Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

Derek R. Vardon; Amy E. Settle; Vassili Vorotnikov; Martin J. Menart; Todd R. Eaton; Kinga A. Unocic; K. Xerxes Steirer; Kevin N. Wood; Nicholas S. Cleveland; Kathleen E. Moyer; William E. Michener; Gregg T. Beckham

doi:10.1021/acscatal.7b02015

Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

Derek R. Vardon, Amy E. Settle, Vassili Vorotnikov, Martin J. Menart, Todd R. Eaton, Kinga A. Unocic, K. Xerxes Steirer, Kevin N. Wood, Nicholas S. Cleveland, Kathleen E. Moyer, William E. Michener, Gregg T. Beckham

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Abstract

Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ∼1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that are colocated and surface-enriched with Sn. Postbatch reaction characterization confirmed stable Ru-Sn material properties; however, upon a transition to continuous conditions, significant Ru-Sn/AC deactivation occurred due to stainless steel leaching of Ni that resulted in Ru-Sn metal crystallite restructuring to form discrete Ni-Sn sites. Computational modeling confirmed favorable energetics for Ru-Sn segregation and Ni-Sn formation at submonolayer Sn incorporation. To address stainless steel leaching, reactor walls were treated with an inert silica coating by chemical vapor deposition. With leaching reduced, stable Ru-Sn/AC performance was observed that resulted in a molar yield of 71% BDO and 15% tetrahydrofuran for 96 h of time on stream. Postreaction catalyst characterization confirmed low levels of Ni and Cr deposition, although early-stage islanding of Ni-Sn will likely be problematic for industrially relevant time scales (i.e., thousands of hours). Overall, these results (i) demonstrate the performance of Ru-Sn/AC for aqueous phase succinic acid reduction, (ii) provide insight into the Ru-Sn bimetallic structure and deactivation in the presence of leached Ni, and (iii) underscore the importance of compatible reactor metallurgy and durable catalysts.

Original language	American English
Pages (from-to)	6207-6219
Number of pages	13
Journal	ACS Catalysis
Volume	7
Issue number	9
DOIs	https://doi.org/10.1021/acscatal.7b02015 https://doi.org/10.1021/acscatal.7b02015
State	Published - 1 Sep 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

NREL Publication Number

NREL/JA-5100-70060

Keywords

biobased chemical
catalyst stability
leaching
lignocellulose
restructuring
Ru-Sn/AC

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Vardon, D. R., Settle, A. E., Vorotnikov, V., Menart, M. J., Eaton, T. R., Unocic, K. A., Steirer, K. X., Wood, K. N., Cleveland, N. S., Moyer, K. E., Michener, W. E., & Beckham, G. T. (2017). Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions. ACS Catalysis, 7(9), 6207-6219. https://doi.org/10.1021/acscatal.7b02015, https://doi.org/10.1021/acscatal.7b02015

@article{f7f681fe0642475cb29943e9e0196d05,

title = "Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions",

abstract = "Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ∼1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that are colocated and surface-enriched with Sn. Postbatch reaction characterization confirmed stable Ru-Sn material properties; however, upon a transition to continuous conditions, significant Ru-Sn/AC deactivation occurred due to stainless steel leaching of Ni that resulted in Ru-Sn metal crystallite restructuring to form discrete Ni-Sn sites. Computational modeling confirmed favorable energetics for Ru-Sn segregation and Ni-Sn formation at submonolayer Sn incorporation. To address stainless steel leaching, reactor walls were treated with an inert silica coating by chemical vapor deposition. With leaching reduced, stable Ru-Sn/AC performance was observed that resulted in a molar yield of 71% BDO and 15% tetrahydrofuran for 96 h of time on stream. Postreaction catalyst characterization confirmed low levels of Ni and Cr deposition, although early-stage islanding of Ni-Sn will likely be problematic for industrially relevant time scales (i.e., thousands of hours). Overall, these results (i) demonstrate the performance of Ru-Sn/AC for aqueous phase succinic acid reduction, (ii) provide insight into the Ru-Sn bimetallic structure and deactivation in the presence of leached Ni, and (iii) underscore the importance of compatible reactor metallurgy and durable catalysts.",

keywords = "biobased chemical, catalyst stability, leaching, lignocellulose, restructuring, Ru-Sn/AC",

