Effect of potassium addition on bimetallic PtSn supported θ-Al 2O3 catalyst for n-butane dehydrogenation to olefins

Bhari Mallanna Nagaraja; Heon Jung; Dae Ryook Yang; Kwang Deog Jung

doi:10.1016/j.cattod.2013.10.070

Effect of potassium addition on bimetallic PtSn supported θ-Al ₂O₃ catalyst for n-butane dehydrogenation to olefins

Bhari Mallanna Nagaraja, Heon Jung, Dae Ryook Yang, Kwang Deog Jung

Department of Chemical and Biological Engineering

Research output: Contribution to journal › Article › peer-review

33 Citations (Scopus)

Abstract

PtSn/θ-Al₂O₃ catalysts with different amount of potassium (0.4, 0.7, 0.95, 1.2 and 1.45 wt.%) were prepared by an impregnation method, and their catalytic activity in n-butane dehydrogenation was investigated at 823 K, an atmospheric pressure and a GHSV of 18,000 mL(g _cat h)^-1. The compositions listed in order of n-C ₄⁼ yields at 823 K were as follows: K_0.95(PtSn) _1.5 > (PtSn)_1.5 > K_0.4(PtSn) _1.5 > K_0.7(PtSn)_1.5 > K _1.2(PtSn)_1.5 > K_1.45(PtSn)_1.5 > K_0.9(Pt)_1.5. The K_0.9(Pt)_1.5 and K_0.95(Sn)_1.5 catalyst severely deactivated in n-butane dehydrogenation. The (PtSn)_1.5 (without K) catalyst showed the highest n-butane conversion, while K_0.95(PtSn)_1.5 did the highest n-C₄⁼ yield. The small amount of potassium on bimetallic PtSn/θ-Al₂O₃ catalyst improved n-C ₄⁼ selectivity, but slightly decreased n-butane conversion, resulting in the increase of n-C₄⁼ yield. The effect of potassium was caused by blocking the acid sites of Pt catalyst. The TPR and HAADF STEM-EDS study suggested the reduction procedure of the Pt, Sn and K species. However, the higher loaded potassium (1.2 and 1.45 wt.%) doped (PtSn)_1.5 catalysts were rather highly deactivated because the sizes of Pt particles were increased by weakening the interaction between Pt and Sn. The n-C₄⁼ selectivity of the (PtSn)_1.5 catalyst increased with respect to the reaction, while that of the potassium doped catalysts maintained the high n-C₄⁼ selectivity from the beginning of the reaction. Also, different alkali metals (Ca, Na and Li) were tested for the comparison with K. The potassium doped catalyst showed the highest n-C₄⁼ yield among the other alkali metals for n-butane dehydrogenation.

Original language	English
Pages (from-to)	40-52
Number of pages	13
Journal	Catalysis Today
Volume	232
DOIs	https://doi.org/10.1016/j.cattod.2013.10.070
Publication status	Published - 2014 Sept 1

Bibliographical note

Funding Information:
This work was supported by the basic research project of KIST and by Converging Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology ( 2011K000660 ).

Keywords

Effect of alkali metal
PtSn alloy formation
n-Butane dehydrogenation
n-Butenes

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1016/j.cattod.2013.10.070

Cite this

@article{9c6f637d146e4009ab741281807c1fa8,

title = "Effect of potassium addition on bimetallic PtSn supported θ-Al 2O3 catalyst for n-butane dehydrogenation to olefins",

abstract = "PtSn/θ-Al2O3 catalysts with different amount of potassium (0.4, 0.7, 0.95, 1.2 and 1.45 wt.%) were prepared by an impregnation method, and their catalytic activity in n-butane dehydrogenation was investigated at 823 K, an atmospheric pressure and a GHSV of 18,000 mL(g cat h)-1. The compositions listed in order of n-C 4= yields at 823 K were as follows: K0.95(PtSn) 1.5 > (PtSn)1.5 > K0.4(PtSn) 1.5 > K0.7(PtSn)1.5 > K 1.2(PtSn)1.5 > K1.45(PtSn)1.5 > K0.9(Pt)1.5. The K0.9(Pt)1.5 and K0.95(Sn)1.5 catalyst severely deactivated in n-butane dehydrogenation. The (PtSn)1.5 (without K) catalyst showed the highest n-butane conversion, while K0.95(PtSn)1.5 did the highest n-C4= yield. The small amount of potassium on bimetallic PtSn/θ-Al2O3 catalyst improved n-C 4= selectivity, but slightly decreased n-butane conversion, resulting in the increase of n-C4= yield. The effect of potassium was caused by blocking the acid sites of Pt catalyst. The TPR and HAADF STEM-EDS study suggested the reduction procedure of the Pt, Sn and K species. However, the higher loaded potassium (1.2 and 1.45 wt.%) doped (PtSn)1.5 catalysts were rather highly deactivated because the sizes of Pt particles were increased by weakening the interaction between Pt and Sn. The n-C4= selectivity of the (PtSn)1.5 catalyst increased with respect to the reaction, while that of the potassium doped catalysts maintained the high n-C4= selectivity from the beginning of the reaction. Also, different alkali metals (Ca, Na and Li) were tested for the comparison with K. The potassium doped catalyst showed the highest n-C4= yield among the other alkali metals for n-butane dehydrogenation.",

keywords = "Effect of alkali metal, PtSn alloy formation, n-Butane dehydrogenation, n-Butenes",

author = "Nagaraja, {Bhari Mallanna} and Heon Jung and Yang, {Dae Ryook} and Jung, {Kwang Deog}",

note = "Funding Information: This work was supported by the basic research project of KIST and by Converging Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology ( 2011K000660 ).",

year = "2014",

month = sep,

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doi = "10.1016/j.cattod.2013.10.070",

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T1 - Effect of potassium addition on bimetallic PtSn supported θ-Al 2O3 catalyst for n-butane dehydrogenation to olefins

AU - Nagaraja, Bhari Mallanna

AU - Jung, Heon

AU - Yang, Dae Ryook

AU - Jung, Kwang Deog

N1 - Funding Information: This work was supported by the basic research project of KIST and by Converging Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology ( 2011K000660 ).

PY - 2014/9/1

Y1 - 2014/9/1

N2 - PtSn/θ-Al2O3 catalysts with different amount of potassium (0.4, 0.7, 0.95, 1.2 and 1.45 wt.%) were prepared by an impregnation method, and their catalytic activity in n-butane dehydrogenation was investigated at 823 K, an atmospheric pressure and a GHSV of 18,000 mL(g cat h)-1. The compositions listed in order of n-C 4= yields at 823 K were as follows: K0.95(PtSn) 1.5 > (PtSn)1.5 > K0.4(PtSn) 1.5 > K0.7(PtSn)1.5 > K 1.2(PtSn)1.5 > K1.45(PtSn)1.5 > K0.9(Pt)1.5. The K0.9(Pt)1.5 and K0.95(Sn)1.5 catalyst severely deactivated in n-butane dehydrogenation. The (PtSn)1.5 (without K) catalyst showed the highest n-butane conversion, while K0.95(PtSn)1.5 did the highest n-C4= yield. The small amount of potassium on bimetallic PtSn/θ-Al2O3 catalyst improved n-C 4= selectivity, but slightly decreased n-butane conversion, resulting in the increase of n-C4= yield. The effect of potassium was caused by blocking the acid sites of Pt catalyst. The TPR and HAADF STEM-EDS study suggested the reduction procedure of the Pt, Sn and K species. However, the higher loaded potassium (1.2 and 1.45 wt.%) doped (PtSn)1.5 catalysts were rather highly deactivated because the sizes of Pt particles were increased by weakening the interaction between Pt and Sn. The n-C4= selectivity of the (PtSn)1.5 catalyst increased with respect to the reaction, while that of the potassium doped catalysts maintained the high n-C4= selectivity from the beginning of the reaction. Also, different alkali metals (Ca, Na and Li) were tested for the comparison with K. The potassium doped catalyst showed the highest n-C4= yield among the other alkali metals for n-butane dehydrogenation.

AB - PtSn/θ-Al2O3 catalysts with different amount of potassium (0.4, 0.7, 0.95, 1.2 and 1.45 wt.%) were prepared by an impregnation method, and their catalytic activity in n-butane dehydrogenation was investigated at 823 K, an atmospheric pressure and a GHSV of 18,000 mL(g cat h)-1. The compositions listed in order of n-C 4= yields at 823 K were as follows: K0.95(PtSn) 1.5 > (PtSn)1.5 > K0.4(PtSn) 1.5 > K0.7(PtSn)1.5 > K 1.2(PtSn)1.5 > K1.45(PtSn)1.5 > K0.9(Pt)1.5. The K0.9(Pt)1.5 and K0.95(Sn)1.5 catalyst severely deactivated in n-butane dehydrogenation. The (PtSn)1.5 (without K) catalyst showed the highest n-butane conversion, while K0.95(PtSn)1.5 did the highest n-C4= yield. The small amount of potassium on bimetallic PtSn/θ-Al2O3 catalyst improved n-C 4= selectivity, but slightly decreased n-butane conversion, resulting in the increase of n-C4= yield. The effect of potassium was caused by blocking the acid sites of Pt catalyst. The TPR and HAADF STEM-EDS study suggested the reduction procedure of the Pt, Sn and K species. However, the higher loaded potassium (1.2 and 1.45 wt.%) doped (PtSn)1.5 catalysts were rather highly deactivated because the sizes of Pt particles were increased by weakening the interaction between Pt and Sn. The n-C4= selectivity of the (PtSn)1.5 catalyst increased with respect to the reaction, while that of the potassium doped catalysts maintained the high n-C4= selectivity from the beginning of the reaction. Also, different alkali metals (Ca, Na and Li) were tested for the comparison with K. The potassium doped catalyst showed the highest n-C4= yield among the other alkali metals for n-butane dehydrogenation.

KW - Effect of alkali metal

KW - PtSn alloy formation

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KW - n-Butenes

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