ZTIF基疏水微介孔碳的制备及5-羟甲基糠醛吸附分离性能

doi:10.11949/0438-1157.20231418

摘要/Abstract

摘要：

经过生物质酸性催化转化的5-羟甲基糠醛（5-HMF）原液的组成为低浓度水溶液、多组分酸性副产物乙酰丙酸（LA）和甲酸（FA），因此需要设计疏水、耐酸和高选择性的吸附剂来分离5-HMF。以高N的沸石型四氮唑-咪唑骨架材料（ZTIFs）为前体，通过调控碳化和活化条件制备具有耐酸性、疏水性和合适微介孔分布的多孔碳，利用多孔碳和5-HMF的π-π作用可实现含酸水溶液中5-HMF的高效富集分离。以ZTIF-8为前体，通过调控碳化温度和活化碱碳比，制备并筛选三种具有不同N含量和微介孔分布的ZTIF-8基多孔碳；建立ZTIF-8基多孔碳N含量和微介孔分布与5-HMF吸附分离性能的关系；具有低N含量和丰富大微孔小介孔（12～30 Å，1 Å=0.1 nm）的NC_ZTIF-8700C-800A₂是从含酸性副产物水溶液中高效富集分离5-HMF的吸附剂。

关键词: 吸附, 分离, 回收, 多孔碳, 疏水, 微介孔, 5-羟甲基糠醛

Abstract:

The stock solution of 5-hydroxymethylfurfural (5-HMF) that has undergone acidic catalytic conversion of biomass is composed of a low-concentration aqueous solution and multi-component acidic by-products levulinic acid (LA) and formic acid (FA). Therefore, the design of 5-HMF separation adsorbents requires hydrophobicity, acid resistance, and high selectivity. In this work, porous carbon with acid resistance, hydrophobicity and suitable micro-mesoporous distribution were obtained by controlling carbonization temperature and activation conditions using high N-content zeolitic tetrazolate-imidazolate frameworks (ZTIFs) as precursors, and the π-π interaction between porous carbon and 5-HMF can be used to achieve efficient enrichment and separation of 5-HMF in acid-containing aqueous solution. Three types of ZTIF-8 based porous carbon with different N-content and micro-mesoporous distribution were obtained by controlling carbonization temperature and activating alkali carbon ratio using ZTIF-8 as precursor. The relationship between the N-content and micro-mesoporous distribution of ZTIF-8 based porous carbon and the adsorption and separation performance of 5-HMF has been established. NC_ZTIF-8700C-800A₂, with low N-content and abundant large micropores and small mesopores (12—30 Å), is an adsorbent for efficient enrichment and separation of 5-HMF from aqueous solutions containing acidic by-products.

Key words: adsorption, separation, recovery, porous carbon, hydrophobic, micro-mesoporous, 5-HMF

中图分类号:

TQ 028.3

吕田田, 原敏, 王江, 高美珍, 杨佳辉, 徐红, 董晋湘, 石琪. ZTIF基疏水微介孔碳的制备及5-羟甲基糠醛吸附分离性能[J]. 化工学报, 2024, 75(4): 1642-1654.

Tiantian LYU, Min YUAN, Jiang WANG, Meizhen GAO, Jiahui YANG, Hong XU, Jinxiang DONG, Qi SHI. Preparation of ZTIF based hydrophobic micro-mesoporous carbon and their adsorption and separation performance of 5-hydroxymethylfurfural[J]. CIESC Journal, 2024, 75(4): 1642-1654.

图/表 16

图1 ZIF-8、ZTIF-8和Zn(5-mttz)2的基本表征结果

Fig.1 Basic characterizations of ZIF-8, ZTIF-8 and Zn(5-mttz)2

表1 ZTIF-8、NCZTIF-8700C和NCZTIF-8700C-800A z 的孔结构和元素分析

Table 1 Pore structures and elemental analysis of ZTIF-8， NCZTIF-8700C and NCZTIF-8700C-800A z

