One-pot synthesis of the highly efficient bifunctional Ni-SAPO-11 catalyst

doi:10.1016/j.jmst.2020.10.033

Abstract

Abstract:

Hydroisomerization of linear alkanes to branched isomers is an important petrochemical process for production of gasoline with high octane number. Non-noble metal bifunctional catalysts used in this process always suffer from low metal dispersion and poor metal-acid synergy. Herein, a facile one-pot synthesis method was used to simultaneously regulate metal particle sizes and acidity of the Ni-SAPO-11 hydroisomerization catalyst. The physicochemical properties are investigated using XANES, EXAFS, TEM/STEM, FT-IR, XPS, UV-vis and NH₃-TPD. Apart from the highly dispersed nickel nanoparticles with an average diameter of 8 nm, the framework Ni²⁺ ions are generated via substituting framework Al³⁺ ions of the SAPO-11. The formed NiP-OH structures have lower deprotonation energy (DPE) than the SiAl-OH ones, contributing more and stronger acid sites to the Ni-SAPO-11 catalyst. The great metal-acid synergy including high metal to acid sites ratio (n_Ni/n_A) and close intimacy is obtained for the Ni-SAPO-11 catalyst. The Ni-SAPO-11 catalyst outperforms the counterpart prepared by the impregnation method and exhibits comparable activity and isomers selectivity to the Pt/SAPO-11 catalyst in the n-hexane hydroisomerization.

Key words: One-pot synthesis, Nickel, SAPO-11, Hydroisomerization, Metal-acid synergy

Yuchao Lyu, Weilong Zhan, Zhumo Yu, Xinmei Liu, , Xiaoxing Wang, Chunshan Song, Zifeng Yan. One-pot synthesis of the highly efficient bifunctional Ni-SAPO-11 catalyst[J]. J. Mater. Sci. Technol., 2021, 76: 86-94.

Figures/Tables 17

Fig. 1. (a) n-C6 Conversion and (b) i-C6 yield as a function of reaction temperatures, (c) selectivity to i-C6 against n-C6 conversion at 2.0 MPa, H2/n-C6 = 4.0 and WHSV =1.0 h-1; (d) The catalytic performance of the catalysts at 613 K, 2.0 MPa, H2/n-C6 = 4.0 and WHSV =1.0 h-1.

Fig. 2. The DMB and MP selectivity as a function of n-C6 conversion over the Ni/SAC-11 and Ni-SAC-11 catalysts.

Fig. 3. XRD patterns of the SAC-11, Ni-SAC-11 and Ni/SAC-11 samples.

Fig. 4. Nitrogen adsorption isotherms of the SAC-11, Ni-SAC-11 and Ni/SAC-11 samples.

Fig. 5. XPS spectra in Ni 2p3/2 region of the NiO, Ni-SAC-11 and Ni/SAC-11 catalysts.

Fig. 6. FT-IR spectra of the Ni-SAC-11, Ni/SAC-11 and SAC-11 samples.

Table 1 Textural properties of the SAC-11, Ni-SAC -11 and Ni/SAC-11 samples.

Sample	S_BET (m²/g)	V_Total (cm³/g)	V_Meso (cm³/g)	V^a (Å³)
SAC-11	236	0.141	0.068	2034
Ni-SAC-11	305	0.231	0.166	2050
Ni/SAC-11	167	0.108	0.058	-

Fig. 7. XANES spectra (a) at the Ni K-edge of Ni-SAC-11, NiO reference and Ni foil reference; EXAFS curves (b) of the Ni-SAC-11 catalyst at R space.

Fig. 8. TEM and STEM images as well as elemental maps of nickel for the Ni-SAC-11 (a, b, c) and Ni/SAC-11 (d, e, f) catalysts.

Fig. 9. H2-TPR profiles of the Ni-SAC-11 and Ni/SAC-11 catalysts.

Fig. 10. FT-IR spectra of pyridine adsorbed on the SAC-11, reduced Ni-SAC-11 and Ni/SAC-11 samples.

Fig. 11. NH3-TPD profiles of the SAC-11, reduced Ni-SAC-11and Ni/SAC-11 samples.

Table 2 Acid distribution of the SAC-11, reduced Ni-SAC-11 and Ni/SAC-11 samples.

Sample	Acidity (μmol/g)
Sample	Weak	Medium	Strong	Total
SAC-11	78.4	95.4	104.9	278.7
Ni-SAC-11	92.3	167.7	143.7	403.7
Ni/SAC-11	46.3	77.4	99.5	223.2

Fig. 12. 3D structures showing the optimized cluster of the SAPO-11 (a), SAPO-11 interacting with NH3 (b), NiP-OH clusters in the Ni-SAPO-11 (c) and NiP-OH clusters interacting with NH3 (d).

Fig. 13. Specific chemical bond angles of T-O-T (T = Al, P, Si or Ni) in the 10-membered ring pore channel of AlPO-11 (a), SAPO-11 (SAC-11, b) and nickel substituted SAPO-11 (Ni-SAC-11, c).

Table 3 The selected bond length (dO-H), Mulliken charge (qO), the NH3 adsorption energy (ΔEads) and deprotonation energy (DPE) of the bridging O-H groups from SiAl-OH and NiP-OH structures.

Structures	d_O-H (Å)	q_O	ΔE_ads (kJ/mol)	DPE (kJ/mol)
SiAl-OH^a	0.965	-0.646	-70.3	1260.4
NiP-OH^b	0.993	-0.303	-80.4	1188.8

Fig. 14. The schematic for the hydroisomerization of n-alkanes over the biunctional catalyst.

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