Preparation of Efficient Pd/MgAl-LDO@Al2O3 Catalyst for Phenol Hydrogenation to Cyclohexanone

doi:10.6023/A21070343

Abstract

Cyclohexanone is an important intermediate for the synthesis of nylon, but the direct hydrogenation reaction of phenol to cyclohexanone can easily generate cyclohexanol. In this paper, the in situ synthesis strategy is used to grow the layered double hydrotalcites on alumina. Compared with the pristine alumina, the modified support has increased specific surface area, average pore size and abundant acid-base sites on the surface. Pd/MgAl-LDO@Al₂O₃ catalyst was then prepared by the calcination of precursor with layered structure, followed by the impregnation of Pd. The catalyst is used for the selective hydrogenation of phenol (reaction conditions: phenol/Pd=1000 mol/mol, 80 ℃, 0.4 MPa H₂). The obtained Pd/MgAl-LDO@Al₂O₃ shows enhanced catalytic performance under a high substrate/Pd ratio. Detailly, when the phenol conversion is 97%, the cyclohexanone selectivity can reach 88%. High-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analysis are performed to characterize the catalyst, and it is found that in situ growth of hydrotalcite-like structure on alumina can effectively decrease the average particle size of Pd and then increase the dispersion of active component. Moreover, when Ni is introduced into the layered structure, PdNi alloy structure could be obtained by the easy reduction process of using NaBH₄. Kinetics study indicates the energy barrier of the phenol hydrogenation reaction over Pd/NiAl-LDO@Al₂O₃is lower than that over Pd/MgAl-LDO@Al₂O₃ due to the formation of PdNi alloy. But the alloy structure leads to an obvious decrease of cyclohexanone selectivity. According to the product distribution and characterization results, a possible mechanism is proposed. Phenol is adsorbed on the surface of the basic sites on the Pd/MgAl-LDO@Al₂O₃ catalyst in a non-coplanar manner, which is conducive to the selective hydrogenation of phenol to produce cyclohexanone and inhibits the over-hydrogenation of cyclohexanone. After repeated use for 5 times, the Pd/MgAl-LDO@Al₂O₃ catalyst shows excellent stability. The phenol conversion could keep at ca. 90% and the cyclohexanone selectivity maintains ca. 90%.

Key words: selective hydrogenation of phenol, cyclohexanone, high substrate/Pd ratio, in situ growth, basic site

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Min Zhao, Xue Wang, Yanan Liu, Yufei He, Dianqing Li. Preparation of Efficient Pd/MgAl-LDO@Al₂O₃ Catalyst for Phenol Hydrogenation to Cyclohexanone[J]. Acta Chimica Sinica, 2021, 79(12): 1518-1525.

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Fig. & Tab. 11

Figure 1. (A) XRD patterns of support precursor and (B) XRD patterns of catalyst (a) Al2O3, (b) MgAl-LDHs@Al2O3, (c) NiAl-LDHs@Al2O3, (d) Pd/Al2O3, (e) Pd/MgAl-LDO@Al2O3 and (f) Pd/NiAl-LDO@Al2O3

Figure 2. SEM images of support precursor, support and catalyst (a) Al2O3, (b) MgAl-LDHs@Al2O3, (c) NiAl-LDHs@Al2O3, (d) Pd/Al2O3, (e) Pd/MgAl-LDO@Al2O3 and (f) Pd/NiAl-LDO@Al2O3

样品	比表面积/(m²•g^–1)	孔容/(cm³•g^–1)	平均孔径/nm	负载量/%	分散度/%
Pd/Al₂O₃	107	0.19	5.8	0.90	26.1
Pd/MgAl-LDO@Al₂O₃	139	0.34	9.8	0.83	33.2
Pd/NiAl-LDO@Al₂O₃	148	0.27	7.1	0.87	35.9

Table 1. Results of pore structure, loading and dispersion

Figure 3. (A) N2 adsorption and desorption curve of catalyst and (B) pore size distribution of catalyst

Figure 4. Profiles of (A) NH3-TPD and (B) CO2-TPD over catalysts (a, d) Pd/Al2O3, (b, e) Pd/MgAl-LDO@Al2O3 and (c, f) Pd/NiAl-LDO@Al2O3

Figure 5. Catalyst HRTEM images, particle size statistics and grain lattice fringe spacing diagrams (a, d) Pd/Al2O3, (b, e) Pd/MgAl-LDO@Al2O3 and (c, f) Pd/NiAl-LDO@Al2O3

Figure 6. XPS images of Pd catalysts (a) Pd/Al2O3, (b) Pd/MgAl-LDO@Al2O3 and (c) Pd/NiAl-LDO@Al2O3

Figure 7. (A) Curve of phenol conversion over time, (B) curve of cyclohexanone selectivity over conversion, (C) curve of cyclohexanol selectivity over conversion, (D) plots of the natural logarithm of TOF versus inversed temperature showing the apparent activation energy at low temperatures Reaction conditions: phenol/Pd=1000 mol/mol, 80 ℃, 0.4 MPa H2, 800 r/min

Figure 8. Proposed mechanism diagram of selective hydrogenation of phenol (A) Pd/MgAl-LDO@Al2O3 and (B) Pd/NiAl-LDO@Al2O3

Figure 9. Stability diagram of catalysts (A) Pd/MgAl-LDO@Al2O3, (B) Pd/NiAl-LDO@Al2O3

Figure 10. After the reaction, (A) XRD pattern, (B) thermogravimetric curve, HRTEM images and particle size statistics of the catalyst (C, D) (a) Pd/MgAl-LDO@Al2O3 and (b) Pd/NiAl-LDO@Al2O3

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苯酚加氢制环己酮用高效Pd/MgAl-LDO@Al₂O₃催化剂的制备及性能研究

Preparation of Efficient Pd/MgAl-LDO@Al₂O₃ Catalyst for Phenol Hydrogenation to Cyclohexanone

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苯酚加氢制环己酮用高效Pd/MgAl-LDO@Al2O3催化剂的制备及性能研究