Fine adjustment of elliptical windows of ZIFs and performances of adsorptive separation of furfural/5-hydroxymethylfurfural

doi:10.11949/0438-1157.20201071

Abstract

Abstract:

In the process of refining furan compounds through biomass catalysis, a mixture of low concentration furfural (Fur) and 5-hydroxymethylfurfural (5-HMF) aqueous solution is usually obtained. Based on the fact that both Fur and 5-HMF are elliptical molecules, the sieving separation of Fur and 5-HMF can be achieved by designing and adjusting the elliptical windows of the adsorbents. In this paper, we used divalent cobalt salts and three imidazole ligands with gradually increasing alkyl substituent groups (2-ethylimidazole/2-eIm, 2-propylimidazole/2-pIm and 2-butylimidazole/2-bIm) to synthesize three ANA topology ZIFs materials with gradually decreasing elliptical windows: ANA-[Co(eIm)₂], ANA-[Co(pIm)₂] and ANA-[Co(bIm)₂]. Firstly, the crystal structures of these three ZIFs were analyzed, and basic characterizations such as PXRD, water vapor adsorption, N₂ adsorption and desorption, and SEM were performed, and then batch adsorption and dynamic column adsorption were used to study the adsorptive separation performance of the three materials for Fur and 5-HMF. The results of batch adsorption, single-component dynamic column adsorption and general rate model simulation calculations show that: narrow and elliptical window of ANA-[Co(pIm)₂] is close to the Fur molecular size, but smaller than 5-HMF, so that Fur molecular can be adsorbed into the elliptical windows, while 5-HMF molecular is hardly adsorbed and cannot pass through. Furthermore, the adsorption capacity of ANA-[Co(pIm)₂] for Fur in the binary-component Fur/5-HMF (5%/5%,mass ratio) dynamic column adsorption is 91.7 mg·g^-1, and 5-HMF is not adsorbed. Therefore, by changing the imidazole ligand substituent groups, the size of the elliptical windows of ZIFs was finely adjusted, and the steric hindrance effect of the elliptical windows of ZIFs was used to achieve the sieve separation of Fur and 5-HMF.

Key words: zeolitic imidazolate frameworks, furfural, 5-hydroxymethylfurfural, adsorption, separation, recovery

摘要：

在生物质催化炼制呋喃化合物的过程中，通常得到的是低浓度糠醛（Fur）和5-羟甲基糠醛（5-HMF）的混合物。基于Fur和5-HMF都是椭圆形分子，因此通过设计构筑和调控椭圆形孔窗的吸附剂可以实现Fur和5-HMF的筛分分离。选用二价钴盐和三种烷基取代基团逐渐增大的咪唑配体（2-乙基咪唑/2-eIm、2-丙基咪唑/2-pIm和2-丁基咪唑/2-bIm）合成了三种椭圆形孔窗尺寸逐渐减小的ANA拓扑ZIFs材料：ANA-[Co(eIm)₂]、ANA-[Co(pIm)₂]和ANA-[Co(bIm)₂]。首先解析了这三种ZIFs材料的晶体结构，并对其进行了PXRD、水蒸气吸附、N₂吸脱附和SEM等基本表征，然后采用静态吸附和动态柱吸附研究了这三种材料对Fur和5-HMF的吸附分离性能。静态吸附、单组分动态柱吸附以及综合速率模型模拟计算结果显示：ANA-[Co(pIm)₂]狭窄的椭圆形孔窗与Fur分子尺寸接近，但小于5-HMF，使得Fur分子可以吸附进入椭圆形孔窗，而5-HMF分子几乎不能通过。进一步在双组分Fur/5-HMF（5%/5%，质量分数）动态柱吸附中，ANA-[Co(pIm)₂]对Fur的吸附量为91.7 mg·g^-1，不吸附5-HMF。因此，通过改变咪唑配体取代基团精细调控ZIFs椭圆形孔窗尺寸，并利用ZIFs椭圆形孔窗的位阻效应实现了Fur和5-HMF的筛分分离。

关键词: 沸石咪唑酯骨架材料, 糠醛, 5-羟甲基糠醛, 吸附, 分离, 回收

CLC Number:

TQ 028.3

ZHAO Yu, SHI Qi, DONG Jinxiang. Fine adjustment of elliptical windows of ZIFs and performances of adsorptive separation of furfural/5-hydroxymethylfurfural[J]. CIESC Journal, 2021, 72(1): 555-568.

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.

Figures/Tables 15

Fig.1 The fine adjustment of the elliptical windows of ZIFs based on adsorptive separation of Fur/5-HMF

Table 1 Crystal structure parameters of ZIFs materials

ZIFs

(CCDC number)

Cell parameter

a /?

Density/

(g·cm^-3)

Window/?²

S_BET /

(m²·g^-1)

Pore volume/(cm³·g^-1)

ANA-[Co(eIm)₂]

(2017658)

C₁₀H₁₄CoN₄

249.18

cubic

I a 3 ˉ d

ANA-[Co(pIm)₂]

(2017659)

C₁₂H₁₈CoN₄

277.23

cubic

I a 3 ˉ d

ANA-[Co(bIm)₂]

(2017657)

C₁₄H₂₂CoN₄

305.28

cubic

I a 3 ˉ d

Table 1 Crystal structure parameters of ZIFs materials

ZIFs

(CCDC number)

Empirical formula

Molecular weight

Crystal system

Space group

Cell parameter

a /?

