Combined experimental and kinetic modelling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst

Luong H Nguyen, Tanya Vazhnova, Stan T Kolaczkowski, Dmitry B Lukyanov

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Abstract

Kinetic studies of propane and n -butane aromatization were performed over H-ZSM-5 at 500 Deg at the conversions between 1% and 88%. Based on the results obtained, a kinetic model for aromatization of both alkanes was developed. The model contains 38 rate consts., two adsorption consts., and 38 reaction steps to describe transformation of 13 components involved in these two reactions. Anal. of the exptl. and kinetic modeling data has confirmed that propane and n-butane transformation over H-ZSM-5 occurs via two routes: (i) protolytic cracking (PC) of C-C and C-H bonds in alkane mols. and (ii) hydrogen transfer (HT) between the feed alkane and product alkenes adsorbed on acid sites. Cracking of C-C bonds is favored over cracking of C-H bonds for both alkanes; and the n -butane reactivity in the PC steps is 5 times higher than that of propane. The contribution of the HT route into propane and n-butane transformations was estd. quant. for the first time and was shown to increase with alkane conversion, being always higher for the n-butane reaction (e.g., at conversion of 10%, this contribution was around 10% and 25% for propane and n-butane reactions, resp.). As a result, an increase in the reaction rate was obsd. at low n-butane conversions, demonstrating for the first time the autocatalytic character of this reaction. However, in agreement with the lower contribution of the HT steps in conversion of propane, the autocatalysis was not obsd. in the propane reaction. Light alkenes formed in the initial reaction steps give rise to fast alkene oligomerization/cracking steps that control alkene distribution during alkane aromatization. The rate consts. of the alkene oligomerization/cracking steps are .apprx.10 times higher than those of the aromatization steps, which, in turn, are .apprx.1000 times higher than the sum of the rate consts. of the propane PC steps. Direct comparison of the aroms. formation in propane and n -butane reactions shows that the aroms. concn., when detd. at the same conversions of two alkanes, is always higher for propane reaction. This finding is explained by the difference in the propane and n -butane reactivity, and allows us to predict higher aroms. concn./selectivity in conversion of ethane as compared to reaction of propane. [on SciFinder (R)]
LanguageEnglish
Pages5881-5894
Number of pages14
JournalChemical Engineering Science
Volume61
Issue number17
StatusPublished - 2006

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Aromatization
Propane
Butane
Alkanes
Catalysts
Kinetics
Paraffins
Alkenes
Olefins
Hydrogen
Oligomerization
butane
Ethane
Reaction rates
Data structures

Keywords

  • kinetic modeling propane butane aromatization HZSM5 catalyst
  • CAT (Catalyst use)
  • Aromatization catalysts
  • RACT (Reactant or reagent) (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst)
  • Aromatization kinetics
  • Hydrogen transfer (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst)
  • Alkanes Role
  • Zeolite HZSM-5 Role
  • Cracking
  • Aromatization
  • USES (Uses) (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst)
  • RCT (Reactant)

Cite this

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title = "Combined experimental and kinetic modelling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst",
abstract = "Kinetic studies of propane and n -butane aromatization were performed over H-ZSM-5 at 500 Deg at the conversions between 1{\%} and 88{\%}. Based on the results obtained, a kinetic model for aromatization of both alkanes was developed. The model contains 38 rate consts., two adsorption consts., and 38 reaction steps to describe transformation of 13 components involved in these two reactions. Anal. of the exptl. and kinetic modeling data has confirmed that propane and n-butane transformation over H-ZSM-5 occurs via two routes: (i) protolytic cracking (PC) of C-C and C-H bonds in alkane mols. and (ii) hydrogen transfer (HT) between the feed alkane and product alkenes adsorbed on acid sites. Cracking of C-C bonds is favored over cracking of C-H bonds for both alkanes; and the n -butane reactivity in the PC steps is 5 times higher than that of propane. The contribution of the HT route into propane and n-butane transformations was estd. quant. for the first time and was shown to increase with alkane conversion, being always higher for the n-butane reaction (e.g., at conversion of 10{\%}, this contribution was around 10{\%} and 25{\%} for propane and n-butane reactions, resp.). As a result, an increase in the reaction rate was obsd. at low n-butane conversions, demonstrating for the first time the autocatalytic character of this reaction. However, in agreement with the lower contribution of the HT steps in conversion of propane, the autocatalysis was not obsd. in the propane reaction. Light alkenes formed in the initial reaction steps give rise to fast alkene oligomerization/cracking steps that control alkene distribution during alkane aromatization. The rate consts. of the alkene oligomerization/cracking steps are .apprx.10 times higher than those of the aromatization steps, which, in turn, are .apprx.1000 times higher than the sum of the rate consts. of the propane PC steps. Direct comparison of the aroms. formation in propane and n -butane reactions shows that the aroms. concn., when detd. at the same conversions of two alkanes, is always higher for propane reaction. This finding is explained by the difference in the propane and n -butane reactivity, and allows us to predict higher aroms. concn./selectivity in conversion of ethane as compared to reaction of propane. [on SciFinder (R)]",
keywords = "kinetic modeling propane butane aromatization HZSM5 catalyst, CAT (Catalyst use), Aromatization catalysts, RACT (Reactant or reagent) (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst), Aromatization kinetics, Hydrogen transfer (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst), Alkanes Role, Zeolite HZSM-5 Role, Cracking, Aromatization, USES (Uses) (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst), RCT (Reactant)",
author = "Nguyen, {Luong H} and Tanya Vazhnova and Kolaczkowski, {Stan T} and Lukyanov, {Dmitry B}",
year = "2006",
language = "English",
volume = "61",
pages = "5881--5894",
journal = "Chemical Engineering Science",
issn = "0009-2509",
publisher = "Elsevier",
number = "17",

