低硅CHA型沸石的低温合成及其CO2/N2吸附分离性能研究

doi:10.19964/j.issn.1006-4990.2025-0083

Abstract

Abstract:

CHA zeolite，with its unique eight-membered ring pore structure，has potential industrial application prospects in the field of CO₂ adsorption and separation.In order to achieve the research goal of low-cost and green synthesis of high-performance zeolites，zeolite CHA was synthesized at low temperature without the use of organic structure-directing agents，and its CO₂/N₂ separation properties were investigated.The effects of crystallization temperature，time，and K⁺ content on the synthesis of pure-phase CHA zeolite were comprehensively investigated using characterization techniques including XRD，SEM，FT-IR，EDS and TGA.The CO₂ and N₂ adsorption isotherms at 273 K and 298 K were measured，and the CO₂/N₂ IAST（Ideal Adsorption Solution Theory） selectivities were calculated.The results showed that the conditions of crystallization at 353 K for 288 h，the CHA zeolite prepared with the synthesis formula of n（SiO₂）∶n（Al₂O₃）∶n（K₂O）∶n（H₂O）=1∶0.2∶0.4∶35 exhibited high CO₂/N₂ adsorption and separation performance（IAST selectivity value of 51.2）.Adsorption mechanism studies were conducted.The four-parameter Dual-site Langmuir model and the three-parameter Langmuir-Freundlich model were used to fit the CO₂ and N₂ adsorption data，both showing high goodness of fit with coefficient of determination（R²） exceeding 0.999.Additionally，isosteric heats calculations and CO₂-TPD tests were performed.The results indicated that the CO₂ adsorption behavior belonged to heterogeneous physical adsorption.The method of low-temperature hydrothermal synthesis of CHA zeolite was simple and low-cost，and it had good CO₂ adsorption and separation，and cyclic regeneration performance，which had strong industrial application value.

Key words: CHA zeolite, low-silica zeolite, hydrothermal synthesis, CO₂ adsorption, CO₂/N₂ separation

CLC Number:

TQ127.2

XU Fan, YIN Xiaoyan, SONG Feng. Study on low-temperature synthesis of low-silica CHA zeolite and its CO₂/N₂ adsorption and separation performance[J]. Inorganic Chemicals Industry, 2026, 58(3): 41-48.

