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

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

55 Scopus Citations

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.

NLR 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",

issn = "2155-5435",

number = "9",

}

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

UR - https://www.scopus.com/pages/publications/85029034757

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

NLR Publication Number

Keywords

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