Preparation of ZTIF based hydrophobic micro-mesoporous carbon and their adsorption and separation performance of 5-hydroxymethylfurfural

doi:10.11949/0438-1157.20231418

Abstract

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

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

CLC Number:

TQ 028.3

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.

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.

Figures/Tables 16

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

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

Fig.2 Basic characterizations of NCZTIF-8XC

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

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

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

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

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

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

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

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

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

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

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

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

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

References 37

1	Gervais E, Shammugam S, Friedrich L, et al. Raw material needs for the large-scale deployment of photovoltaics—effects of innovation-driven roadmaps on material constraints until 2050[J]. Renewable and Sustainable Energy Reviews, 2021, 137: 110589.
2	Galimova T, Ram M, Bogdanov D, et al. Global demand analysis for carbon dioxide as raw material from key industrial sources and direct air capture to produce renewable electricity-based fuels and chemicals[J]. Journal of Cleaner Production, 2022, 373: 133920.
3	Martin N, Madrid-López C, Villalba-Méndez G, et al. New techniques for assessing critical raw material aspects in energy and other technologies[J]. Environmental Science & Technology, 2022, 56(23): 17236-17245.
4	Mujtaba M, Fernandes Fraceto L, Fazeli M, et al. Lignocellulosic biomass from agricultural waste to the circular economy: a review with focus on biofuels, biocomposites and bioplastics[J]. Journal of Cleaner Production, 2023, 402: 136815.
5	Zhang B, Biswal B K, Zhang J J, et al. Hydrothermal treatment of biomass feedstocks for sustainable production of chemicals, fuels, and materials: progress and perspectives[J]. Chemical Reviews, 2023, 123(11): 7193-7294.
6	Xu C, Paone E, Rodríguez-Padrón D, et al. Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural[J]. Chemical Society Reviews, 2020, 49(13): 4273-4306.
7	Zhang X G, Wilson K, Lee A F. Heterogeneously catalyzed hydrothermal processing of C₅—C₆ sugars[J]. Chemical Reviews, 2016, 116(19): 12328-12368.
8	Slak J, Pomeroy B, Kostyniuk A, et al. A review of bio-refining process intensification in catalytic conversion reactions, separations and purifications of hydroxymethylfurfural (HMF) and furfural[J]. Chemical Engineering Journal, 2022, 429: 132325.
9	Wang H Y, Zhu C H, Li D, et al. Recent advances in catalytic conversion of biomass to 5-hydroxymethylfurfural and 2, 5-dimethylfuran[J]. Renewable and Sustainable Energy Reviews, 2019, 103: 227-247.
10	Hu L, Wu Y R, Li M W, et al. Highly selective adsorption of 5-hydroxymethylfurfural from multicomponent mixture by simple pH controlled in batch and fixed-bed column studies: competitive isotherms, kinetic and breakthrough curves simulation[J]. Separation and Purification Technology, 2022, 299: 121756.
11	Hu L, Wu Z, Jiang Y T, et al. Recent advances in catalytic and autocatalytic production of biomass-derived 5-hydroxymethylfurfural[J]. Renewable and Sustainable Energy Reviews, 2020, 134: 110317.
12	石宁, 刘琪英, 王铁军, 等. 葡萄糖催化脱水制取5-羟甲基糠醛研究进展[J]. 化工进展, 2012, 31(4): 792-800.
	Shi N, Liu Q Y, Wang T J, et al. Preparation of 5-hydroxymethylfurfural from glucose by catalytic dehydration[J]. Chemical Industry and Engineering Progress, 2012, 31(4): 792-800.
13	Chen S, Wojcieszak R, Dumeignil F, et al. How catalysts and experimental conditions determine the selective hydroconversion of furfural and 5-hydroxymethylfurfural[J]. Chemical Reviews, 2018, 118(22): 11023-11117.
14	Sayed M, Warlin N, Hulteberg C, et al. 5-Hydroxymethylfurfural from fructose: an efficient continuous process in a water-dimethyl carbonate biphasic system with high yield product recovery[J]. Green Chemistry, 2020, 22(16): 5402-5413.
15	Jeong G T, Kim S K. Statistical optimization of levulinic acid and formic acid production from lipid-extracted residue of Chlorella vulgaris [J]. Journal of Environmental Chemical Engineering, 2021, 9(2): 105142.
