A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions

doi:10.1016/S1872-2067(21)63811-1

Abstract

Abstract:

S olid acid catalyst plays a crucial role in the petroleum refinery industry and bio-refinery technology. In this work, p-phenolsulfonic acid (PSA) was successfully grafted onto the surface of KH560-modified zirconium phosphate (K-ZrP) in a facile routine. The structure and property of this organic-inorganic combined solid acid PSA/K-ZrP-x were characterized via XRD, FTIR, ¹³C solid-state NMR, TG, N₂ adsorption-desorption, SEM, pyridine-adsorption FTIR and XPS technologies. The characterization results showed that KH560 can bond with ZrP and promote the grafting of PSA on the surface of K-ZrP via the condensation reaction between its epoxy ring and the phenolic hydroxyl group in PSA. Consequently, PSA/K-ZrP-2 exhibited excellent performance and stability in the transesterification between glycerol and methyl acetate among the tested H₃PW₁₂O₄₀, Amberlyst-45, HBEA, HZSM-5, ZrP, AlCl₃ and FeCl₃ catalysts. The calculated conversion of glycerol reached 81.3% with a 97.9% selectivity for monoacetin (MAG) and diacetin (DAG) with a 2.2% dosage of [H⁺] at 100 °C for 4 h. The highest specific activity of PSA/K-ZrP-2 reached 24028.2 mg-glycerol/g-cat/h in a short reaction time (at 0.17 h), and it could be recycled five times without obvious deactivation.

Key words: Solid acid catalyst, p-Phenolsulfonic acid, Zirconium phosphate, Glycerol, Transesterification

Yuanyuan Jiang, Ruru Zhou, Huaiyuan Zhao, Boyong Ye, Yihua Long, Zhengbao Wang, Zhaoyin Hou. A highly active and stable organic-inorganic combined solid acid for the transesterification of glycerol under mild conditions[J]. Chinese Journal of Catalysis, 2021, 42(10): 1772-1781.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63811-1

https://www.cjcatal.com/EN/Y2021/V42/I10/1772

Figures/Tables 17

Scheme 1. Transesterification of glycerol with methyl acetate.

Scheme 2. Synthesis routine of PSA/K-ZrP-2.

Fig. 1. XRD patterns of ZrP, K-ZrP and PSA/K-ZrP-2.

Fig. 2. FTIR spectra of ZrP, K-ZrP and PSA/K-ZrP-2.

Fig. 3. 13C solid-state NMR spectrum of PSA/K-ZrP-2.

Fig. 4. Thermal analysis curves of PSA/K-ZrP-2.

Table 1 Properties of ZrP, K-ZrP and PSA/K-ZrP-x.

Sample	Surface area (m²/g)	PSA content^a (wt%)	Bulk S content^b (%)	Surface S content^c (%)	[H⁺] content^d (mmol/g_-cat)	Acid density ^e (mmol/m²)
ZrP	43.6	—	—	—	1.300 ^f	0.0298
K-ZrP	13.9	—	—	—	—	—
PSA/K-ZrP-0.2	6.3	3.1	0.4	—	0.188	0.0298
PSA/K-ZrP-1	3.8	16.2	2.2	—	0.938	0.247
PSA/K-ZrP-2	2.1	38.2	4.8	5.6	2.190	1.043
PSA/K-ZrP-3	1.7	45.2	5.3	5.4	2.594	1.526

Fig. 5. N2 adsorption-desorption isotherms of ZrP, K-ZrP and PSA/K-ZrP-2.

Fig. 6. SEM images of ZrP (a), K-ZrP (b), PSA/K-ZrP-2 (c) and line-EDS of PSA/K-ZrP-2.

Table 2 Transesterification of glycerol with methyl acetate over PSA/K-ZrP-x a.

Catalyst	Conversion (%)	Specific activity^b (mg-glycerol/g-cat/h)	Product selectivity (%)			Carbon balance ^c
Catalyst	Conversion (%)	Specific activity^b (mg-glycerol/g-cat/h)	MAG	DAG	TAG	Carbon balance ^c
ZrP	0 1.4	32.2	100	0	0	99.5
K-ZrP	0.7	16.1	100	0	0	99.5
PSA/K-ZrP-0.2	44.9	1032.7	96.1	3.9	0	99.0
PSA/K-ZrP-1	67.9	1561.7	71.8	27.3	0.9	98.5
PSA/K-ZrP-2	81.3	1869.9	63.8	34.1	2.1	98.3
PSA/K-ZrP-3	80.9	1860.7	65.8	32.5	1.7	98.0
PSA	85.4	1964.2	61.9	34.8	3.3	97.5

Table 3 Transesterification of glycerol with methyl acetate over acid catalysts a.

Catalyst	Conversion (%)	Specific activity (mg-glycerol/g-cat/h) ^b	Product selectivity (%)			Carbon balance ^c
Catalyst	Conversion (%)	Specific activity (mg-glycerol/g-cat/h) ^b	MAG	DAG	TAG	Carbon balance ^c
Amberlyst-45	86.6	1991.8	59.5	37.3	3.2	99.0
H₃PW₁₂O₄₀	82.5	1897.5	68.9	28.3	2.8	97.8
HBEA ^d	51.3	1179.9	79.1	19.9	1.0	99.3
HZSM-5 ^d	1.8	41.4	100	0	0	99.3
PSA/K-ZrP-2	81.3	1869.9	63.8	34.1	2.1	98.3
AlCl₃	40.1	922.3	92.0	7.9	0.1	98.5
FeCl₃	18.2	418.6	100	0	0	98.5

Fig. 7. Recycle usage of PSA/K-ZrP-2. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, initial 0.1 g catalyst, 100 °C, 0.5 h, 1 MPa N2.

Fig. 8. Transesterification of glycerol at varied temperature over PSA/K-ZrP-2. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, 0.1 g catalyst, 4 h, 1 MPa N2.

Fig. 9. Transesterification of glycerol with different molar ratios of methyl acetate/glycerol in feed. Reaction conditions: 10 mmol glycerol, 0.1 g catalyst, 100 °C, 4 h, 1 MPa N2.

Fig. 10. Transesterification of glycerol with methyl acetate with different dosages of PSA/K-ZrP-2. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, 100 °C, 4 h, 1 MPa N2.

Fig. 11. Time course of transesterification of glycerol with methyl acetate. Reaction conditions: 10 mmol glycerol, 100 mmol methyl acetate, 0.1 g catalyst, 100 °C, 1 MPa N2.

Table 4 Transesterification of glycerol with different esters over PSA/K-ZrP-2 a.

Entry	Esters	Temperature, time	Conv. (%)	Product selectivity (%)
Entry	Esters	Temperature, time	Conv. (%)	MG	DG	TG
1		100 °C, 4 h	75.6	88.5	10.5	1.0
2		100 °C, 4 h	83.3	54.0	43.0	3.0
3		100 °C, 4 h	90.2	27.4	54.9	17.6
4		120 °C, 4 h	80.5	61.3	36.7	2.0
5		120 °C, 6 h	81.9	54.5	42.3	3.2

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