Figures/Tables 15

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References 23

[1]	YUSUF M， IBRAHIM H.A comprehensive review on recent trends in carbon capture，utilization，and storage techniques［J］.Journal of Environmental Chemical Engineering，2023，11（6）：111393.
[2]	邢淑建，臧甲忠，刘伟，等.分子筛吸附剂的工业应用研究进展［J］.无机盐工业，2009，41（3）：13-16.
	XING Shujian， ZANG Jiazhong， LIU Wei，et al.Progress on industrial application of molecular sieve adsorbents［J］.Inorganic Chemicals Industry，2009，41（3）：13-16.
[3]	DAS A， PEU S D， HOSSAIN M S，et al.Advancements in adsorption based carbon dioxide capture technologies：A comprehensive review［J］.Heliyon，2023，9（12）：e22341.
[4]	杨晨，吴俊书，王金淑，等.硅藻土的可控沸石化及其对铅离子的吸附固定［J］.无机盐工业，2022，54（4）：128-134.
	YANG Chen， WU Junshu， WANG Jinshu，et al.Controlled zeolitization of diatomite for the adsorption and its immobilization of Pb（Ⅱ） ions［J］.Inorganic Chemicals Industry，2022，54（4）：128-134.
[5]	QIAN Jingyun， ZHANG Wenna， YANG Xue，et al.Tailoring zeolite ERI aperture for efficient separation of CO₂ from gas mixtur-es［J］.Separation and Purification Technology，2023，309：123078.
[6]	唐轩，白晓炜，张飞飞，等.沸石分子筛用于CO₂-N₂-CH₄筛分分离的研究进展［J］.化工进展，2025，44（7）：3938-3949.
	TANG Xuan， BAI Xiaowei， ZHANG Feifei，et al.Research progress on zeolite for CO₂-N₂-CH₄ sieving separation［J］.Chemical Industry and Engineering Progress，2025，44（7）：3938-3949.
[7]	CHAWLA A， MALLETTE A J， JAIN R，et al.Crystallization of potassium-zeolites in organic-free media［J］.Microporous and Me- soporous Materials，2022，341：112026.
[8]	程妍，于天胤，张宏洋.利用稻壳灰水热合成A型沸石的研究［J］.无机盐工业，2025，57（6）：43-48.
	CHENG Yan， YU Tianyin， ZHANG Hongyang.Study on hydrothermal synthesis of A-type zeolite from rice husk ash［J］.Inorganic Chemicals Industry，2025，57（6）：43-48.
[9]	SKOFTELAND B M， ELLESTAD O H， LILLERUD K P.Potassium merlinoite：Crystallization，structural and thermal properti-es［J］.Microporous and Mesoporous Materials，2001，43（1）：61- 71.
[10]	KIM M Z， SHARMA P， KIM Y，et al.One-step template-free hydrothermal synthesis of partially Sr-incorporated hierarchical K-CHA zeolite microspheres［J］.Microporous and Mesoporous Materials，2019，286：65-76.
[11]	钱磊.“分子门效应”的菱沸石制备及气体分离性能研究［D］.沈阳：东北大学，2020.
	QIAN Lei.Preparation of Chabazite with molecular trapdoor effect and its performance of gas separation［D］.Shenyang：Northeastern University，2020.
[12]	CHEN Wenting， SONG Guoqiang， LIN Youyuan，et al.A green and efficient strategy for utilizing of coal fly ash to synthesize K-MER zeolite as catalyst for cyanoethylation and adsorbent of CO₂ ［J］.Microporous and Mesoporous Materials，2021，326：111353.
[13]	王睿，张学建，李永涛，等.油页岩灰渣制备Na-X型沸石及其吸附性能研究［J］.吉林建筑大学学报，2024，41（3）：29-34.
	WANG Rui， ZHANG Xuejian， LI Yongtao，et al.Reparation of Na-X zeolite derived from oil shale ash and its adsorption properties［J］.Journal of Jilin Jianzhu University，2024，41（3）：29-34.
[14]	GHOJAVAND S， CLATWORTHY E B， VICENTE A，et al.The role of mixed alkali metal cations on the formation of nanosized CHA zeolite from colloidal precursor suspension［J］.Journal of Colloid and Interface Science，2021，604：350-357.
[15]	崔家新，王连勇，卢思盟，等.几种不同产地粉煤灰水热法合成沸石性能探究［J］.无机盐工业，2022，54（5）：96-100.
	CUI Jiaxin， WANG Lianyong， LU Simeng，et al.Research on performance of hydrothermally synthesized zeolite with fly ash from different producing areas［J］.Inorganic Chemicals Industry，2022，54（5）：96-100.
[16]	MADHU J， MADURAI RAMAKRISHNAN V， SANTHANAM A，et al.Comparison of three different structures of zeolites prepared by template-free hydrothermal method and its CO₂ adsorption properties［J］.Environmental Research，2022，214：113949.
[17]	刘有毅，黄艳，何嘉杰，等.CO/N₂/CO₂在MOF-74（Ni）上吸附相平衡和选择性［J］.化工学报，2015，66（11）：4469-4475.
	LIU Youyi， HUANG Yan， HE Jiajie，et al.Adsorption isotherms and selectivity of CO/N₂/CO₂ on MOF-74（Ni）［J］.CIESC Journal，2015，66（11）：4469-4475.
[18]	SUN Mingzhe， GU Qinfen， HANIF A，et al.Transition metal cation-exchanged SSZ-13 zeolites for CO₂ capture and separation from N₂ ［J］.Chemical Engineering Journal，2019，370：1450-1458.
[19]	CHOI H J，JO D， BONG HONG S.Effect of framework Si/Al ratio on the adsorption mechanism of CO₂ on small-pore zeolites：II.Merlinoite［J］.Chemical Engineering Journal，2022，446：137100.
[20]	KENCANA K S， CHOI H J， KEMP K C，et al.Enhancing the CO₂ adsorption kinetics on Na-RHO and Cs-MER zeolites by NH₄F/H₂O₂ etching induced mesoporosity［J］.Chemical Engineering Journal，2023，451：138520.
[21]	NIE Yuanyuan， LI Linzhe， LIU Jing，et al.Fabrication of highly uniform ultra-small zeolite T nanocrystals［J］.Materials Chemistry and Physics，2023，298：127465.
[22]	JUNE C， BONG H.Effect of framework Si/Al ratio on the mechanism of CO₂ adsorption on the small-pore zeolite gismondine［J］.Chemical Engineering Journal，2022，433：133800.
[23]	MURIITHI G N， PETRIK L F， DOUCET F J.Synthesis，characterisation and CO₂ adsorption potential of NaA and NaX zeolites and hydrotalcite obtained from the same coal fly ash［J］.Journal of CO₂ Utilization，2020，36：220-230.