Density/

(g·cm^-3)

Window/?²

S_BET /

(m²·g^-1)

Pore volume/(cm³·g^-1)

ANA-[Co(eIm)₂]

(2017658)

C₁₀H₁₄CoN₄

249.18

cubic

I a 3 ˉ d

26.581(2)

1.058

7.4×4.9/4.2

610

0.268

ANA-[Co(pIm)₂]

(2017659)

C₁₂H₁₈CoN₄

277.23

cubic

I a 3 ˉ d

26.606(2)

1.173

7.5×3.1/4.2

333

0.139

ANA-[Co(bIm)₂]

(2017657)

C₁₄H₂₂CoN₄

305.28

cubic

I a 3 ˉ d

26.340(3)

1.332

7.5×1.3/4.1

—

Fig.2 The basic characterizations of ANA-[Co(eIm)2], ANA-[Co(pIm)2] and ANA-[Co(bIm)2]

Fig.3 SEM images and particles pictures of ZIFs

Fig.4 Static adsorption isotherms of ZIFs for single-component Fur and 5-HMF at the temperature of 25℃ (Error bars correspond to the standard deviation at each point)

Table 2 Langmuir adsorption and Freundlich adsorption model for single-component batch adsorption fitting results

ZIFs	Langmuir model						Freundlich model
	Fur			5-HMF			Fur			5-HMF
	K_L/ (L·mg^-1)	q_max/(mg·g^-1)	R²	K_L/ (L·mg^-1)	q_max/(mg·g^-1)	R²	K_F/(mg·g^-1)	n	R²	K_F/ (mg·g^-1)	n	R²
ANA-[Co(eIm)₂]	3.144	271.8	0.981	0.367	318.1	0.981	176.153	3.108	0.841	79.946	1.569	0.941
ANA-[Co(pIm)₂]	0.622	145.2	0.991	0.344	9.2	0.901	52.038	1.968	0.952	2.376	1.710	0.942
ANA-[Co(bIm)₂]	0.064	44.1	0.950	1.014	3.1	0.958	2.672	1.145	0.945	1.403	2.263	0.937

Fig.5 Breakthrough curves of single-component Fur and 5-HMF on ZIFs at the temperature of 25℃ (length: 25 cm; diameter: 0.4 cm; rate: 0.05 ml·min-1)

Table 3 Fitting results of the general rate model (GRM) for single-component dynamic column adsorption

GRM parameter	ANA-[Co(eIm)₂]		ANA-[Co(pIm)₂]		ANA-[Co(bIm)₂]
GRM parameter	Fur	5-HMF	Fur	5-HMF	Fur	5-HMF
D_ax /(cm²·min^-1)	5.730×10^-4	1.567×10^-4	4.820×10^-4	1.773×10^-4	1.720×10^-4	4.675×10^-4
K_film/(cm·min^-1)	2.740×10^-2	2.360×10^-2	3.510×10^-2	1.350×10^-2	3.490×10^-2	1.900×10^-2
D_pore /(cm²·min^-1)	2.176×10^-3	2.054×10^-4	1.534×10^-3	8.035×10^-5	8.712×10^-5	8.006×10^-5

Table 4 Summary of adsorption capacity of single-component batch adsorption and dynamic column adsorption

Item	ANA-[Co(eIm)₂] /(mg·g^-1)				ANA-[Co(pIm)₂] /(mg·g^-1)				ANA-[Co(bIm)₂]/(mg·g^-1)
	2%		5%		2%		5%		2%		5%
	Fur	5-HMF	Fur	5-HMF	Fur	5-HMF	Fur	5-HMF	Fur	5-HMF	Fur	5-HMF
single-component batch adsorption	222.3	129.3	251.4	190.8	77.7	3.3	105.1	6.5	4.4	1.9	10.1	2.8
dynamic column adsorption
single	212.8	125.8	245.3	195.8	76.5	3.9	93.8	7.3	4.2	0.1	9.9	1.5
binary	208.9	2.7	239.1	2.3	77.1	—	91.7	—	4.1	—	9.1	—

Fig.6 Breakthrough curves of binary-component Fur/5-HMF diluted in water on ZIFs at the temperature of 25℃(length: 25 cm; diameter: 0.4 cm; rate: 0.05 ml·min-1)

Fig.7 Adsorption-desorption breakthrough curves of binary-component Fur/5-HMF (5%/5%) diluted in water on ANA-[Co(pIm)2] at different flow rates (length: 33 cm, diameter: 0.6 cm, adsorption temperature: 25℃, desorption temperature: 40℃; error bars correspond to the standard deviation at each point)

Fig.8 Adsorption-desorption breakthrough curves of binary-component Fur/5-HMF (5%/5%) diluted in water on ANA-[Co(pIm)2] in 5 adsorption-desorption cycles at a flow rate of 0.1 ml·min-1 (length: 33 cm, diameter: 0.6 cm, adsorption temperature: 25℃, desorption temperature: 40℃)

Fig.9 PXRD patterns of ZIFs before and after adsorption Fur and 5-HMF and solvent regeneration

Fig.10 Breakthrough curves of binary-component Fur/5-HMF (5%/5%) diluted in water on ZSM-5 and ANA-[Co(pIm)2] at the temperature of 25℃(length: 25 cm, diameter: 0.4 cm, rate: 0.05 ml·min-1)

Table 5 Summary of adsorption capacity and selectivity of dynamic column adsorption for ZSM-5, MAF-5[21], ANA-[Co(eIm)2] and ANA-[Co(pIm)2]

Adsorbent	q_Fur/(mg·g^-1)	q_5-HMF /(mg·g^-1)	S_Fur,5-HMF
ZSM-5	112.7	30.1	3.7
MAF-5	220.0	1.9	115.8
ANA-[Co(eIm)₂]	239.1	2.3	104.0
ANA-[Co(pIm)₂]	91.7	—	—

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