Preparation and performance optimization of liquefied residue-based CO2 adsorbents

doi:10.16085/j.issn.1000-6613.2023-0090

Abstract

Abstract:

Using coal liquefaction residue (CLR) as the raw material to prepare CO₂adsorbents can effectively improve the economic and environmental value of direct coal liquefaction process while achieving carbon emission reduction, which is of great significance. The direct liquefaction residue of Shenhua coal was used as carbon source, and the CO₂adsorbents with better adsorption performance were prepared through the process of pre-oxidation and carbonization activation. The microstructure, pore size structure and adsorption properties of the adsorbents were characterized and tested by thermogravimetric analyzer (TGA), low temperature nitrogen adsorption instrument (BET), scanning electron microscope (SEM) and transmission electron microscope (TEM). The results showed that the adsorbents prepared from low ash liquefied residue had higher specific surface area and more microporous structure, which were more conducive to the adsorption of CO₂. The CO₂adsorbent prepared from low ash liquefied residue under optimal activation conditions (mass ratio of activator/raw material was 1∶1, heating rate was 5℃/min, activation time was 1h) showed good adsorption performance. The CO₂ adsorption capacity at 40℃ and 15%CO₂ simulated flue gas was 4.47%. At 0℃ and 1bar, the CO₂adsorption capacity could be up to 27.70%, the low temperature adsorption performance was excellent, the adsorption rate was fast, and it had good cycle stability.

Key words: coal liquefaction residual, carbon dioxide, CO₂ capture, adsorbents, low temperature adsorption

摘要：

以煤液化残渣（CLR）为原料制备CO₂吸附剂，在实现碳减排的同时，可有效提高煤直接液化工艺的经济性和环保价值。本文采用神华煤直接液化残渣为碳源，通过预氧化、炭化活化等工艺，制备出了吸附性能较优的CO₂吸附剂。利用热重分析仪（TGA）、低温氮吸附仪（BET）、扫描电镜（SEM）以及透射电子显微镜（TEM）等分析手段对吸附材料的微观形貌、孔径结构以及吸附性能进行了表征测试。结果显示，低灰分液化残渣所制备的吸附材料具有更高的比表面积和更多的微孔结构，更有利于CO₂的吸附。以低灰分液化残渣为原料，在较优活化条件下（活化剂/原料质量比为1∶1、升温速率5℃/min、活化时间1h）制备的CO₂吸附剂表现出良好的吸附性能，在40℃、15%（体积分数）CO₂模拟烟气条件下的CO₂吸附容量为4.47%（质量分数），在0℃、1bar（1bar=10⁵Pa）条件下的CO₂吸附容量可高达27.70%（质量分数），低温吸附性能优异，吸附速率快且具有良好的循环稳定性。

关键词: 煤液化残渣, 二氧化碳, 二氧化碳捕集, 吸附剂, 低温吸附

CLC Number:

TQ028

CUI Qian, WANG Annan, CHEN Zaiming, SUN Qiaoyi, WANG Baodeng, WANG Yongsheng, SUN Nannan, HU Jian, LI Jingfeng, XIONG Rihua. Preparation and performance optimization of liquefied residue-based CO₂ adsorbents[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6620-6630.

崔倩, 王岸楠, 陈再明, 孙峤昳, 王保登, 王永胜, 孙楠楠, 胡剑, 李井峰, 熊日华. 液化残渣基CO₂吸附剂的制备与性能优化[J]. 化工进展, 2023, 42(12): 6620-6630.

Figures/Tables 19

References 32

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样品	工业分析				元素分析
样品	M_ad	A_d	V_d	FC_d	C	H	N	S
CLR	0.31	26.28	33.56	40.17	67.60	4.26	0.53	4.99
DCLR	0.26	0.35	51.91	47.75	91.20	6.41	1.14	0.21

样品	工业分析				元素分析
样品	M_ad	A_d	V_d	FC_d	C	H	N	S
CLR	0.31	26.28	33.56	40.17	67.60	4.26	0.53	4.99
DCLR	0.26	0.35	51.91	47.75	91.20	6.41	1.14	0.21

样品	成分
样品	Fe₂O₃	CaO	SO₃	SiO₂	Al₂O₃	TiO₂	MgO	Na₂O	其他
CLR	53.48	12.39	12.19	11.79	5.77	1.16	1.05	1.02	1.15
DCLR	45.88	11.92	22.33	7.13	4.70	1.08	1.57	3.99	1.40

样品	成分
样品	Fe₂O₃	CaO	SO₃	SiO₂	Al₂O₃	TiO₂	MgO	Na₂O	其他
CLR	53.48	12.39	12.19	11.79	5.77	1.16	1.05	1.02	1.15
DCLR	45.88	11.92	22.33	7.13	4.70	1.08	1.57	3.99	1.40

样品	S_BET/m²·g^-1	S_mic /m²·g^-1	V_tol /cm³·g^-1	V_mic /cm³·g^-1	D_a/nm
CLR-1-10C-0.5h	1308	1103	0.61	0.46	4.73
CLR-1-10C-1h	1259	1121	0.59	0.47	2.98
CLR-1-10C-1.5h	1251	1038	0.57	0.43	4.65
CLR-1-10C-2h	1328	996	0.78	0.39	4.84

Preparation and performance optimization of liquefied residue-based CO₂ adsorbents

液化残渣基CO₂吸附剂的制备与性能优化

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Figures/Tables 19

References 32

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样品	S_BET/m²·g^-1	S_mic/m²·g^-1	V_tol/cm³·g^-1	V_mic/cm³·g^-1	D_a/nm
CLR-1-3C-1h	1311	1244	0.60	0.53	1.83
CLR-1-5C-1h	1389	1221	0.63	0.52	2.22
CLR-1-10C-1h	1259	1121	0.59	0.47	2.98

样品	S_BET/m²·g^-1	S_mic/m²·g^-1	V_tol/cm³·g^-1	V_mic/cm³·g^-1	D_a/nm
CLR-0-5C-1h	49	36	0.03	0.01	3.98
CLR-0.5-5C-1h	708	630	0.37	0.24	2.10
CLR-1-5C-1h	1389	1221	0.63	0.52	2.22
CLR-2-5C-1h	1528	1103	0.95	0.50	2.87

样品	灰分	Fe₂O₃	CaO	SO₃	SiO₂	Al₂O₃	TiO₂	MgO	Na₂O	K₂O	其他
CLR-1-10C-0.5h	2.54	36.37	1.31	0.63	50.14	3.62	2.44	0.47	2.81	2.00	0.21
DCLR-1-10C-0.5h	1.21	23.83	0.80	0.70	63.49	2.87	0.42	0.25	3.11	4.24	0.29

项目	前体	活化剂	吸附温度/℃	吸附压力/bar	CO₂吸附量/%
DCLR-1-5C-1h	液化残渣	KOH	40	0.15	4.47
DCLR-1-5C-1h	液化残渣	KOH	0	1	27.70
文献[27]	淀粉/纤维素/木屑	KOH	0	1	25.52
文献[28]	莴笋叶	KOH	0	1	26.40
文献[29]	亚烟煤	K₂CO₃+ CO₂	0	1	19.18
文献[30]	榛子壳	NaNH₂	0	1	26.00
文献[31]	无烟煤	H₂O	0	1	12.89
文献[32]	咖啡渣	CO₂	0	1	14.08
市售活性炭1	煤质	—	40	0.15	2.57
市售活性炭2	椰壳	—	40	0.15	3.48
市售活性炭3	椰壳	—	40	0.15	2.91

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