应用化学 ›› 2022, Vol. 39 ›› Issue (11): 1735-1745.DOI: 10.19894/j.issn.1000-0518.220043

• 研究论文 • 上一篇    下一篇

沸石咪唑酯骨架结构材料ZIF-71用于低浓度生物基2,3-丁二醇/1,3-丙二醇的吸附分离性能

张健爽, 高美珍, 王梦瑶, 石琪(), 董晋湘   

  1. 太原理工大学化学工程与技术学院,太原 030024
  • 收稿日期:2022-02-21 接受日期:2022-05-19 出版日期:2022-11-01 发布日期:2022-11-09
  • 通讯作者: 石琪
  • 基金资助:
    国家自然科学基金(21822808)

Zeolitic Imidazolate Framework ZIF‑71 for Adsorption and Separation of 2,3‑Butanediol/1,3‑Propanediol From Dilute Aqueous Solutions

Jian-Shuang ZHANG, Mei-Zhen GAO, Meng-Yao WANG, Qi SHI(), Jin-Xiang DONG   

  1. Taiyuan University of Technology,Taiyuan 030024,China
  • Received:2022-02-21 Accepted:2022-05-19 Published:2022-11-01 Online:2022-11-09
  • Contact: Qi SHI
  • About author:shiqi594@163.com
  • Supported by:
    the National Natural Science Foundation of China(21822808)

摘要:

1,3-丙二醇是一种重要的化工原料,生物发酵法生产1,3-丙二醇往往会产生副产物2,3-丁二醇,限制了生物基1,3-丙二醇的进一步工业化应用。1,3-丙二醇与2,3-丁二醇亲水性强,导致其在低浓度发酵液中分离困难。基于2,3-丁二醇比1,3-丙二醇具有长的碳链和大的极化率,本文采用含有―Cl基团(憎水且具有大的极化率)的ZIF-71吸附分离水中低浓度的2,3-丁二醇/1,3-丙二醇。结果表明,ZIF-71对双组分2,3-丁二醇/1,3-丙二醇(50 g/L,50 g/L)中2,3-丁二醇的静态竞争吸附容量为123.6 mg/g,对2,3-丁二醇/1,3-丙二醇分离选择性高达7.6,分离效果优于沸石材料Beta。在3次循环吸附-解吸实验中ZIF-71依旧保持着稳定的结构和对2,3-丁二醇的选择性吸附能力。通过分子模拟,揭示了ZIF-71对1,3-丙二醇和2,3-丁二醇的吸附分离机制。ZIF-71与1,3-丙二醇之间主要通过弱的范德华力作用;而ZIF-71与2,3-丁二醇之间则是通过强的范德华力与弱的氢键协同作用,从而对2,3-丁二醇产生选择性吸附。可以看出, ZIFs材料有望成为选择性吸附分离低浓度副产物2,3-丁二醇的吸附剂,推动生物法制1,3-丙二醇的工业化发展。

关键词: 沸石咪唑酯骨架结构材料, ZIF-71, 吸附分离, 1, 3-丙二醇, 2, 3-丁二醇

Abstract:

1,3-Propanediol is an important chemical material, and the production of 1,3-propanediol by biological fermentation often produces 2,3-butanediol, which limits the further industrial application of bio-based 1,3-propanediol. 1,3-Propanediol and 2,3-butanediol have strong hydrophilicity, which makes it difficult to separate in low-concentration fermentation broth. ZIF-71 containing group —Cl (hydrophobicity and large polarizability) is selected to adsorb and separate 2,3-butanediol/1,3-propanediol from dilute aqueous solutions since 2,3-butanediol has a longer carbon chain and larger polarizability than 1,3-propanediol. The results show that the binary competitive adsorption capacity of ZIF-71 for 2,3-butanediol is 123.6 mg/g, the binary competitive separation selectivity for 2,3-butanediol/1,3-propanediol is up 7.6 and is better than Beta. In the three-cycle adsorption and desorption experiments, ZIF-71 still maintains a stable structure and selective adsorption for 2,3-butanediol. We reveal the separation mechanism of ZIF-71 for 1,3-propanediol and 2,3-butanediol through molecular simulation. The interaction between ZIF-71 and 1,3-propanediol is mainly through weak van der Waals force; while the interaction between ZIF-71 and 2,3-butanediol is through the synergistic effect of strong van der Waals force and weak hydrogen bonding, which causes the selective adsorption of 2,3-butanediol by ZIF-71. Therefore, ZIFs materials are expected to be candidate adsorbents for the selective adsorption and separation of by-product 2,3-butanediol from dilute aqueous solutions, which promotes the industrialization of biological production of 1,3-propanediol.

Key words: Zeolitic imidazolate frameworks, ZIF-71, Adsorption separation, 1, 3-Propanediol, 2, 3-Butanediol

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