Preparation process development of UiO-66-NH2@PVAm mixed matrix membranes for CO2 capture

doi:10.11949/0438-1157.20251009

Abstract

Abstract:

Post-combustion capture technology is the main research and application direction of CO₂ capture technology at present. The physicochemical structure of UiO-66-NH₂ was functionalized with the polymer matrix polyvinylamine (PVAm) to prepare the novel UiO-66-NH₂@PVAm nanofiller. This nanofiller was subsequently incorporated into the PVAm matrix to fabricate mixed matrix membranes (MMMs), allowing for the regulation of transport channels and interfacial morphology microstructures. The modification process not only narrowed the pore size distribution of the filler but also improved the interface morphology between the fillers and the PVAm matrix. Additionally, a slot-die coating process was developed to achieve performance enhancement and scale-up preparation of the MMMs. Through optimization of the coating parameters and nanoparticle loading, the resulting MMMs achieved a CO₂ permeance of 2528 GPU and a CO₂/N₂ selectivity of 120 at the feed gas pressure of 0.2 MPa. Compared with industrial-scale pure polymer membranes, the permeance of MMMs has increased by 64.26%, and the selectivity has increased by 37.93%. The membrane performance remained stable over a 240-hour operational period, demonstrating its potential for practical industrial application.

Key words: CO₂ capture, mixed matrix, membrane, separation, slot-die coating process, industrial-scale preparation

摘要：

以聚乙烯基胺（PVAm）修饰UiO-66-NH₂制备了新型纳米填料UiO-66-NH₂@PVAm，并将其与PVAm基质共混制备混合基质膜（mixed matrix membranes， MMMs），设计调控了膜传递通道与界面形态等微结构。修饰过程不仅使填料的孔道结构分布变窄，还优化颗粒与PVAm基质之间界面形态；开发了狭缝涂布工艺实现了MMMs的性能强化与放大制备。通过优化涂布工艺参数与填料含量，所制MMMs在0.2 MPa进料气压力下的CO₂渗透率为2528 GPU，CO₂/N₂选择性为120。与工业规模纯聚合物膜相比，MMMs的渗透率提升了64.26%，选择性提升了37.93%。同时，该膜在240 h操作过程中CO₂分离性能保持稳定，证明其有实际工业应用的潜力。

关键词: 二氧化碳捕集, 混合基质, 膜, 分离, 狭缝涂布工艺, 工业级制备

CLC Number:

TQ 028.8

Qiyuan ZHENG, Fei SHI, Xiaowang REN, Weifan WANG, Yi YANG, Ye YUAN, Zhi WANG. Preparation process development of UiO-66-NH₂@PVAm mixed matrix membranes for CO₂ capture[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251009.

郑淇元, 时飞, 任肖旺, 王卫凡, 杨毅, 原野, 王志. 用于CO₂捕集的UiO-66-NH₂@PVAm混合基质膜制备工艺开发[J]. 化工学报, DOI: 10.11949/0438-1157.20251009.

Figures/Tables 14

Fig.1 The preparation process of UiO-66-NH2@PVAm

Fig.2 (a) Schematic diagram of the large-scale preparation process of MMMs and (b) membrane preparation device

Fig.3 The (a) SEM and (b-c) TEM images of UiO-66-NH2; the (d) SEM and TEM (e-f) images of UiO-66-NH2@PVAm

Fig.4 The (a) ATR-FTIR; (b) WXRD results of UiO-66-NH2 and UiO-66-NH2@PVAm

Fig.5 Adsorption-desorption isotherms of nano-fillers at 77K: (a) UiO-66-NH2; (c) UiO-66-NH2@PVAm and pore size distribution map: (b) UiO-66-NH2; (d) UiO-66-NH2@PVAm

Table 1 The pore parameters of UiO-66-NH2 and UiO-66-NH2@PVAm

样品

BET比表面积/

(m²·g^-1)

总孔体积/

(cm³·g^-1)

平均微孔孔径/

(nm)

Fig.6 The picture of 0.15wt % filler dispersion in water: (a) UiO-66-NH2; (b) UiO-66-NH2@PVAm

Table 2 The physical parameters of the dispersion and coating solution prepared by UiO-66-NH2 and UiO-66-NH2@PVAm

填料类型	流体力学粒径/(nm)	Zeta电位/(mV)	粘度/(mPa·s)	接触角/(°)
UiO-66-NH₂	441.20	20.70	73.06	64.06
UiO-66-NH₂@PVAm	376.60	42.50	83.41	59.69