样品	n（SiO₂）∶n（Al₂O₃）∶n（K₂O）∶n（H₂O）	晶化温度/K	晶化时间/h	晶相
1	1∶0.2∶0.5∶35	353	192	CHA+Am
2	1∶0.2∶0.5∶35	353	240	CHA
3	1∶0.2∶0.5∶35	373	120	CHA+MER
4	1∶0.2∶0.4∶35	353	240	CHA+Am
5	1∶0.2∶0.4∶35	353	288	CHA
6	1∶0.2∶0.4∶35	373	72	CHA
7	1∶0.2∶0.4∶35	373	120	CHA
8	1∶0.2∶0.4∶35	373	168	CHA

样品	原子数分数/%				n（Si）/n（Al）
样品	O	Al	Si	K	n（Si）/n（Al）
2	48.52	7.20	14.95	5.92	2.08
5	67.97	9.13	16.14	6.76	1.77
6	59.89	6.82	13.18	4.91	1.93
7	41.81	4.33	8.40	3.05	1.94
8	68.72	9.19	15.59	6.50	1.70

样品	比表面积/ （m²·g^-1）	孔体积/ （cm³·g^-1）	CO₂吸附量/（cm³·g^-1）		N₂吸附量/（cm³·g^-1）		CO₂/N₂ 选择性
样品	比表面积/ （m²·g^-1）	孔体积/ （cm³·g^-1）	273 K	298 K	273 K	298 K	273 K	298 K
2	378	0.217	79.1	77.7	12.8	8.3	33.4	49.3
5	272	0.167	67.1	59.7	10.1	6.1	35.7	51.2
6	419	0.242	72.4	86.5	14.7	9.8	26.9	47.5
7	392	0.227	79.4	81.3	15.5	10.1	27.7	43.9
8	326	0.188	67.7	67.2	11.3	8.3	32.6	42.0

样品	吸附量/（cm³·g^-1）	CO₂/N₂选择性
5号（本工作）	59.7	51.2
Co-SSZ-13^［18］	26.0	40.0
Na-LTA-1.0^［19］	88.2	42.0
Cs-MER （10N）^［20］	29.4	27.0
T^［21］	73.2	47.6
Na-GIS-2.5^［22］	73.5	16.0

样品	DSL（CO₂）					LF（N₂）
样品	q_m1/（cm³·g^-1）	q_m2/（cm³·g^-1）	b₁	b₂	R²	q_m/（cm³·g^-1）	b	n	R²
2	65.0	20.2	0.596	0.022	0.999 88	32.6	0.002	1.087	0.999 93
5	48.2	20.9	0.852	0.013	0.999 90	24.8	0.004	0.963	0.999 92

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Inorganic Acid-Base-Salt Committee of CIESC

Study on low-temperature synthesis of low-silica CHA zeolite and its CO₂/N₂ adsorption and separation performance

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Study on low-temperature synthesis of low-silica CHA zeolite and its CO2/N2 adsorption and separation performance