On methanol to hydrocarbons reactions in a hierarchically structured ZSM-5 zeolite catalyst

Heejoong Kim, Hoi Gu Jang, Eunhee Jang, Sung Jun Park, Taehee Lee, Yanghwan Jeong, Hionsuck Baik, Sung June Cho, Jungkyu Choi

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Two type ZSM-5 catalysts (Si/Al ratio of ∼30) with different mesoporosity were synthesized by using a structure directing agent of tetra-n-butylphosphonium hydroxide. In particular, the molar compositions of ethanol and water in the synthetic precursor were changed in order to acquire the two type ZSM-5 catalysts. The resulting ZSM-5 catalysts were formed via the interconnection of very thin pillars or lamellae; (1) ∼6. nm thick with marked mesoporosity (H_30; high mesoporous ZSM-5) and (2) ∼13. nm thick without any considerable mesoporosity (L_30; low mesoporous ZSM-5). The pyridine-based acid titration reveals that H_30 had internal Brønsted acid sites similar to those in the commercially available ZSM-5 with a Si/Al ratio of 75 (referred to as C_75), though H_30 contained a large amount of external Brønsted acid sites. The methanol to hydrocarbons (MTH) reaction performance of these two ZSM-5 catalysts demonstrates that H_30 preferred to produce propene over ethene compared to C_75, while L_30 showed a very poor MTH performance mainly due to the lower amount of internal Brønsted acid sites. More desirably, a very short diffusional length (∼18,600 times lower than that in C_75) in H_30 considerably disfavored the aromatic dealkylation that is known to produce ethene. With this, H_30 allowed for achieving the ratio of propene to ethene as high as ∼9.1, which is, to the best of our knowledge, a highest value among the MTH results on ZSM-5 catalysts without any co-feed. Furthermore, ceria-doped H_30 not only enhanced the stability for the MTH reaction via a passivation of the external Brønsted acid sites, but also improved a propene to ethene ratio up to ∼15.0.

Original languageEnglish
JournalCatalysis Today
DOIs
Publication statusAccepted/In press - 2017

Fingerprint

Hydrocarbons
Methanol
Catalysts
Acids
Propylene
Cerium compounds
Titration
Passivation
Pyridine
Ethanol
ZSM-5 zeolite
ethylene
Water
Chemical analysis
propylene

Keywords

  • Acid site titration
  • Hierarchically structured ZSM-5
  • Methanol-to-hydrocarbons reaction
  • Propene/ethene ratio
  • Self-pillared ZSM-5

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

On methanol to hydrocarbons reactions in a hierarchically structured ZSM-5 zeolite catalyst. / Kim, Heejoong; Jang, Hoi Gu; Jang, Eunhee; Park, Sung Jun; Lee, Taehee; Jeong, Yanghwan; Baik, Hionsuck; Cho, Sung June; Choi, Jungkyu.

In: Catalysis Today, 2017.

Research output: Contribution to journalArticle

Kim, Heejoong ; Jang, Hoi Gu ; Jang, Eunhee ; Park, Sung Jun ; Lee, Taehee ; Jeong, Yanghwan ; Baik, Hionsuck ; Cho, Sung June ; Choi, Jungkyu. / On methanol to hydrocarbons reactions in a hierarchically structured ZSM-5 zeolite catalyst. In: Catalysis Today. 2017.
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abstract = "Two type ZSM-5 catalysts (Si/Al ratio of ∼30) with different mesoporosity were synthesized by using a structure directing agent of tetra-n-butylphosphonium hydroxide. In particular, the molar compositions of ethanol and water in the synthetic precursor were changed in order to acquire the two type ZSM-5 catalysts. The resulting ZSM-5 catalysts were formed via the interconnection of very thin pillars or lamellae; (1) ∼6. nm thick with marked mesoporosity (H_30; high mesoporous ZSM-5) and (2) ∼13. nm thick without any considerable mesoporosity (L_30; low mesoporous ZSM-5). The pyridine-based acid titration reveals that H_30 had internal Br{\o}nsted acid sites similar to those in the commercially available ZSM-5 with a Si/Al ratio of 75 (referred to as C_75), though H_30 contained a large amount of external Br{\o}nsted acid sites. The methanol to hydrocarbons (MTH) reaction performance of these two ZSM-5 catalysts demonstrates that H_30 preferred to produce propene over ethene compared to C_75, while L_30 showed a very poor MTH performance mainly due to the lower amount of internal Br{\o}nsted acid sites. More desirably, a very short diffusional length (∼18,600 times lower than that in C_75) in H_30 considerably disfavored the aromatic dealkylation that is known to produce ethene. With this, H_30 allowed for achieving the ratio of propene to ethene as high as ∼9.1, which is, to the best of our knowledge, a highest value among the MTH results on ZSM-5 catalysts without any co-feed. Furthermore, ceria-doped H_30 not only enhanced the stability for the MTH reaction via a passivation of the external Br{\o}nsted acid sites, but also improved a propene to ethene ratio up to ∼15.0.",
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AU - Lee, Taehee

AU - Jeong, Yanghwan

AU - Baik, Hionsuck

AU - Cho, Sung June

AU - Choi, Jungkyu

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AB - Two type ZSM-5 catalysts (Si/Al ratio of ∼30) with different mesoporosity were synthesized by using a structure directing agent of tetra-n-butylphosphonium hydroxide. In particular, the molar compositions of ethanol and water in the synthetic precursor were changed in order to acquire the two type ZSM-5 catalysts. The resulting ZSM-5 catalysts were formed via the interconnection of very thin pillars or lamellae; (1) ∼6. nm thick with marked mesoporosity (H_30; high mesoporous ZSM-5) and (2) ∼13. nm thick without any considerable mesoporosity (L_30; low mesoporous ZSM-5). The pyridine-based acid titration reveals that H_30 had internal Brønsted acid sites similar to those in the commercially available ZSM-5 with a Si/Al ratio of 75 (referred to as C_75), though H_30 contained a large amount of external Brønsted acid sites. The methanol to hydrocarbons (MTH) reaction performance of these two ZSM-5 catalysts demonstrates that H_30 preferred to produce propene over ethene compared to C_75, while L_30 showed a very poor MTH performance mainly due to the lower amount of internal Brønsted acid sites. More desirably, a very short diffusional length (∼18,600 times lower than that in C_75) in H_30 considerably disfavored the aromatic dealkylation that is known to produce ethene. With this, H_30 allowed for achieving the ratio of propene to ethene as high as ∼9.1, which is, to the best of our knowledge, a highest value among the MTH results on ZSM-5 catalysts without any co-feed. Furthermore, ceria-doped H_30 not only enhanced the stability for the MTH reaction via a passivation of the external Brønsted acid sites, but also improved a propene to ethene ratio up to ∼15.0.

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