Kinetics of hydrodeoxygenation of stearic acid using supported nickel catalysts: Effects of supports

•Nickel supported γ-Al2O3, SiO2, and HZSM-5 were used as catalysts.•n-heptadecane was major product over Ni/γ-Al2O3 and Ni/SiO2.•Acidic nature of supports diverted products selectivity towards n-octadecane.•Reaction mechanism was delineated based on products distribution.•An empirical kinetic model...

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Veröffentlicht in:Applied catalysis. A, General General, 2014-02, Vol.471, p.28-38
Hauptverfasser: Kumar, Pankaj, Yenumala, Sudhakara Reddy, Maity, Sunil K., Shee, Debaprasad
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container_start_page 28
container_title Applied catalysis. A, General
container_volume 471
creator Kumar, Pankaj
Yenumala, Sudhakara Reddy
Maity, Sunil K.
Shee, Debaprasad
description •Nickel supported γ-Al2O3, SiO2, and HZSM-5 were used as catalysts.•n-heptadecane was major product over Ni/γ-Al2O3 and Ni/SiO2.•Acidic nature of supports diverted products selectivity towards n-octadecane.•Reaction mechanism was delineated based on products distribution.•An empirical kinetic model was developed to correlate experimental data. The hydrodeoxygenation of fatty acids derived from vegetable and microalgal oils is a novel process for production of liquid hydrocarbon fuels well-suited with existing internal combustion engines. The hydrodeoxygenation of stearic acid was investigated in a high pressure batch reactor using n-dodecane as solvent over nickel metal catalysts supported on SiO2, γ-Al2O3, and HZSM-5 in the temperature range of 533–563K. Several supported nickel oxide catalysts with nickel loading up to 25wt.% were prepared by incipient wetness impregnation method and reduced using hydrogen. The catalysts were then characterized by BET, TPR, H2 pulse chemisorption, TPD, XRD, and ICP-AES. Characterization studies revealed that only dispersed nickel oxide was present up to 15wt.% nickel loading on γ-Al2O3. The acidity of the supports depends on nickel loading of oxidized catalysts and increases with increasing nickel loading up to 15wt.%. n-Pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and l-octadecanol were identified as products of hydrodeoxygenation of stearic acid with n-heptadecane being primary product. The catalytic activity and selectivity to products for hydrodeoxygenation of stearic acid depends strongly on acidity of the supports. The maximum selectivity to n-heptadecane was observed with nickel supported γ-Al2O3 catalyst. A suitable reaction mechanism of hydrodeoxygenation of stearic acid was delineated based on products distribution. The conversion of stearic acid was increased with increasing reaction time, nickel loading on γ-Al2O3, temperature, and catalyst loading. Complete conversion of stearic acid was accomplished with more than 80% selectivity to n-heptadecane at reasonable reaction temperature of 563K after 240min of reaction using 15wt.% Ni/γ-Al2O3 catalyst. An empirical kinetic model was also developed to correlate the experimental data.
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The hydrodeoxygenation of fatty acids derived from vegetable and microalgal oils is a novel process for production of liquid hydrocarbon fuels well-suited with existing internal combustion engines. The hydrodeoxygenation of stearic acid was investigated in a high pressure batch reactor using n-dodecane as solvent over nickel metal catalysts supported on SiO2, γ-Al2O3, and HZSM-5 in the temperature range of 533–563K. Several supported nickel oxide catalysts with nickel loading up to 25wt.% were prepared by incipient wetness impregnation method and reduced using hydrogen. The catalysts were then characterized by BET, TPR, H2 pulse chemisorption, TPD, XRD, and ICP-AES. Characterization studies revealed that only dispersed nickel oxide was present up to 15wt.% nickel loading on γ-Al2O3. The acidity of the supports depends on nickel loading of oxidized catalysts and increases with increasing nickel loading up to 15wt.%. n-Pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and l-octadecanol were identified as products of hydrodeoxygenation of stearic acid with n-heptadecane being primary product. The catalytic activity and selectivity to products for hydrodeoxygenation of stearic acid depends strongly on acidity of the supports. The maximum selectivity to n-heptadecane was observed with nickel supported γ-Al2O3 catalyst. A suitable reaction mechanism of hydrodeoxygenation of stearic acid was delineated based on products distribution. The conversion of stearic acid was increased with increasing reaction time, nickel loading on γ-Al2O3, temperature, and catalyst loading. Complete conversion of stearic acid was accomplished with more than 80% selectivity to n-heptadecane at reasonable reaction temperature of 563K after 240min of reaction using 15wt.% Ni/γ-Al2O3 catalyst. An empirical kinetic model was also developed to correlate the experimental data.</description><identifier>ISSN: 0926-860X</identifier><identifier>EISSN: 1873-3875</identifier><identifier>DOI: 10.1016/j.apcata.2013.11.021</identifier><language>eng</language><publisher>Kidlington: Elsevier B.V</publisher><subject>Catalysis ; Catalysts ; Chemisorption ; Chemistry ; Emission analysis ; Exact sciences and technology ; General and physical chemistry ; Green diesel ; Hydrodeoxygenation ; Inductively coupled plasma ; Modeling ; Ni/γ-Al2O3 ; Nickel ; Selectivity ; Stearic acid ; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><ispartof>Applied catalysis. 