Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors

Peterson, Braden H.; Engtrakul, Chaiwat; Wilson, Nolan; Dellorco, Stefano; Orton, Kellene A.; Deutch, Stephen P.; Yung, Matthew M.; Starace, Anne K.; Parent, Yves O.; Chiaramonti, David; Magrini, Kimberly A.

doi:10.1021/acssuschemeng.9b03188

Title: Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors

Abstract

During ex situ catalytic fast pyrolysis (CFP) of biomass, the separation of reactive char and alkali/alkaline particulates from biomass pyrolysis vapors by hot-gas filtration (HGF) leads to improved vapor stability and quality. HGF in tandem with chemical tailoring (e.g., partial deoxygenation) of the clean pyrolysis vapors, denoted as catalytic hot-gas filtration (CHGF), has the potential to further improve vapor composition by removing reactive oxygen moieties and protect downstream upgrading catalysts from fouling. Downstream upgrading refers to both vapor phase upgrading (e.g., ex situ CFP) and condensed phase upgrading (e.g., hydrotreating). Consequently, CHGF (as a single unit operation) was evaluated for preconditioning pyrolysis vapors for downstream upgrading processes. In order to understand the effective operating conditions that successfully filter and partially deoxygenate pyrolysis vapors, a titania-supported molybdenum heteropolyacid (Mo-HPA/TiO₂) catalyst was studied for use in CHGF. Here, pine pyrolysis vapors were generated in a small pilot-scale pyrolyzer and transferred to a CHGF unit via a continuous-flow slipstream. In the CHGF unit, the pyrolysis vapors were filtered and upgraded over a packed Mo-HPA/TiO₂ catalyst bed. Real-time monitoring and identification of the products formed were achieved by molecular beam mass spectrometry. The results showed that under a hydrogen-rich environment, the pine vapors weremore »« less

Authors:

Peterson, Braden H. ^[1];

^[1];

^[1]; Dellorco, Stefano ^[2]; Orton, Kellene A. ^[1]; Deutch, Stephen P. ^[1];

^[1]; Starace, Anne K. ^[1]; Parent, Yves O. ^[1]; Chiaramonti, David ^[2];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of Florence (Italy); Renewable Energy Consortium for Research and Demonstration (RE-CORD), Florence (Italy)

Publication Date:: Tue Aug 13 00:00:00 EDT 2019

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1559778

Report Number(s):: NREL/JA-5100-73297
Journal ID: ISSN 2168-0485

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: ACS Sustainable Chemistry & Engineering

Additional Journal Information:: Journal Volume: 7; Journal Issue: 17; Journal ID: ISSN 2168-0485

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 09 BIOMASS FUELS; biomass pyrolysis vapors; catalytic hot-gas filtration; hot-gas filtration; heteropolyacid; keggin-type structure; preconditioning; process intensification; partial upgrading; fractional condensation; separation

Citation Formats


                    Peterson, Braden H., Engtrakul, Chaiwat, Wilson, Nolan, Dellorco, Stefano, Orton, Kellene A., Deutch, Stephen P., Yung, Matthew M., Starace, Anne K., Parent, Yves O., Chiaramonti, David, and Magrini, Kimberly A. Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors.  United States: N. p., 2019. 
Web.  doi:10.1021/acssuschemeng.9b03188.

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                    Peterson, Braden H., Engtrakul, Chaiwat, Wilson, Nolan, Dellorco, Stefano, Orton, Kellene A., Deutch, Stephen P., Yung, Matthew M., Starace, Anne K., Parent, Yves O., Chiaramonti, David, & Magrini, Kimberly A. Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors.  United States.  https://doi.org/10.1021/acssuschemeng.9b03188

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                    Peterson, Braden H., Engtrakul, Chaiwat, Wilson, