MIL-101（Cr）批量化生产中的絮凝工艺研究

doi:10.11949/0438-1157.20241223

摘要/Abstract

摘要：

近年来，金属有机骨架材料（MOF）因其比表面积大、孔尺寸高度可调及功能多样等特点，在气体吸附与分离、催化、传感等领域展现出广阔的应用前景。然而，大多数MOF材料仍局限于实验室的小规模合成，MOF宏量制备面临着许多挑战，包括合成条件严苛、产量低以及后处理困难等，限制了其广泛应用的可能性。在众多MOF材料中，MIL-101（Cr）因其卓越的热稳定性、化学稳定性以及超高的孔隙率和比表面积而备受研究者青睐。MIL-101（Cr）可以通过简单的水热合成法，使用成本较低的对苯二甲酸和铬盐进行合成，展现出优异的工业应用潜力。然而，传统水热合成过程中，MIL-101（Cr）颗粒因粒径较小导致沉降困难，需要多次过滤洗涤，这些因素限制了其生产效率。为了解决这一问题，引入了絮凝剂并通过调控絮凝剂的种类和用量，缩短了过滤时间，提高了生产效率。重要的是，加入絮凝剂后MIL-101（Cr）热稳定性得以保持，BET比表面积达到3211 m²/g，二氧化碳吸附量达到40 cm³/g，性能得到了良好的保持。

关键词: 金属有机骨架材料, 绿色规模化生产, 絮凝剂, 快速沉降, 提升效率

Abstract:

In recent years, metal-organic frameworks (MOF) have garnered significant attention due to their large specific surface area, highly tunable pore sizes, and diverse functionalities. These characteristics render MOF promising materials for applications in gas adsorption and separation, catalysis, and sensing. However, the majority of MOF materials remain confined to small-scale synthesis in laboratories. The large-scale production of MOF faces numerous challenges, including stringent synthesis conditions, low yields, and difficult post-processing, limiting their widespread application. Among the various MOF materials, MIL-101(Cr) has gained particular favor from researchers due to its exceptional thermal stability, chemical stability, and ultra-high porosity and specific surface area. MIL-101(Cr) can be synthesized via a simple hydrothermal method using relatively low-cost terephthalic acid and chromium salts, demonstrating significant potential for industrial applications. Nevertheless, in the conventional hydrothermal synthesis process, the small particle size of MIL-101(Cr) leads to difficulties in sedimentation and requires multiple washing steps, which limit the production efficiency. To address this issue, we introduced a flocculant and optimized the flocculation process by adjusting the types and amounts of flocculant used, thereby reducing filtration time and improving production efficiency. Importantly, after adding flocculants, the thermal stability of MIL-101(Cr) was maintained, the BET specific surface area reached 3211 m²/g, and the carbon dioxide adsorption reached 40 cm³/g, and the performance was well maintained.

Key words: metal-organic frameworks, green scaled production, flocculating agent, rapid sedimentation, improved efficiency

中图分类号:

TQ 028.8

宁丹东, 李建惠, 陈杨, 李晋平, 李立博. MIL-101（Cr）批量化生产中的絮凝工艺研究[J]. 化工学报, 2025, 76(5): 2327-2336.

Dandong NING, Jianhui LI, Yang CHEN, Jinping LI, Libo LI. Study on flocculation techniques in the large-scale production of MIL-101(Cr)[J]. CIESC Journal, 2025, 76(5): 2327-2336.

图/表 7

图1 MIL-101(Cr)混合液未添加(a)和添加(b)絮凝剂辅助沉降示意图

Fig.1 Schematic diagram of the sedimentation process of MIL-101(Cr) suspension without (a) and with (b) the addition of flocculants

图2 (a)添加不同种类絮凝剂处理得到的MIL-101(Cr)样品的PXRD谱图；(b)添加不同种类絮凝剂处理得到的MIL-101(Cr)样品在77 K下的N2吸附等温线；(c)、(d)不同种类絮凝剂沉降30 min后效果图

Fig.2 (a) PXRD patterns of MIL-101 (Cr) samples obtained by adding different kinds of flocculants; (b) N2 sorption isotherms at 77 K for MIL-101(Cr) samples obtained by adding different kinds of flocculants; (c), (d) Effects of different types of flocculants after 30 minutes of sedimentation

表1 不同体积混合液过滤效率对比参数

Table 1 Parameters for comparing filtration efficiencies of different volume mixtures

Volume mixtures/L	T_add/h	T_without/h	T_add/T_without	M_add/g	M_without/g	M_add/M_without
1	0.2	2	0.10	36	21	1.71
3	0.7	8	0.09	107	61	1.75
5	1.3	15	0.08	180	99	1.82

图3 (a)不同浓度的絮凝剂处理得到的MIL-101(Cr)样品的PXRD谱图；(b)不同浓度的絮凝剂处理得到的MIL-101(Cr)样品在77 K下的N2吸附等温线；(c)、(d)不同浓度絮凝剂30 min后沉降效果图

Fig.3 (a) PXRD patterns of MIL-101(Cr) samples treated with different concentrations of flocculants; (b) N2 sorption isotherms at 77 K for MIL-101(Cr) samples treated with different concentrations of flocculants; (c), (d) Effects of different types of flocculants after 30 min of sedimentation

图4 (a)添加不同浓度的氨水处理得到的MIL-101(Cr)样品的PXRD谱图；(b)添加不同浓度氨水处理得到的MIL-101(Cr)样品在77 K下的N2吸附等温线

Fig.4 (a) PXRD patterns of MIL-101(Cr) samples obtained by adding different concentrations of ammonia; (b) N2 sorption isotherms at 77 K for MIL-101(Cr) samples obtained by adding different concentrations of ammonia

图5 (a)、(b)未加絮凝剂的SEM图；(c)~(e)加入絮凝剂的SEM图；(f)原始MIL-101(Cr)与加入絮凝剂后的MIL-101(Cr)的TGA曲线

Fig.5 (a), (b) SEM images of sample without flocculant; (c)—(e) SEM images of sample with the addition of flocculant; (f) TGA curves of pristine MIL-101(Cr) and MIL-101(Cr) obtained by adding flocculants

图6 (a)不同浓度絮凝剂处理得到的MIL-101(Cr)样品在298 K和1 bar（1 bar=0.1 MPa）下的CO2吸附等温线图；(b)在25℃和1 bar下，加入絮凝剂与未加絮凝剂处理的MIL-101(Cr)样品CO2/N2（15/85，体积比）混合气穿透曲线；(c)加入絮凝剂穿透循环性能测试图；(d)未加入絮凝剂穿透循环性能测试图

Fig.6 (a) CO2 adsorption isotherms of MIL-101(Cr) samples treated with different concentrations of flocculants at 298 K and 1 bar; (b) The breakthrough curves of CO₂/N₂ (15/85, volume) mixed gas for MIL-101(Cr) samples treated with and without the addition of flocculant at 25 °C and 1 bar; (c) Test chart of breakthrough cycling performance with the addition of flocculant; (d) Test chart of breakthrough cycling performance without the addition of flocculant

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