Synthesis of Cu-BTC modified by CTAB and its adsorption and separation of xylene isomers

doi:10.16085/j.issn.1000-6613.2023-0226

Abstract

Abstract:

In this work, cetyltrimethylammonium bromide (CTAB) was added in the process of hydrothermal synthesis of Cu-BTC crystal, and the morphology and pore structure of the adsorbed material were modified by adjusting the addition amount of CTAB. Compared with the original Cu-BTC, the static adsorption capacity of the modified Cu-BTC material was significantly increased. It was higher than m-xylene (MX) and o-xylene (OX), which improved the adsorption selectivity of isomers. The static and kinetic properties of xylene isomers on Cu-BTC-CTAB adsorbent were systematically studied. A series of adsorption equilibrium experiments on xylene organic vapor were conducted at 298K, 318K and 338K, and the static adsorption rate curves and adsorption isotherms were obtained. In the modified material, the adsorption capacity and selectivity of PX in Cu-BTC-CTAB sample with 0.08% CTAB were the best. Kinetic studies showed that the adsorption of xylene isomers on Cu-BTC-CTAB could be described by a pseudo-first-order kinetic model.

Key words: Cu-BTC, CTAB modification, adsorption separation, xylene isomers

摘要：

通过水热法合成Cu-BTC晶体的过程中添加十六烷基三甲基溴化铵（CTAB），通过调节CTAB的添加量对吸附材料的形貌和孔结构进行改性，改性后的Cu-BTC材料与原Cu-BTC相比，其对对二甲苯（PX）的静态吸附量明显提高，且高于间二甲苯（MX）和邻二甲苯（OX），从而提高了异构体的吸附选择性。研究了二甲苯异构体在Cu-BTC-CTAB材料上的静态吸附性能和吸附动力学性能。在298K、318K和338K温度下进行了一系列二甲苯有机蒸气吸附平衡实验，得到了静态吸附速率曲线和吸附等温线。改性材料中CTAB添加量为0.08%的Cu-BTC-CTAB样品对PX的吸附量和选择性最优。动力学研究表明，二甲苯异构体在Cu-BTC-CTAB上的吸附过程可以用一级动力学模型来描述。

关键词: Cu-BTC, CTAB改性, 吸附分离, 二甲苯异构体

CLC Number:

TQ424

CHEN Le, CHONG Hailing, ZHANG Zhihui, HE Mingyang, CHEN Qun. Synthesis of Cu-BTC modified by CTAB and its adsorption and separation of xylene isomers[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 455-464.

陈乐, 种海玲, 张致慧, 何明阳, 陈群. CTAB改性Cu-BTC材料的合成及其吸附分离二甲苯异构体的性能[J]. 化工进展, 2024, 43(1): 455-464.

Figures/Tables 13

References 28

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样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	微孔孔容 /cm³·g^-1	孔径/nm
Cu-BTC	1139.6	0.439	0.399	2.07
Cu-BTC-CTAB(0.08%)	1140.2	0.506	0.393	2.38
Cu-BTC-CTAB(0.16%)	1052.0	0.484	0.361	2.40
Cu-BTC-CTAB(0.24%)	743.8	0.425	0.255	3.08
Cu-BTC-CTAB(0.35%)	576.8	0.523	0.196	4.78

样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	微孔孔容 /cm³·g^-1	孔径/nm
Cu-BTC	1139.6	0.439	0.399	2.07
Cu-BTC-CTAB(0.08%)	1140.2	0.506	0.393	2.38
Cu-BTC-CTAB(0.16%)	1052.0	0.484	0.361	2.40
Cu-BTC-CTAB(0.24%)	743.8	0.425	0.255	3.08
Cu-BTC-CTAB(0.35%)	576.8	0.523	0.196	4.78

吸附剂类型	吸附剂	PX吸附量/mg·g^-1	分离系数		参考文献
堆叠效应的吸附	MIL-125(Ti)	150	PX/MX=1.5	PX/OX=1.6	[19]
	Cu-(CDC)	—	PX/MX=7.0	PX/OX=10	[20]
	MIL-47	483	PX/MX=1.10	PX/OX=0.60	[21]
分子筛效应的吸附	NaY^a	110	MX/PX=2.90	MX/OX=3.16	[22]
	NaY	99.6	MX/PX=2.62	MX/OX=2.83	[23]
	MIL-53(Al)	357.8	OX/PX=3.50	OX/MX=2.70	[24]
OMSs的吸附	HKUST-1	297	OX/PX=1.08~1.21	—	[25]
	CPO-27-Ni	210	OX/PX=3.3	OX/MX=1.7	[13]
开门或呼吸效应的吸附	ZIF-8	210	MX/PX=3.1	PX/OX=8.8	[26]
	ZIF-76	260	OX/PX=1.1		[27]
	Mn-dhbq	—	PX/OX=37.9	PX/MX=34.8	[28]
	Cu-BTC-CTAB(0.08%)	426	PX/OX=2.20	—	本工作

吸附剂类型	吸附剂	PX吸附量/mg·g^-1	分离系数		参考文献
堆叠效应的吸附	MIL-125(Ti)	150	PX/MX=1.5	PX/OX=1.6	[19]
	Cu-(CDC)	—	PX/MX=7.0	PX/OX=10	[20]
	MIL-47	483	PX/MX=1.10	PX/OX=0.60	[21]
分子筛效应的吸附	NaY^a	110	MX/PX=2.90	MX/OX=3.16	[22]
	NaY	99.6	MX/PX=2.62	MX/OX=2.83	[23]
	MIL-53(Al)	357.8	OX/PX=3.50	OX/MX=2.70	[24]
OMSs的吸附	HKUST-1	297	OX/PX=1.08~1.21	—	[25]
	CPO-27-Ni	210	OX/PX=3.3	OX/MX=1.7	[13]
开门或呼吸效应的吸附	ZIF-8	210	MX/PX=3.1	PX/OX=8.8	[26]
	ZIF-76	260	OX/PX=1.1		[27]
	Mn-dhbq	—	PX/OX=37.9	PX/MX=34.8	[28]
	Cu-BTC-CTAB(0.08%)	426	PX/OX=2.20	—	本工作

温度/K	二甲苯	一级动力学方程的非线性拟合				二级动力学方程的非线性拟合
温度/K	二甲苯	Q_m/mg·g^-1	Q_e/mg·g^-1	k₁/min	R₁²	Q_e /mg·g^-1	k₂/g·mg^-1·min^-1	R₂²
298	OX	183.59	-9.411	4.6×10^-3	0.987	3380407	1.7×10^-12	0.786
	MX	333.98	571488	-8.4×10^-7	0.939	380213	3.3×10^-12	0.939
	PX	426.45	432.8	-0.7×10^-2	0.862	552.35	1.2×10^-5	0.836
318	OX	240.27	213.12	-8.7×10^-2	0.918	220.19	6.1×10^-4	0.951
	MX	261.94	223.05	-3.1×10^-2	0.883	237.61	2.1×10^-4	0.929
	PX	300.52	278.10	-2.6×10^-2	0.972	306.23	1.3×10^-4	0.990
338	OX	215.49	207.99	-1.2×10^-2	0.978	211.53	1.3×10^-3	0.989
	MX	259.09	248.703	-1.2×10^-2	0.988	282.47	5.5×10^-5	0.975
	PX	127.43	274.810	-1.0×10^-2	0.941	324.16	3.9×10^-5	0.916