Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5

Lin, Longfei; Qiu, Caifeng; Zhuo, Zuoxi; Zhang, Dawei; Zhao, Shufang; Wu, Haihong; Liu, Yueming; He, Min

doi:10.1016/j.jcat.2013.09.011

Cited by 161 publications

(136 citation statements)

References 36 publications

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“…Compared to the previous studies on olefin transformation [2,8,10,14,15,31,32], the temperature investigated in this work is in moderate range. The temperature dependence indicates that, under the high temperature, the bimolecular cracking will be insignificant and the monomolecular cracking becomes dominant.…”

Section: Negative Temperature Dependence Of Cracking Ratementioning

confidence: 99%

“…The multimolecular reactions, e.g., dimerization, trimerization and etc., of the parent olefin are initiated and followed by the secondary reactions such as isomerization or cracking, yielding a variety of derivative olefins [2,13]. Lin et al [14] found the catalyst acid strength had great effect on the reaction pathways and product distribution for 1-butene over ZSM-5. In a study on C 2 -C 4 olefins, Borges et al [15] found that, though the consumption rate of butene increased, those of ethene and propene decreased with the temperature increasing.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reaction pathway and kinetics of C3–C7 olefin transformation over high-silicon HZSM-5 zeolite at 400–490°C

Huang

Aihemaitijiang

Xiao

2015

Chemical Engineering Journal

116

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Section: Negative Temperature Dependence Of Cracking Ratementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reaction pathway and kinetics of C3–C7 olefin transformation over high-silicon HZSM-5 zeolite at 400–490°C

Huang

Aihemaitijiang

Xiao

2015

Chemical Engineering Journal

116

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“…Secondary reactions of aromatization and hydrogen transfer are catalyzed by strong acid sites and they are suppressed in high silica zeolites to some extent [40]. These reactions are involved in the formation of aromatics BTX and C 2 -C 4 paraffins [68].…”

Section: Catalysts Performancementioning

confidence: 99%

“…The literature reports the complexity of the 1-butene cracking reaction scheme (including oligomerization-cracking, dehydrogenation-aromatization and hydrogen transfer reactions) [37,38] and the significant effect of MFI zeolite properties on product distribution and stability [5,31,39]. Lin et al [40] proposed several reaction pathways for the catalytic cracking of 1-butene on MFI zeolites and established an optimum amount of acid sites (0.181 mmol g -1 ) in order to achieve high propylene selectivity.…”

Section: Introductionmentioning

confidence: 99%

Controlling coke deactivation and cracking selectivity of MFI zeolite by H3PO4 or KOH modification

Epelde

Santos

Florian

et al. 2015

Applied Catalysis A: General

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2 -Graphical abstract Highlights -3 --Effect of ZSM-5 zeolite treatment with H3PO4 or KOH on its acidity and structure -Catalytic features linked with 1-butene oligomerization-cracking into propylene -Diffusion length of precursors controls catalytic deactivation by coke -Acid strength controls propylene selectivity and 1-butene conversion Abstract The effect of the basic (KOH) or acid (H 3 PO 4 ) treatment of the MFI (HZSM-5) zeolite has been studied comparing the structural and acidic features with the catalytic performance and deactivation of a set of unmodified and modified zeolites (SiO 2 /Al 2 O 3 = 30-280, 0-3 wt% of K or P). The properties of the catalysts have been elucidated using XRD, 27 Al and 29 Si NMR, N 2 adsorption-desorption, and adsorption-TPD of tertbutylamine. The catalytic performance has been evaluated in the cracking of 1-butene by means of initial, 5 h on-stream activity and coke formation. Our results point to the fact that using zeolites with high SiO 2 /Al 2 O 3 ratio or neutralizing the strongest acid sites with KOH or H 3 PO 4 increases propylene selectivity while decreases 1-butene conversion. The overall pathway of reaction involve propylene and other olefins as primary products that condensate in further steps to aromatics and ultimately to coke.This pathway can be controlled with less severe acidic features and by desilication with KOH or H 3 PO 4 (particularly with the former).

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“…It should be noted that around 21% pentene is a byproduct with propene in the catalytic cracking of 1-butene. 31 Thus, an investigation of the catalytic cracking of 1-pentene rather than 1-butene is more significant. The side reactions of 1-pentene catalytic cracking are similar to those of 1-butene catalytic cracking, 31,32 but still there are some essential differences.…”

Section: Introductionmentioning

confidence: 99%

Acid Strength Controlled Reaction Pathways for the Catalytic Cracking of 1-Pentene to Propene over ZSM-5

et al. 2015

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The influence of acid strength was evaluated toward the selectivity to propene on conversion of 1-pentene. For the catalytic cracking of 1-pentene, the main reaction pathways and the molar ratio of propene to ethene (P/E ratio) were controlled by acid strength with the appropriate amount of total acid sites. The results showed that the P/E ratio increased with decreasing amounts of strong acid sites, since the activation energies of individual reaction pathways were influenced by acid strength to a different extent. Strong acid sites could promote pathway I′ (C 5 2− → C 2 2− + C 3 2− ) and pathway II′-1 (C 6 2− → C 2 2− + C 4 2− ), while weak acid sites preferred pathway II′ (2C 5 2− → C 10 + → C 4 2− + C 6 2− ) and pathway II′-2 (C 6 2− → 2C 3 2− ), since pathways II′ and II′-2 underwent some energetically favorable routes (tertiary− secondary, secondary−secondary) of carbenium ion intermediates. By manipulation of the acid strength distribution on ZSM-5, the P/E ratio and selectivity of propene could be significantly improved, suggesting that this can provide an important guideline for improving such a process. In addition, we also designed a coupled process combing butene and pentene coconversion, as pentene and butene could be produced during C 4 2− and C 5 2− catalytic cracking. The coupled process could offer a promising solution to gain high selectivity of propene from C 4 and C 5 olefin cracking.

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Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5

Cited by 161 publications

References 36 publications

Reaction pathway and kinetics of C3–C7 olefin transformation over high-silicon HZSM-5 zeolite at 400–490°C

Reaction pathway and kinetics of C3–C7 olefin transformation over high-silicon HZSM-5 zeolite at 400–490°C

Controlling coke deactivation and cracking selectivity of MFI zeolite by H3PO4 or KOH modification

Acid Strength Controlled Reaction Pathways for the Catalytic Cracking of 1-Pentene to Propene over ZSM-5

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