author = "Vardon, {Derek R.} and Settle, {Amy E.} and Vassili Vorotnikov and Menart, {Martin J.} and Eaton, {Todd R.} and Unocic, {Kinga A.} and Steirer, {K. Xerxes} and Wood, {Kevin N.} and Cleveland, {Nicholas S.} and Moyer, {Kathleen E.} and Michener, {William E.} and Beckham, {Gregg T.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = sep,

day = "1",

doi = "10.1021/acscatal.7b02015",

language = "American English",

volume = "7",

pages = "6207--6219",

journal = "ACS Catalysis",

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Vardon, DR, Settle, AE, Vorotnikov, V, Menart, MJ, Eaton, TR, Unocic, KA, Steirer, KX, Wood, KN, Cleveland, NS, Moyer, KE, Michener, WE & Beckham, GT 2017, 'Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions', ACS Catalysis, vol. 7, no. 9, pp. 6207-6219. https://doi.org/10.1021/acscatal.7b02015, https://doi.org/10.1021/acscatal.7b02015

TY - JOUR

T1 - Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

AU - Vardon, Derek R.

AU - Settle, Amy E.

AU - Vorotnikov, Vassili

AU - Menart, Martin J.

AU - Eaton, Todd R.

AU - Unocic, Kinga A.

AU - Steirer, K. Xerxes

AU - Wood, Kevin N.

AU - Cleveland, Nicholas S.

AU - Moyer, Kathleen E.

AU - Michener, William E.

AU - Beckham, Gregg T.

PY - 2017/9/1

Y1 - 2017/9/1

N2 - Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ∼1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that are colocated and surface-enriched with Sn. Postbatch reaction characterization confirmed stable Ru-Sn material properties; however, upon a transition to continuous conditions, significant Ru-Sn/AC deactivation occurred due to stainless steel leaching of Ni that resulted in Ru-Sn metal crystallite restructuring to form discrete Ni-Sn sites. Computational modeling confirmed favorable energetics for Ru-Sn segregation and Ni-Sn formation at submonolayer Sn incorporation. To address stainless steel leaching, reactor walls were treated with an inert silica coating by chemical vapor deposition. With leaching reduced, stable Ru-Sn/AC performance was observed that resulted in a molar yield of 71% BDO and 15% tetrahydrofuran for 96 h of time on stream. Postreaction catalyst characterization confirmed low levels of Ni and Cr deposition, although early-stage islanding of Ni-Sn will likely be problematic for industrially relevant time scales (i.e., thousands of hours). Overall, these results (i) demonstrate the performance of Ru-Sn/AC for aqueous phase succinic acid reduction, (ii) provide insight into the Ru-Sn bimetallic structure and deactivation in the presence of leached Ni, and (iii) underscore the importance of compatible reactor metallurgy and durable catalysts.

AB - Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ∼1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that are colocated and surface-enriched with Sn. Postbatch reaction characterization confirmed stable Ru-Sn material properties; however, upon a transition to continuous conditions, significant Ru-Sn/AC deactivation occurred due to stainless steel leaching of Ni that resulted in Ru-Sn metal crystallite restructuring to form discrete Ni-Sn sites. Computational modeling confirmed favorable energetics for Ru-Sn segregation and Ni-Sn formation at submonolayer Sn incorporation. To address stainless steel leaching, reactor walls were treated with an inert silica coating by chemical vapor deposition. With leaching reduced, stable Ru-Sn/AC performance was observed that resulted in a molar yield of 71% BDO and 15% tetrahydrofuran for 96 h of time on stream. Postreaction catalyst characterization confirmed low levels of Ni and Cr deposition, although early-stage islanding of Ni-Sn will likely be problematic for industrially relevant time scales (i.e., thousands of hours). Overall, these results (i) demonstrate the performance of Ru-Sn/AC for aqueous phase succinic acid reduction, (ii) provide insight into the Ru-Sn bimetallic structure and deactivation in the presence of leached Ni, and (iii) underscore the importance of compatible reactor metallurgy and durable catalysts.

KW - biobased chemical

KW - catalyst stability

KW - leaching

KW - lignocellulose

KW - restructuring

KW - Ru-Sn/AC

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U2 - 10.1021/acscatal.7b02015

DO - 10.1021/acscatal.7b02015

M3 - Article

AN - SCOPUS:85029034757

SN - 2155-5435

VL - 7

SP - 6207

EP - 6219

JO - ACS Catalysis

JF - ACS Catalysis

IS - 9

ER -

Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

Abstract

Bibliographical note

NREL Publication Number

Keywords

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