}

TY - JOUR

T1 - Combined experimental and kinetic modelling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst

AU - Nguyen,Luong H

AU - Vazhnova,Tanya

AU - Kolaczkowski,Stan T

AU - Lukyanov,Dmitry B

PY - 2006

Y1 - 2006

N2 - Kinetic studies of propane and n -butane aromatization were performed over H-ZSM-5 at 500 Deg at the conversions between 1% and 88%. Based on the results obtained, a kinetic model for aromatization of both alkanes was developed. The model contains 38 rate consts., two adsorption consts., and 38 reaction steps to describe transformation of 13 components involved in these two reactions. Anal. of the exptl. and kinetic modeling data has confirmed that propane and n-butane transformation over H-ZSM-5 occurs via two routes: (i) protolytic cracking (PC) of C-C and C-H bonds in alkane mols. and (ii) hydrogen transfer (HT) between the feed alkane and product alkenes adsorbed on acid sites. Cracking of C-C bonds is favored over cracking of C-H bonds for both alkanes; and the n -butane reactivity in the PC steps is 5 times higher than that of propane. The contribution of the HT route into propane and n-butane transformations was estd. quant. for the first time and was shown to increase with alkane conversion, being always higher for the n-butane reaction (e.g., at conversion of 10%, this contribution was around 10% and 25% for propane and n-butane reactions, resp.). As a result, an increase in the reaction rate was obsd. at low n-butane conversions, demonstrating for the first time the autocatalytic character of this reaction. However, in agreement with the lower contribution of the HT steps in conversion of propane, the autocatalysis was not obsd. in the propane reaction. Light alkenes formed in the initial reaction steps give rise to fast alkene oligomerization/cracking steps that control alkene distribution during alkane aromatization. The rate consts. of the alkene oligomerization/cracking steps are .apprx.10 times higher than those of the aromatization steps, which, in turn, are .apprx.1000 times higher than the sum of the rate consts. of the propane PC steps. Direct comparison of the aroms. formation in propane and n -butane reactions shows that the aroms. concn., when detd. at the same conversions of two alkanes, is always higher for propane reaction. This finding is explained by the difference in the propane and n -butane reactivity, and allows us to predict higher aroms. concn./selectivity in conversion of ethane as compared to reaction of propane. [on SciFinder (R)]

AB - Kinetic studies of propane and n -butane aromatization were performed over H-ZSM-5 at 500 Deg at the conversions between 1% and 88%. Based on the results obtained, a kinetic model for aromatization of both alkanes was developed. The model contains 38 rate consts., two adsorption consts., and 38 reaction steps to describe transformation of 13 components involved in these two reactions. Anal. of the exptl. and kinetic modeling data has confirmed that propane and n-butane transformation over H-ZSM-5 occurs via two routes: (i) protolytic cracking (PC) of C-C and C-H bonds in alkane mols. and (ii) hydrogen transfer (HT) between the feed alkane and product alkenes adsorbed on acid sites. Cracking of C-C bonds is favored over cracking of C-H bonds for both alkanes; and the n -butane reactivity in the PC steps is 5 times higher than that of propane. The contribution of the HT route into propane and n-butane transformations was estd. quant. for the first time and was shown to increase with alkane conversion, being always higher for the n-butane reaction (e.g., at conversion of 10%, this contribution was around 10% and 25% for propane and n-butane reactions, resp.). As a result, an increase in the reaction rate was obsd. at low n-butane conversions, demonstrating for the first time the autocatalytic character of this reaction. However, in agreement with the lower contribution of the HT steps in conversion of propane, the autocatalysis was not obsd. in the propane reaction. Light alkenes formed in the initial reaction steps give rise to fast alkene oligomerization/cracking steps that control alkene distribution during alkane aromatization. The rate consts. of the alkene oligomerization/cracking steps are .apprx.10 times higher than those of the aromatization steps, which, in turn, are .apprx.1000 times higher than the sum of the rate consts. of the propane PC steps. Direct comparison of the aroms. formation in propane and n -butane reactions shows that the aroms. concn., when detd. at the same conversions of two alkanes, is always higher for propane reaction. This finding is explained by the difference in the propane and n -butane reactivity, and allows us to predict higher aroms. concn./selectivity in conversion of ethane as compared to reaction of propane. [on SciFinder (R)]

KW - kinetic modeling propane butane aromatization HZSM5 catalyst

KW - CAT (Catalyst use)

KW - Aromatization catalysts

KW - RACT (Reactant or reagent) (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst)

KW - Aromatization kinetics

KW - Hydrogen transfer (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst)

KW - Alkanes Role

KW - Zeolite HZSM-5 Role

KW - Cracking

KW - Aromatization

KW - USES (Uses) (combined exptl. and kinetic modeling studies of the pathways of propane and n-butane aromatization over H-ZSM-5 catalyst)

KW - RCT (Reactant)

M3 - Article

VL - 61

SP - 5881

EP - 5894

JO - Chemical Engineering Science

T2 - Chemical Engineering Science

JF - Chemical Engineering Science

SN - 0009-2509

IS - 17

ER -