Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water

doi:10.1016/S1872-2067(21)63842-1

Abstract

Abstract:

Tandem catalysis for the hydrogenation rearrangement of furfural (FA) provides an attractive solution for manufacturing cyclopentanone (CPO) from renewable biomass resources. The CuNi/Al-MCM-41 catalyst was synthesized and afforded excellent catalytic performance with 99.0% conversion and 97.7% selectivity to CPO in a near-neutral solution under 2.0 MPa H₂ at 160 °C for 5 h, much higher than those on other molecular sieve supports including MCM-41, SBA-15, HY, and ZSM-5. A small amount of Al highly dispersed in MCM-41 plays an anchoring role and ensures the formation of highly dispersed CuNi bimetallic nanoparticles (NPs). The remarkably improved catalytic performance may be attributed to the bimetallic synergistic and charge transfer effects. In addition, the initial FA concentration and the aqueous system pH required precise control to minimize polymerization and achieve high selectivity of CPO. Fourier transform infrared spectroscopy and mass spectra results indicated that polymerization was sensitive to pH values. Under acidic conditions, FA and intermediate furfuryl alcohol polymerize, while the intermediate 4-hydroxy-2-cyclopentenone mainly polymerizes under alkaline conditions, blocking the cascade of multiple reactions. Therefore, near-neutral conditions are most suitable for minimizing the impact of polymerization. This study provides a useful solution for the current universal problems of polymerization side reactions and low carbon balance for biomass conversion.

Key words: Tandem catalysis, Bimetallic synergic effect, Cyclopentanone, Furfural, Hydrogenation-rearrangement

Shujing Zhang, Hong Ma, Yuxia Sun, Xin Liu, Meiyun Zhang, Yang Luo, Jin Gao, Jie Xu. Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water[J]. Chinese Journal of Catalysis, 2021, 42(12): 2216-2224.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63842-1

https://www.cjcatal.com/EN/Y2021/V42/I12/2216

Figures/Tables 11

Fig. 1. (a) Schematic illustration of the synthesis route for the CuNi/Al-MCM-41 catalyst; TEM images of Cu/Al-MCM-41 (b), Ni/Al-MCM-41 (c), and CuNi/Al-MCM-41 (d,f,g); (e,h) HRTEM images of CuNi/Al-MCM-41; (i) XRD patterns of CuNi/Al-MCM-41 (1), Cu/Al-MCM-41 (2), and Ni/Al-MCM-41 (3).

Fig. 2. Scanning TEM high angle annular dark field (STEM-HAADF) image, the corresponding EDX elemental mapping of the O, Si, Al, Ni, and Cu, and line-scanning profiles recorded along the line marked for CuNi/Al-MCM-41 catalyst.

Fig. 3. Hydrogenation rearrangement of FA over CuNi bimetallic catalysts. Reaction condition: 0.5 g FA, 0.0625 g catalysts, 160 °C, 2.0 MPa H2, 5 h, 5 mL H2O. a: 10 mL H2O.

Fig. 4. XRD patterns of different CuNi bimetallic catalysts.

Fig. 5. XPS spectra of different catalysts. (a) Ni 2p of Ni/Al-MCM-41 and CuNi/Al-MCM-41; (b) Cu 2p of Cu/Al-MCM-41 and CuNi/Al-MCM-41; (c) Cu Auger 2p of Cu/Al-MCM-41 and CuNi/Al-MCM-41.

Table 1 Catalytic performance of the FA hydrogenation rearrangement with different catalysts.

Entry	Catalyst	Conversion (mol%)	Product yield (mol%)
Entry	Catalyst	Conversion (mol%)	FAL	CPO	CPL	THFA	Others
1	CuNi/Al-MCM-41	98.3	1.5	67.7	1.7	8.0	19.4
2	Ni/Al-MCM-41	66.8	2.6	16.8	n.d.	2.6	44.8
3	Cu/Al-MCM-41	49.6	5.3	1.2	n.d.	0.9	42.2
4	Cu/Al-MCM-41+ Ni/Al-MCM-41 Ni/Al-MCM-41	63.9	7.0	38.8	n.d.	3.0	15.1

Fig. 6. Relevance of pH and catalytic performance of CuNi/Al-MCM-41. Reaction condition: 0.5 g FA, 0.0625 g CuNi/Al-MCM-41, 160 °C, 2.0 MPa, 5 h, 10 mL H2O (regulated by H2SO4 and NaOH).

Fig. 7. Comparison of reactions in solutions at different pH values without catalysts using starting substrates of FA (a), FAL (b), and HCP (c), respectively, and the corresponding typical IR spectraofpolymers extracted from reaction of FA (d), FAL (e), and HCP (f) at the pH of 11.45. Reaction conditions: 0.5 g substrate, 2.0 MPa H2, 160 °C, and 10 mL H2O with initial pH of 2.81, 7.05, 11.45 (regulated by H2SO4 and NaOH).

Fig. 8. MALDI-TOF characteristic of polymer extracted from spent catalysts at pH = 2.86 (a) and 11.13 (b).

Table 2 Influence of FA concentration and temperature on hydrogenation rearrangement over CuNi/Al-MCM-41.

Entry	FA:H₂O (wt%)	Temperature (°C)	Conversion (mol%)	Selectivity (mol%)
Entry	FA:H₂O (wt%)	Temperature (°C)	Conversion (mol%)	FAL	CPO	CPL	THFA	Others	Excessive hydrogenation
1	5	80	38.1	64.7	n.d.	2.4	3.3	29.6	5.7
2	5	120	83.3	45.0	14.7	1.1	1.5	37.7	2.6
3	5	140	89.6	7.3	53.6	0.3	2.8	36.1	3.1
4	5	160	96.4	2.1	83.6	2.4	6.2	5.7	8.6
5	5	180	97.7	0.6	60.7	1.2	6.1	31.3	7.4
6	20	160	96.0	2.7	44.2	2.2	9.9	41.0	12.1
7	10	160	94.5	1.1	59.2	1.3	6.3	32.1	7.6
8	2.5	160	96.6	1.3	91.1	3.2	1.2	3.1	4.4
9 ^a	1.2	160	99.0	n.d.	97.7	0.6	n.d.	1.7	0.6
10 ^b	5	160	99.6	0.6	37.0	15.2	21.0	26.2	36.2
11 ^c	5	160	99.7	0.5	42.4	9.3	4.4	43.4	13.7

Scheme 1. Mechanism of the FA hydrogenation rearrangement and side reactions without the presence of a catalyst.

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