory of Naval Architecture & Ocean Engineering, Institute of Marine Engineering, Jimei University, Xiamen 361021, China

Funds: The project was supported by National Natural Science Foundation of China (51979121), Natural Science Foundation of Fujian Province (2020J02041) and Xiamen Municipal Bureau of Sciences & Technology (3502Z20226011)

摘要

摘要: 吸附模型预测的准确性对吸附工艺系统后续的工程设计极为关键。针对吸附天然气（ANG）应用的吸附剂研发，试制了SAC-02活性炭、HKUST-1和MIL-101(Cr)，通过微观形貌观察、氮气物理吸附和293.15–313.15 K、0–4 MPa条件下甲烷吸附等温线测定，采用Toth、D-A和Ono-Kondo等方程对实验数据进行关联预测比较，由等量吸附热和吸附相密度分析这些吸附剂样品对甲烷的吸附性能。结果发现，在测试范围内，Toth方程预测的吸附平衡数据精度最高，可用于ANG系统的吸附平衡分析；甲烷在MIL-101(Cr)上的平均等量吸附热最大，吸附相密度比液态甲烷的密度小但随压力的增高而增大，比活性炭和HKUST-1更适合于甲烷吸附。
- 甲烷 /
- 活性炭 /
- MOF_S /
- 吸附平衡
Abstract: The accuracy of the adsorption model in predicting equilibrium data is crucial to the design of the adsorption system. To develop adsorbents suitable for the storage of natural gas by adsorption, activated carbon SAC-02, HKUST-1 and MIL-101(Cr) were synthesized and characterized in terms of structural morphology observation, nitrogen physisorption at 77.15 K, and methane adsorption at 293.15–323.15 K、 0–4 MPa. The methane adsorption isotherms were comparatively correlated with the Toth, D-A and Ono-Kondo equations and the performances of the adsorbent samples were evaluated in terms of the isosteric adsorption heat and the adsorbed phase density. The results indicate that in comparison with the D-A and Ono-Kondo equations, the Toth equation displays much smaller relative errors in correlating the methane adsorption data and is then more suitable for the adsorption equilibrium analysis on the adsorbed natural gas (ANG) system. MIL-101(Cr) exhibits the largest mean isosteric heat for methane adsorption and the density of the adsorbed methane phase is smaller than that of the liquid methane but increases with the equilibrium pressure; overall, MIL-101(Cr) with highest adsorption capacity is more suitable for methane adsorption than activated carbon and HKUST-1.
- methane /
- activated carbon /
- MOF_S /
- adsorption equilibrium

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图 1 实验装置示意图

Figure 1 Schematic design of the experimental setup for methane adsorption

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图 2 HKUST-1 的 XRD谱图(a)和晶体颗粒的 SEM 照片(b)

Figure 2 XRD pattern (a) and SEM image (b) of the HKUST-1 adsorbent

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图 3 MIL-101(Cr)的 XRD谱图(a)和晶体颗粒的 SEM照片(b)

Figure 3 XRD pattern (a) and SEM image (b) of the MIL-101(Cr) adsorbent

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图 4 77.15 K时氮在样品上的吸附等温线(a)及其孔径分布(b)

Figure 4 Isotherms of nitrogen adsorption at 77.15 K (a) and the pore size distribution curves of three adsorbent samples (b)

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图 5 甲烷在 SAC-02 活性炭 (a)、HKUST-1(b)和 MIL-101(Cr) (c)上的吸附等温线

Figure 5 Adsorption isotherms of methane at a low pressure on SAC-02 activated carbon (a), HKUST-1 (b) and MIL-101(Cr) (c)

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图 6 甲烷在 SAC-02 活性炭(a)、HKUST-1(b)和 MIL-101 (Cr) (c)上的吸附等温线

Figure 6 Isotherms of methane adsorption on the activated carbon SAC-02 (a), HKUST-1 (b) and MIL-101(Cr) (c)

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图 7 模型预测甲烷在 SAC-02 活性炭(a)、HKUST-1(b) 和 MIL-101 (Cr)(c) 上吸附平衡数据的相对误差