Fig.7 (a) The effects of slit gap distance on the supply volume of the slot-die coating device and (b) the CO2/N2 separation performance of PVAm TFC membranes (feed gas: CO2:N2=15:85, humidified, 0.5 MPa, 25°C)

Fig.8 The cross-section SEM images of PVAm TFCMs prepared with different size of slit gap: (a) 180 μm; (b) 330 μm; (c) 430 μm

Fig.9 The surface SEM images of MMMs prepared with different UiO-66-NH2@PVAm loading: (a) 0 wt%, (b) 5 wt%, (c) 10 wt%, (d) 20 wt% and (e) 30 wt%; (f) the high-resolution SEM image of MMMs with 30 wt% UiO-66-NH2@PVAm loading

Fig.10 (a) The CO2/N2 separation performance and (b) the N2 permeance of MMMs prepared by slot-die coating process (feed gas: CO2:N2=15:85, humidified, 0.5 MPa, 25℃)

Fig.11 (a) The effects of feed gas pressure on the CO2/N2 separation performance of PVAm/UiO-66-NH2@PVAm(20) membrane (hollow symbol) and PVAm membrane (solid symbol) (feed gas: CO2:N2=15:85, humidified, 25°C); (b) Long-term performance stability of PVAm/UiO-66-NH2@PVAm(20) membrane (feed gas A: CO2:N2=15:85, feed gas B: 10 ppm SO2+30 ppm NO2+15 ppm CO+15% CO2+N2 balance, humidified, 0.5 MPa, 25℃)

Table 3 Comparison of the CO2/N2 separation performance of the MMMs produced in this chapter with the membranes reported in the literatures

膜	原料气条件	规模	$R C O 2$ /(GPU)	$α C O 2 / N 2$	Ref.
Pebax-C₆₀(OH)₂₄/PAN	0.5 MPa，35 ℃ 混合气，RH=0	实验室规模	388	41	[28]
Pebax-MXene	0.5 MPa，25 ℃ 混合气，RH=0	实验室规模	1360	31.4	[29]
PEG-SiO₂	0.45 MPa，35 ℃ 纯气，RH=0	实验室规模	1300	27	[30]
MKP-PVAm/mPSf	0.5 MPa，25 ℃ 混合气，RH=100%	实验室规模	823	242	[8]
PVAm/HNTs	0.2 MPa，25 ℃ 混合气，RH=100%	实验室规模	179	127.9	[31]
Pebax/UiO-66-NH₂	0.4 MPa，35 ℃ 混合气，RH=0	实验室规模	277	44.6	[32]
GO MMMs	0.2 MPa，25 ℃ 混合气，RH=0	中试规模	1200	54	[9]
PVAm/UiO-66-NH₂@PVAm(20)	0.2 MPa，25 ℃ 混合气，RH=100%	工业规模	2528	120	本工作
PVAm/UiO-66-NH₂@PVAm(20)	0.5 MPa，25 ℃ 混合气，RH=100%	工业规模	1046	63	本工作

Table 3 Comparison of the CO2/N2 separation performance of the MMMs produced in this chapter with the membranes reported in the literatures

膜	原料气条件	规模	$R C O 2$ /(GPU)	$α C O 2 / N 2$	Ref.
Pebax-C₆₀(OH)₂₄/PAN	0.5 MPa，35 ℃ 混合气，RH=0	实验室规模	388	41	[28]
Pebax-MXene	0.5 MPa，25 ℃ 混合气，RH=0	实验室规模	1360	31.4	[29]
PEG-SiO₂	0.45 MPa，35 ℃ 纯气，RH=0	实验室规模	1300	27	[30]
MKP-PVAm/mPSf	0.5 MPa，25 ℃ 混合气，RH=100%	实验室规模	823	242	[8]
PVAm/HNTs	0.2 MPa，25 ℃ 混合气，RH=100%	实验室规模	179	127.9	[31]
Pebax/UiO-66-NH₂	0.4 MPa，35 ℃ 混合气，RH=0	实验室规模	277	44.6	[32]
GO MMMs	0.2 MPa，25 ℃ 混合气，RH=0	中试规模	1200	54	[9]
PVAm/UiO-66-NH₂@PVAm(20)	0.2 MPa，25 ℃ 混合气，RH=100%	工业规模	2528	120	本工作
PVAm/UiO-66-NH₂@PVAm(20)	0.5 MPa，25 ℃ 混合气，RH=100%	工业规模	1046	63	本工作

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Preparation process development of UiO-66-NH₂@PVAm mixed matrix membranes for CO₂ capture

用于CO₂捕集的UiO-66-NH₂@PVAm混合基质膜制备工艺开发

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