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A, General</title><description>•Nickel supported γ-Al2O3, SiO2, and HZSM-5 were used as catalysts.•n-heptadecane was major product over Ni/γ-Al2O3 and Ni/SiO2.•Acidic nature of supports diverted products selectivity towards n-octadecane.•Reaction mechanism was delineated based on products distribution.•An empirical kinetic model was developed to correlate experimental data. The hydrodeoxygenation of fatty acids derived from vegetable and microalgal oils is a novel process for production of liquid hydrocarbon fuels well-suited with existing internal combustion engines. The hydrodeoxygenation of stearic acid was investigated in a high pressure batch reactor using n-dodecane as solvent over nickel metal catalysts supported on SiO2, γ-Al2O3, and HZSM-5 in the temperature range of 533–563K. Several supported nickel oxide catalysts with nickel loading up to 25wt.% were prepared by incipient wetness impregnation method and reduced using hydrogen. The catalysts were then characterized by BET, TPR, H2 pulse chemisorption, TPD, XRD, and ICP-AES. Characterization studies revealed that only dispersed nickel oxide was present up to 15wt.% nickel loading on γ-Al2O3. The acidity of the supports depends on nickel loading of oxidized catalysts and increases with increasing nickel loading up to 15wt.%. n-Pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and l-octadecanol were identified as products of hydrodeoxygenation of stearic acid with n-heptadecane being primary product. The catalytic activity and selectivity to products for hydrodeoxygenation of stearic acid depends strongly on acidity of the supports. The maximum selectivity to n-heptadecane was observed with nickel supported γ-Al2O3 catalyst. A suitable reaction mechanism of hydrodeoxygenation of stearic acid was delineated based on products distribution. The conversion of stearic acid was increased with increasing reaction time, nickel loading on γ-Al2O3, temperature, and catalyst loading. Complete conversion of stearic acid was accomplished with more than 80% selectivity to n-heptadecane at reasonable reaction temperature of 563K after 240min of reaction using 15wt.% Ni/γ-Al2O3 catalyst. An empirical kinetic model was also developed to correlate the experimental data.</description><subject>Catalysis</subject><subject>Catalysts</subject><subject>Chemisorption</subject><subject>Chemistry</subject><subject>Emission analysis</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Green diesel</subject><subject>Hydrodeoxygenation</subject><subject>Inductively coupled plasma</subject><subject>Modeling</subject><subject>Ni/γ-Al2O3</subject><subject>Nickel</subject><subject>Selectivity</subject><subject>Stearic acid</subject><subject>Theory of reactions, general kinetics. Catalysis. 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The hydrodeoxygenation of fatty acids derived from vegetable and microalgal oils is a novel process for production of liquid hydrocarbon fuels well-suited with existing internal combustion engines. The hydrodeoxygenation of stearic acid was investigated in a high pressure batch reactor using n-dodecane as solvent over nickel metal catalysts supported on SiO2, γ-Al2O3, and HZSM-5 in the temperature range of 533–563K. Several supported nickel oxide catalysts with nickel loading up to 25wt.% were prepared by incipient wetness impregnation method and reduced using hydrogen. The catalysts were then characterized by BET, TPR, H2 pulse chemisorption, TPD, XRD, and ICP-AES. Characterization studies revealed that only dispersed nickel oxide was present up to 15wt.% nickel loading on γ-Al2O3. The acidity of the supports depends on nickel loading of oxidized catalysts and increases with increasing nickel loading up to 15wt.%. n-Pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and l-octadecanol were identified as products of hydrodeoxygenation of stearic acid with n-heptadecane being primary product. The catalytic activity and selectivity to products for hydrodeoxygenation of stearic acid depends strongly on acidity of the supports. The maximum selectivity to n-heptadecane was observed with nickel supported γ-Al2O3 catalyst. A suitable reaction mechanism of hydrodeoxygenation of stearic acid was delineated based on products distribution. The conversion of stearic acid was increased with increasing reaction time, nickel loading on γ-Al2O3, temperature, and catalyst loading. Complete conversion of stearic acid was accomplished with more than 80% selectivity to n-heptadecane at reasonable reaction temperature of 563K after 240min of reaction using 15wt.% Ni/γ-Al2O3 catalyst. An empirical kinetic model was also developed to correlate the experimental data.</abstract><cop>Kidlington</cop><pub>Elsevier B.V</pub><doi>10.1016/j.apcata.2013.11.021</doi><tpages>11</tpages></addata></record>
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subjects Catalysis
Catalysts
Chemisorption
Chemistry
Emission analysis
Exact sciences and technology
General and physical chemistry
Green diesel
Hydrodeoxygenation
Inductively coupled plasma
Modeling
Ni/γ-Al2O3
Nickel
Selectivity
Stearic acid
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
title Kinetics of hydrodeoxygenation of stearic acid using supported nickel catalysts: Effects of supports
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