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

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-Snmore » 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.« less
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
  2. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  3. Interfacial and Surface Science, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
Publication Date:
Report Number(s):
NREL/JA-5100-70060
Journal ID: ISSN 2155-5435
Grant/Contract Number:
AC36-08GO28308; AC05-00OR22725; MCB09159
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 9; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; biobased chemical; catalyst stability; leaching; lignocellulose; restructuring; Ru-Sn/AC; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1394395
Alternate Identifier(s):
OSTI ID: 1389739