Fabrication of PVA/SA/CPO Mixed Matrix Membranes via Biomimetic Mineralization for Dehydration of Esterification Systems

doi:10.11949/0438-1157.20250815

Abstract

Abstract:

To address the challenge of dehydrating azeotropic ethyl acetate/water and acetic acid/water mixtures in esterification reaction systems, a biomimetic mineralization strategy was employed to prepare calcium phosphate oligomers (CPO) through calcium and phosphate ionic assembly. Sodium alginate (SA) was further utilized to construct polyvinyl alcohol (PVA)/SA/CPO mixed matrix membranes (MMMs) via carboxyl bridging. The membrane materials were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), water contact angle (WCA)and mechanical property tests. The results revealed ionic crosslinking between calcium ions of CPO and carboxyl group of SA, as well as hydrogen bonding between PVA and SA, which enhanced the hydrophilicity of the membrane material. The effects of CPO loading, feed composition and feed temperature on the separation performance for ethyl acetate/water and acetic acid/water systems were investigated through pervaporation experiments. For the ethyl acetate/water system, the pervaporation separation index (PSI) reached the maximum value at 2 wt.% CPO loading, showing 2.6-fold improvement compared to the pure PVA membrane. The permeation flux increased while the separation factor decreased with higher water content in the feed concentration. Both the permeation flux and separation factor increased with rising feed temperature. In the acetic acid/water system, the optimal PSI value was achieved at 6 wt.% CPO loading. The total permeation flux exhibited a continuous upward trend with increasing CPO content, whereas the separation factor initially increased and then declined. This study provides a novel approach for applying biomineralized materials in pervaporation membranes, demonstrating the industrial potential of the fabricated membranes for integrated esterification reaction dehydration systems.

Key words: mixed matrix membranes, biomimetic mineralization, poly(vinyl alcohol), calcium phosphate oligomers, sodium alginate, pervaporation

摘要：

针对酯化反应体系中乙酸乙酯/水和乙酸/水共沸物物脱水难题，基于仿生矿化策略，通过钙-磷酸根离子组装制备磷酸钙寡聚物（CPO），并利用海藻酸钠（SA）的羧基桥联作用，构建PVA/SA/CPO混合基质膜（MMMs）。通过扫描电镜（SEM）、傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、水接触角（WCA）、机械性能测试等对膜材料进行表征。结果表明，CPO的钙离子与SA的羧基之间存在离子交联，PVA与SA之间形成了氢键，氢键使膜材料的亲水性增加。通过渗透汽化实验考察CPO填充量、进料组成和进料温度对乙酸乙酯/水、乙酸/水分离性能的影响。当CPO填充量为2 wt.%时，乙酸乙酯/水体系的渗透汽化分离指数（PSI）达到最大，较纯PVA膜提升2.6倍；随进料中水的质量分数增加，渗透通量增加，分离因子降低；随进料温度升高，渗透通量和分离因子增加。在乙酸/水体系中，当CPO填充量为6 wt.%时，PSI值最大，随CPO填充量的增加，总渗透通量呈增加趋势，分离因子先增加后降低。该工作为生物矿化材料在渗透汽化膜中的应用提供了新思路，所制膜在酯化反应脱水集成系统中展现工业化应用潜力。

关键词: 混合基质膜, 仿生矿化, 聚乙烯醇, 磷酸钙寡聚物, 海藻酸钠, 渗透汽化

CLC Number:

TQ 028.8

Yu ZHANG, Xiliang QIAN, Jiatian GAN, Yun ZOU, Zhangfa TONG. Fabrication of PVA/SA/CPO Mixed Matrix Membranes via Biomimetic Mineralization for Dehydration of Esterification Systems[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250815.

张宇, 钱锡亮, 甘嘉添, 邹昀, 童张法. 基于仿生矿化的PVA/SA/CPO混合基质膜制备与酯化体系脱水性能[J]. 化工学报, DOI: 10.11949/0438-1157.20250815.

Figures/Tables 13

Fig.1 SEM image of CPO and PVA/SA/CPO membranes with different CPO loadings

Fig.2 ATR-FTIR spectra of CPO and PVA/SA/CPO membranes

Fig.3 XRD patterns of CPO and PVA/SA/CPO membranes

Fig.4 Water contact angles of PVA/SA/CPO membranes with different CPO loading

Fig.5 Swelling degree of PVA/SA/CPO membrane in water, ethyl acetate and acetic acid

Table 1 Tensile strength and tensile elongation of PVA/SA/CPO membranes

膜材料	拉伸强度 /MPa	伸长率 /%
PVA	20.03	190
PVA/SA/CPO-2	3.21	185
PVA/SA/CPO-4	4.57	161
PVA/SA/CPO-6	6.84	129
PVA/SA/CPO-8	15.58	110
PVA/SA/CPO-10	10.56	123

Fig.6 Effect of CPO content on the pervaporation performance of PVA/SA/CPO membranes

Fig.7 Effect of feed concentration on the pervaporation performance of PVA/SA/CPO membrane

Fig.8 Effect of feed temperature on the pervaporation performance of PVA/SA/CPO membranes

Fig.9 Effects of CPO content on the pervaporation performance of PVA/SA/CPO membranes

Fig.10 Effect of feed concentration on the pervaporation performance of PVA/SA/CPO membrane

Fig.11 Effects of feed temperature on the pervaporation performance of PVA/SA/CPO membranes

Table 5 Comparison of membranes reported for pervaporation dehydration for ethyl acetate/water and acetic acid/water systems

分离体系	膜材料	进料温度/℃	进料水质量分数/wt.％	渗透通量/ g·m^-2·h^-1	分离因子	参考文献.
水-乙酸乙酯	PVA/ceramic	60	2.6	1108.8	1265	^[9]
水-乙酸乙酯	PVA/ZSM-5	30	4	1231	6072	^[13]
水-乙酸乙酯	PVA/PFSA/Si	40	2	6673	262.7	^[33]
水-乙酸乙酯	BTESE	60	2	840	>10000	^[34]
水-乙酸乙酯	PBI/PEI	60	2	820	2478	^[35]
水-乙酸乙酯	PVA/CS	50	2	200	>10000	^[36]
水-乙酸乙酯	SA-GO/ PVA	70	4	957	3041	^[37]
水-乙酸乙酯	PVA/PAN	40	2	34.5	7270	^[38]
水-乙酸乙酯	NaA	50	2	315	163000	^[39]
水-乙酸乙酯	MXene/CS	50	2	1400	4898	^[40]
水-乙酸乙酯	PVA/SA/CPO	30	3	1132	16755	本文
水-乙酸	PVA/PAA	40	20	140	27	^[41]
水-乙酸	PVA/SA	33	10	49	21.5	^[42]
水-乙酸	PBI/sPBI	70	70	360	9.5	^[43]
水-乙酸	PVA/SPEK-C	50	10	492	59.3	^[44]
水-乙酸	PVA/4-Vinylpyridine	40	40	800	2	^[45]
水-乙酸	PANBA/SA	30	50	150	5.8	^[46]
水-乙酸	PVA/SA/CPO	60	55	4716	4.1	本文

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