Hydrogenolysis of anisole over mesoporous sulfided CoMoW/SBA-15(16) catalysts
[Display omitted] ► The mechanism of anisole transformation over SBA-15(16)-based sulfide Co–Mo–W catalysts is bifunctional, with a major contribution of the acidic function. ► Metal sulfides are better dispersed on SBA-16 than on the SBA-15 substrate. ► The addition of 0.5 wt% of phosphate generate...
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| Published in: | Catalysis today Vol. 172; no. 1; pp. 103 - 110 |
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| Main Authors: | , , , , , , |
| Format: | Journal Article Conference Proceeding |
| Language: | English |
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Elsevier B.V
25-08-2011
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| Abstract | [Display omitted]
► The mechanism of anisole transformation over SBA-15(16)-based sulfide Co–Mo–W catalysts is bifunctional, with a major contribution of the acidic function. ► Metal sulfides are better dispersed on SBA-16 than on the SBA-15 substrate. ► The addition of 0.5 wt% of phosphate generates the largest population of active sites, the highest total acidity and best stability during on-stream condition.
This contribution describes the effect of SBA-15(16) support modification with variable quantity of P
2O
5 (0.5 and 1.0
wt%) on the catalytic response of supported ternary CoMoW catalysts tested in the gas-phase hydrogenolysis of anisole, as a model compound for pyrolysis oil. The catalysts were characterized by a variety of techniques (
S
BET, XRD, TPD-NH
3, XPS, HRTEM and coke combustion followed by TG/DTG). Under steady-state conditions, the sulfided CoMoW/SBA-16 catalyst modified with a small amount of phosphate (0.5
wt%) recorded the highest activity and stability in anisole transformation at 310
°C and 3
MPa of hydrogen pressure. All catalysts exhibited similar selectivities at the same anisole conversion (38%), indicating that catalyst morphology did not influence the catalytic behavior. Regardless of the carrier, deoxygenation was not significant, with demethylation (phenol) and isomerization (
o-cresol,
o-xylenol) being the main reaction routes. The highest activity recorded by the phosphate-containing CoMoW/SBA-16 catalyst is associated with its highest total acidity, the largest population of Mo(W)S
2 phases located mainly within the inner support porous structure, the greatest sulfidation degree of W species and major stability during time-on-stream operation with respect to other catalysts. |
|---|---|
| AbstractList | [Display omitted]
► The mechanism of anisole transformation over SBA-15(16)-based sulfide Co–Mo–W catalysts is bifunctional, with a major contribution of the acidic function. ► Metal sulfides are better dispersed on SBA-16 than on the SBA-15 substrate. ► The addition of 0.5 wt% of phosphate generates the largest population of active sites, the highest total acidity and best stability during on-stream condition.
This contribution describes the effect of SBA-15(16) support modification with variable quantity of P
2O
5 (0.5 and 1.0
wt%) on the catalytic response of supported ternary CoMoW catalysts tested in the gas-phase hydrogenolysis of anisole, as a model compound for pyrolysis oil. The catalysts were characterized by a variety of techniques (
S
BET, XRD, TPD-NH
3, XPS, HRTEM and coke combustion followed by TG/DTG). Under steady-state conditions, the sulfided CoMoW/SBA-16 catalyst modified with a small amount of phosphate (0.5
wt%) recorded the highest activity and stability in anisole transformation at 310
°C and 3
MPa of hydrogen pressure. All catalysts exhibited similar selectivities at the same anisole conversion (38%), indicating that catalyst morphology did not influence the catalytic behavior. Regardless of the carrier, deoxygenation was not significant, with demethylation (phenol) and isomerization (
o-cresol,
o-xylenol) being the main reaction routes. The highest activity recorded by the phosphate-containing CoMoW/SBA-16 catalyst is associated with its highest total acidity, the largest population of Mo(W)S
2 phases located mainly within the inner support porous structure, the greatest sulfidation degree of W species and major stability during time-on-stream operation with respect to other catalysts. This contribution describes the effect of SBA-15(16) support modification with variable quantity of P₂O₅ (0.5 and 1.0wt%) on the catalytic response of supported ternary CoMoW catalysts tested in the gas-phase hydrogenolysis of anisole, as a model compound for pyrolysis oil. The catalysts were characterized by a variety of techniques (SBET, XRD, TPD-NH₃, XPS, HRTEM and coke combustion followed by TG/DTG). Under steady-state conditions, the sulfided CoMoW/SBA-16 catalyst modified with a small amount of phosphate (0.5wt%) recorded the highest activity and stability in anisole transformation at 310°C and 3MPa of hydrogen pressure. All catalysts exhibited similar selectivities at the same anisole conversion (38%), indicating that catalyst morphology did not influence the catalytic behavior. Regardless of the carrier, deoxygenation was not significant, with demethylation (phenol) and isomerization (o-cresol, o-xylenol) being the main reaction routes. The highest activity recorded by the phosphate-containing CoMoW/SBA-16 catalyst is associated with its highest total acidity, the largest population of Mo(W)S₂ phases located mainly within the inner support porous structure, the greatest sulfidation degree of W species and major stability during time-on-stream operation with respect to other catalysts. |
| Author | Fierro, J.L.G. Nava, R. Loricera, C.V. Huirache-Acuña, R. Álvarez-Galván, M.C. Infantes-Molina, A. Pawelec, B. |
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| Keywords | SBA-16 Cobalt–molybdenum–tungsten Hydrodeoxygenation Hydrotreatment Anisole Phosphate SBA-15 Phosphates Modification Support Hydrogen Coke Combustion X ray Cobalt Porous material Supported catalyst Model compound Tungsten Cobalt-molybdenum-tungsten Photoelectron spectrometry Pyrolysis Catalytic reaction Stability Hydrogenolysis Catalyst selectivity Transition metal X ray diffraction Molybdenum Steady state Mesoporosity Ammonia Heterogeneous catalysis Oil Transmission electron microscopy Gas phase Catalyst |
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► The mechanism of anisole transformation over SBA-15(16)-based sulfide Co–Mo–W catalysts is bifunctional, with a major contribution of the... This contribution describes the effect of SBA-15(16) support modification with variable quantity of P₂O₅ (0.5 and 1.0wt%) on the catalytic response of... |
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| SubjectTerms | acidity Anisole Catalysis catalysts catalytic activity Chemistry Cobalt–molybdenum–tungsten Colloidal state and disperse state combustion Exact sciences and technology General and physical chemistry Hydrodeoxygenation hydrogen Hydrotreatment isomerization o-cresol oils phenol Phosphate Porous materials pyrolysis SBA-15 SBA-16 Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry |
| Title | Hydrogenolysis of anisole over mesoporous sulfided CoMoW/SBA-15(16) catalysts |
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