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Title: Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

Abstract

Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, here we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100%more » of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. RTI International, Triangle Park, NC (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1335105
Report Number(s):
NREL/JA-5100-67259
Journal ID: ISSN 2168-0485
Grant/Contract Number:
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; biomass conversion; biorefinery; pyrolysis; reforming; thermochemical conversion; wastewater

Citation Formats

Black, Brenna A., Michener, William E., Ramirez, Kelsey J., Biddy, Mary J., Knott, Brandon C., Jarvis, Mark W., Olstad, Jessica, Mante, Ofei D., Dayton, David C., and Beckham, Gregg T. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis. United States: N. p., 2016. Web. doi:10.1021/acssuschemeng.6b01766.
Black, Brenna A., Michener, William E., Ramirez, Kelsey J., Biddy, Mary J., Knott, Brandon C., Jarvis, Mark W., Olstad, Jessica, Mante, Ofei D., Dayton, David C., & Beckham, Gregg T. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis. United States. doi:10.1021/acssuschemeng.6b01766.
Black, Brenna A., Michener, William E., Ramirez, Kelsey J., Biddy, Mary J., Knott, Brandon C., Jarvis, Mark W., Olstad, Jessica, Mante, Ofei D., Dayton, David C., and Beckham, Gregg T. 2016. "Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis". United States. doi:10.1021/acssuschemeng.6b01766. https://www.osti.gov/servlets/purl/1335105.
@article{osti_1335105,
title = {Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis},
author = {Black, Brenna A. and Michener, William E. and Ramirez, Kelsey J. and Biddy, Mary J. and Knott, Brandon C. and Jarvis, Mark W. and Olstad, Jessica and Mante, Ofei D. and Dayton, David C. and Beckham, Gregg T.},
abstractNote = {Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, here we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg-1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg-1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.},
doi = {10.1021/acssuschemeng.6b01766},
journal = {ACS Sustainable Chemistry & Engineering},
number = 12,
volume = 4,
place = {United States},
year = 2016,
month = 9
}

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  • Catalytic fast pyrolysis (CFP) of biomass produces a liquid product consisting of organic and aqueous streams. The organic stream is typically slated for hydrotreating to produce hydrocarbon biofuels, while the aqueous stream is considered a waste stream, resulting in the loss of residual biogenic carbon. Here, we report the detailed characterization and catalytic conversion of a CFP wastewater stream with the ultimate aim to improve overall biomass utilization within a thermochemical biorefinery. An aqueous stream derived from CFP of beech wood was comprehensively characterized, quantifying 53 organic compounds to a total of 17% organics. The most abundant classes of compoundsmore » are acids, aldehydes, and alcohols. The most abundant components identified in the aqueous stream were C1-C2 organics, comprising 6.40% acetic acid, 2.16% methanol, and 1.84% formaldehyde on wet basis. The CFP aqueous stream was catalytically upgraded to olefins and aromatic hydrocarbons using a Ga/HZSM-5 catalyst at 500 degrees C. When the conversion yield of the upgraded products was measured with fresh, active catalyst, 33% of the carbon in the aqueous stream was recovered as aromatic hydrocarbons and 29% as olefins. The majority of the experiments were conducted using a molecular beam mass spectrometer and separate GC-MS/FID experiments were used to confirm the assignments and quantification of products with fresh excess catalyst. The recovered 62% carbon in the form of olefins and aromatics can be used to make coproducts and/or fuels potentially improving biorefinery economics and sustainability. Spent catalysts were collected after exposure to varying amounts of the feed, and were characterized using multipoint-Brunauer-Emmett-Teller (BET) adsorption, ammonia temperature programmed desorption (TPD), and thermogravimetric analysis (TGA) to monitor deactivation of Ga/HZSM-5. These characterization data revealed that deactivation was caused by coke deposits, which blocked access to active sites of the catalyst and spent catalysts regained total activity after regeneration.« less
  • Hydrogen is of great interest as the cleanest fuel for power generation using fuel cells and for transportation. Biomass can be thermochemically converted to hydrogen via two distinct strategies: (1) gasification followed by shift conversion, and (2) fast pyrolysis of biomass followed by catalytic steam reforming and shift conversion of specific fractions. This paper presents the latter route. The process begins with fast pyrolysis of biomass to produce bio-oil, which (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a shift conversion step. Such a process has been demonstrated at themore » bench scale using model compounds and the aqueous fraction of poplar oil with commercial nickel-based steam-reforming catalysts. Hydrogen yields as high as 85% of the stoichiometric value have been obtained. Initial catalyst activity can be maintained through periodic regeneration via steam or carbon dioxide (CO2) gasification of the carbonaceous deposits.« less