Samples	Bulk N/%	BET/(m²·g^-1)	Total pore volume/ (cm³·g^-1)	Cumulative pore volume/(cm³·g^-1)
Samples	Bulk N/%	BET/(m²·g^-1)	Total pore volume/ (cm³·g^-1)	<12 Å	12~22 Å	22~30 Å	12~30 Å	30~60 Å
ZTIF-8	—	1570.5	0.59	0.31	0.24	0	0.24	0
NC_ZTIF-8700C	21.81	853.3	0.41	0.32	0	0	0	0
NC_ZTIF-8700C-800A_0.5	12.33	1863.5	0.86	0.51	0.29	0	0.29	0
NC_ZTIF-8700C-800A₁	6.85	3096.0	1.96	0.50	0.72	0.63	1.35	0
NC_ZTIF-8700C-800A₂	1.62	2701.4	2.39	0.36	0.36	0.88	1.24	0.67
NC_ZTIF-8700C-800A₄	1.30	2643.5	2.83	0.29	0.43	0.32	0.75	1.43

图2 NCZTIF-8XC的基本表征结果

Fig.2 Basic characterizations of NCZTIF-8XC

图3 NCZTIF-8700C-800A z 的基本表征结果

Fig.3 Basic characterizations of NCZTIF-8700C-800A z

图4 NCZTIF-8700C-800A z 的N2吸脱附表征结果

Fig.4 N2 adsorption-desorption characterizations of NCZTIF-8700C-800A z

图5 ZTIF-8、NCZTIF-8700C和NCZTIF-8700C-800A z 的SEM图

Fig.5 SEM images of ZTIF-8, NCZTIF-8700C and NCZTIF-8700C-800A z

图6 25℃下NCZTIF-8700C-800A z 对单组分5-HMF、LA和FA的静态吸附等温线

Fig.6 Static adsorption isotherms of NCZTIF-8700C-800A z for single-component 5-HMF,LA and FA at 25℃

图7 25℃下NCZTIF-8700C-800A z 对三组分的静态竞争吸附等温线

Fig.7 Static ternary-component competitive adsorption isotherms of NCZTIF-8700C-800A z at 25℃

表2 NCZTIF-8700C-800A z 的静态吸附量和选择性汇总

Table 2 Summary of static adsorption capacity and selectivity of NCZTIF-8700C-800A z

Samples	Single-component Q_e/(mg·g^-1)			Ternary-component Q_i,_e/(mg·g^-1)			S_i,j
Samples	5-HMF (5.0%)	LA (2.5%)	FA (1.0%)	5-HMF (5.0%)	LA (2.5%)	FA (1.0%)	5-HMF/LA	5-HMF/FA
NC_ZTIF-8700C-800A₁	842.0	399.7	86.1	555.8	60.8	9.5	5.0	12.3
NC_ZTIF-8700C-800A₂	1072.7	626.6	111.5	803.6	103.5	5.8	4.2	29.0
NC_ZTIF-8700C-800A₄	968.0	451.0	89.2	727.9	71.6	3.1	5.6	49.4

图8 25℃下NCZTIF-8700C-800A z 对三组分的动态穿透曲线

Fig.8 Dynamic ternary-component breakthrough curves of NCZTIF-8700C-800A z at 25℃

表3 NCZTIF-8700C-800A z 的动态柱吸附量和选择性汇总

Table 3 Summary of dynamic column adsorption capacity and selectivity of NCZTIF-8700C-800A z

Samples	Ternary-component Q_i,_ads/(mg·g^-1)			S_i,j
Samples	5.0% 5-HMF	2.5%LA	1.0%FA	5-HMF/LA	5-HMF/FA
NC_ZTIF-8700C-800A₁	774.3	88.6	29.7	4.4	5.2
NC_ZTIF-8700C-800A₂	1092.3	109.5	15.5	5.2	14.3
NC_ZTIF-8700C-800A₄	1040.3	107.1	6.8	5.1	30.4

图9 25℃下NCZTIF-8700C-800A2对三组分的动态吸脱附曲线

Fig.9 Dynamic ternary-component absorption and desorption curves of NCZTIF-8700C-800A2 at 25℃

图10 不同吸附剂对5-HMF的吸附量对比

Fig.10 Comparison of adsorption capacity of adsorbents for 5-HMF

图11 NCZTIF-8700C-800A2对三组分静态竞争循环吸附量

Fig.11 Static ternary-component competitive cyclic adsorption capacity of NCZTIF-8700C-800A2

图12 5-HMF、LA、FA和H2O与石墨烯片段之间的结合能与作用力

Fig.12 Calculation of binding energies and force between 5-HMF, LA, FA, water and graphene species

图13 5-HMF、LA、FA和H2O与含N物种掺杂石墨烯片段之间的结合能与作用力

Fig.13 Calculation of binding energies and force between 5-HMF, LA, FA, water and N-doped graphene species

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