16	Enomoto K, Hosoya T, Miyafuji H. High-yield production of 5-hydroxymethylfurfural from D-fructose, D-glucose, and cellulose by its in situ removal from the reaction system[J]. Cellulose, 2018, 25(4): 2249-2257.
17	Wei Z J, Liu Y X, Thushara D, et al. Entrainer-intensified vacuum reactive distillation process for the separation of 5-hydroxylmethylfurfural from the dehydration of carbohydrates catalyzed by a metal salt-ionic liquid[J]. Green Chemistry, 2012, 14(4): 1220-1226.
18	Johnson R L, Perras F A, Hanrahan M P, et al. Condensed phase deactivation of solid Brønsted acids in the dehydration of fructose to hydroxymethylfurfural[J]. ACS Catalysis, 2019, 9(12): 11568-11578.
19	Wang H Y, Cui J J, Zhao Y L, et al. Highly efficient separation of 5-hydroxymethylfurfural from imidazolium-based ionic liquids[J]. Green Chemistry, 2021, 23(1): 405-411.
20	Román-Leshkov Y, Chheda J N, Dumesic J A. Phase modifiers promote efficient production of hydroxymethylfurfural from fructose[J]. Science, 2006, 312(5782): 1933-1937.
21	Sun X F, Liu Z H, Xue Z M, et al. Extraction of 5-HMF from the conversion of glucose in ionic liquid [Bmim]Cl by compressed carbon dioxide[J]. Green Chemistry, 2015, 17(5): 2719-2722.
22	Yang Q, Runge T. Cross-linked polyethylenimine for selective adsorption and effective recovery of lignocellulose-derived organic acids and aldehydes[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(1): 933-943.
23	Chen X F, Li H L, Ji X R, et al. Preparation, separation and purification of 5-hydroxymethylfurfural from sugarcane molasses by a self-synthesized hyper-cross-linked resin[J]. Separation and Purification Technology, 2023, 315: 123661.
24	Yabushita M, Li P, Kobayashi H, et al. Complete furanics-sugar separations with metal-organic framework NU-1000[J]. Chemical Communications, 2016, 52(79): 11791-11794.
25	Yoo W C, Rajabbeigi N, Mallon E E, et al. Elucidating structure-properties relations for the design of highly selective carbon-based HMF sorbents[J]. Microporous and Mesoporous Materials, 2014, 184: 72-82.
26	赵宇, 石琪, 董晋湘. ZIFs椭圆形孔窗的精细调控及糠醛/5-羟甲基糠醛吸附分离性能研究[J]. 化工学报, 2021, 72(1): 555-568.
	Zhao Y, Shi Q, Dong J X. Fine adjustment of elliptical windows of ZIFs and performances of adsorptive separation of furfural/5-hydroxymethylfurfural[J]. CIESC Journal, 2021, 72(1): 555-568.
27	Hu L, Zheng J Y, Li Q, et al. Adsorption of 5-hydroxymethylfurfural, levulinic acid, formic acid, and glucose using polymeric resins modified with different functional groups[J]. ACS Omega, 2021, 6(26): 16955-16968.
28	Hu L, Tao S H, Xian J T, et al. Fabricating amide functional group modified hyper-cross-linked adsorption resin with enhanced adsorption and recognition performance for 5-hydroxymethylfurfural adsorption via simple one-step[J]. Chinese Journal of Chemical Engineering, 2022, 43: 230-239
29	Zhang Y B, Luo Q X, Lu M H, et al. Controllable and scalable synthesis of hollow-structured porous aromatic polymer for selective adsorption and separation of HMF from reaction mixture of fructose dehydration [J]. Chemical Engineering Journal, 2019, 358: 467-479.
30	Jin H, Li Y S, Liu X L, et al. Recovery of HMF from aqueous solution by zeolitic imidazolate frameworks[J]. Chemical Engineering Science, 2015, 124: 170-178.
31	Swift T D, Bagia C, Nikolakis V, et al. Reactive adsorption for the selective dehydration of sugars to furans: Modeling and experiments [J]. Aiche Journal, 2013, 59(9): 3378-3390.
32	Dornath P, Fan W. Dehydration of fructose into furans over zeolite catalyst using carbon black as adsorbent[J]. Microporous and Mesoporous Materials, 2014, 191: 10-17.
33	Li M Y, Wang F, Zhang J. Zeolitic tetrazolate-imidazolate frameworks with SOD topology for room temperature fixation of CO₂ to cyclic carbonates[J]. Crystal Growth & Design, 2020, 20(5): 2866-2870.
34	Yuan M, Liu Z Q, Lv T T, et al. Confinement effect and efficient adsorption of furfural onto ZIF-8-derived microporous carbon [J]. Journal of Chemical Technology and Biotechnology, 2023, 98(5): 1166-1174.
35	Gao M Z, Wang J, Rong Z H, et al. A combined experimental-computational investigation on water adsorption in various ZIFs with the SOD and RHO topologies[J]. RSC Advances, 2018, 8(69): 39627-39634.
36	Yuan M, Liu T C, Shi Q, et al. Understanding the KOH activation mechanism of zeolitic imidazolate framework-derived porous carbon and their corresponding furfural/acetic acid adsorption separation performance[J]. Chemical Engineering Journal, 2022, 428: 132016.
37	Yuan M, Gao M Z, Shi Q, et al. Understanding the characteristics of water adsorption in zeolitic imidazolate framework-derived porous carbon materials[J]. Chemical Engineering Journal, 2020, 379: 122412.

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