Figure 7 Relative errors of adsorption equilibrium data predicted by different models on the adsorbents of activated carbon SAC-02 (a), HKUST-1 (b) and MIL-101(Cr) (c)

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图 8 甲烷在吸附剂上的等量吸附热

Figure 8 Isosteric heats of methane adsorption on the different adsorbent samples

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图 9 303.15 K时甲烷在吸附剂上的吸附相密度

Figure 9 Densities of the adsorbed methane phase on different adsorbents at 303.15 K

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表 1 吸附剂的结构参数

Table 1 Textural properties of the adsorbent samples

Sample	Specific surface area / (m²·g⁻¹)	Average pore size / nm	Micropore volume / (cm³·g⁻¹)
SAC-02	1484	1.2	0.58
HKUST-1	1850	0.70	0.77
MIL-101(Cr)	3141	1.86	1.09

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表 2 甲烷在吸附剂上吸附的热力学参数

Table 2 Thermodynamic parameters of methane adsorption on the adsorbent samples

Adsorbent	T / K	H_p /(mmol·Pa⁻¹·g⁻¹)	q_st0 /(kJ·mol⁻¹)	Isosteric adsorption heat /(kJ·mol⁻¹)
SAC-02	293.15	0.00958	23.952	24.035
	303.15	0.00786	24.035
	313.15	0.00544	24.118
HKUST-1	293.15	0.01077	26.601	26.685
	303.15	0.00824	26.685
	323.15	0.00571	26.768
MIL-101(Cr)	293.15	0.00608	29.418	29.501
	303.15	0.00422	29.501
	313.15	0.00358	29.584

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表 3 甲烷在吸附剂上吸附平衡的Toth方程拟合参数

Table 3 Parameters fitted with the Toth equation for methane adsorption on the adsorbents

Sample	T / K	b / MPa⁻¹	t	n_m /(mmol∙g⁻¹)	v_a /(cm³·g⁻¹)
SAC-02	293.15	2.762	0.2426	48.01	0.7241
	303.15	2.103	0.2843	42.00	0.8526
	313.15	0.831	0.3161	35.85	0.8253
HKUST-1	293.15	0.837	0.2940	36.89	0.2164
	303.15	0.250	0.5367	26.86	1.6300
	313.15	0.546	0.6660	6.51	0.4563
MIL-101(Cr)	293.15	0.111	0.4549	141.50	1.9700
	303.15	0.120	0.6155	87.85	2.5360
	313.15	0.159	0.7390	50.63	1.3440

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表 4 甲烷在吸附剂上吸附平衡的D-A方程拟合参数

Table 4 Parameters fitted with the D-A equation for methane adsorption on three adsorbents

Sample	T / K	n₀ /(mmol∙g⁻¹)	E /(J∙mol⁻¹)	q
SAC-02	293.15	6.816	8580	1.816
	303.15	6.686	8508	1.662
	313.15	6.104	8501	1.931
HKUST-1	293.15	4.860	7982	1.645
	303.15	4.640	7769	1.329
	313.15	4.401	8420	1.707
MIL-101(Cr)	293.15	21.210	5485	1.468
	303.15	18.660	5742	1.585
	313.15	18.990	6112	1.614

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表 5 甲烷在吸附剂上吸附平衡的Ono-Kondo方程参数

Table 5 Parameters of the Ono-Kondo equation for methane adsorption on different adsorbents

Sample	T / K	$ C $ /(mmol·g⁻¹)	$ {-(\varepsilon }_{{\rm{A}}}/k) $/ k	$ {\rho }_{{\rm{mc}}} $ /(mol·L⁻¹)
SAC-02	293.15	3.995	893.24	21.03
	303.15	3.670	916.75	20.51
	313.15	3.769	900.70	19.99
HKUST-1	293.15	3.088	1222.06	22.52
	303.15	3.030	1206.65	21.96
	313.15	2.882	1225.57	21.40
MIL-101(Cr)	293.15	29.48	1242.24	24.77
	303.15	13.56	1289.07	24.15
	313.15	13.76	1260.73	23.54

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