Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Ni-BiO_x Metal Oxides Supported on Mesoporous SBA-15

Abstract

A Ni-BiO x /SBA-15 catalyst synthesized using a co-impregnation method was utilized for the oxidative dehydrogenation (ODH) of n-butenes (1butene and 2-butene) to 1,3-butadiene in a fixed-bed reactor. The layered structure of NiO/β-Bi 2 O 3 /Bi 2 SiO 5 /SBA-15 was confirmed using porosity, XRD, and H 2 -TPR measurements. The components of the structure interacted moderately to form an effectively active and selective NiO species as an ODH catalyst. Thermodynamic analysis results revealed the most favorable pathway for butene conversion; however, this catalyst kinetically favored the desired and efficient route of butene conversion via adsorption of butenes, abstraction of αhydrogen, and the formation of highly selective 1,3-butadiene. The selectivity of the oxygen species in the metal oxide system along the efficient route was sustained by co-feeding gas phase oxygen and increasing the reaction temperature. The catalyst comprising 14 wt % Ni-10 wt % Bi-O/SBA-15 exhibited a 2-butene conversion of 83% and a 1,3-butadiene selectivity of 89% at 400 °C and O 2 /C 4 = ratio = 4.0 mol/mol.

Designed Nanoarchitectures of a BiOBr/BiOI Nanosheet Heterojunction Anchored on Dendritic Fibrous Nanosilica as Visible-Light Responsive Photocatalysts

“…Although the template synthesis of Bi 2 O 3 nanoparticles in mesoporous silicas, such as MCM-41, 41,42 TUD-1, 43 and SBA-15, 32,44,45 and silica nanosphere, 46 was attempted as listed in Table S2, the resulting Bi 2 O 3 nanoparticles did not clearly replicate the pores. [41][42][43]45,46 Bi 2 O 3 nanospheres (7.5 nm) formed in the pore channel of SBA-15 by repeated infiltration of an aqueous Bi(NO 3 ) 3 solution into SBA-15 with 5 vol % of pore filling. 32 Limitations in the formation of Bi 2 O 3 nanoparticles in mesoporous silicas included a low loading amount of Bi 2 O 3 nanoparticles, 32,41,42,45 multiple loading steps, 32 and uncontrolled size and location of the Bi 2 O 3 nanoparticles.…”

“…[41][42][43]45,46 Bi 2 O 3 nanospheres (7.5 nm) formed in the pore channel of SBA-15 by repeated infiltration of an aqueous Bi(NO 3 ) 3 solution into SBA-15 with 5 vol % of pore filling. 32 Limitations in the formation of Bi 2 O 3 nanoparticles in mesoporous silicas included a low loading amount of Bi 2 O 3 nanoparticles, 32,41,42,45 multiple loading steps, 32 and uncontrolled size and location of the Bi 2 O 3 nanoparticles. [41][42][43]46 To overcome these limitations, an organobismuth compound (bismuth neodecanoate: C 30 H 57 BiO 6 ) was used as the bismuth precursor in the present study.…”

“…Although the template synthesis of Bi 2 O 3 nanoparticles in mesoporous silicas, such as MCM-41, 41,42 TUD-1, 43 and SBA-15, 32,44,45 and silica nanosphere, 46 was attempted as listed in Table S2, the resulting Bi 2 O 3 nanoparticles did not clearly replicate the pores. [41][42][43]45,46 Bi 2 O 3 nanospheres (7.5 nm) formed in the pore channel of SBA-15 by repeated infiltration of an aqueous Bi(NO 3 ) 3 solution into SBA-15 with 5 vol % of pore filling.…”

“…Due to the difficulty in controlling the polymerization of bismuth nitrate in an aqueous solution, various synthetic pathways have been examined to control the Bi 2 O 3 particle size, and Bi 2 O 3 in the range of 15–70 nm has been obtained via the hydrolysis in aqueous solution, under solvothermal reaction, and supercritical water, as listed in Table S2. Although the template synthesis of Bi 2 O 3 nanoparticles in mesoporous silicas, such as MCM-41, , TUD-1, and SBA-15, ,, and silica nanosphere, was attempted as listed in Table S2, the resulting Bi 2 O 3 nanoparticles did not clearly replicate the pores. − ,, Bi 2 O 3 nanospheres (7.5 nm) formed in the pore channel of SBA-15 by repeated infiltration of an aqueous Bi­(NO 3 ) 3 solution into SBA-15 with 5 vol % of pore filling . Limitations in the formation of Bi 2 O 3 nanoparticles in mesoporous silicas included a low loading amount of Bi 2 O 3 nanoparticles, ,,, multiple loading steps, and uncontrolled size and location of the Bi 2 O 3 nanoparticles. − , To overcome these limitations, an organobismuth compound (bismuth neodecanoate: C 30 H 57 BiO 6 ) was used as the bismuth precursor in the present study.…”

“…Although the template synthesis of Bi 2 O 3 nanoparticles in mesoporous silicas, such as MCM-41, , TUD-1, and SBA-15, ,, and silica nanosphere, was attempted as listed in Table S2, the resulting Bi 2 O 3 nanoparticles did not clearly replicate the pores. − ,, Bi 2 O 3 nanospheres (7.5 nm) formed in the pore channel of SBA-15 by repeated infiltration of an aqueous Bi­(NO 3 ) 3 solution into SBA-15 with 5 vol % of pore filling . Limitations in the formation of Bi 2 O 3 nanoparticles in mesoporous silicas included a low loading amount of Bi 2 O 3 nanoparticles, ,,, multiple loading steps, and uncontrolled size and location of the Bi 2 O 3 nanoparticles. − , To overcome these limitations, an organobismuth compound (bismuth neodecanoate: C 30 H 57 BiO 6 ) was used as the bismuth precursor in the present study. Solutions of bismuth neodecanoate in oleic acid and octadecene were used to prepare metallic Bi, Bi 2 S 3 , and Bi 2 Te 3 colloidal particles.…”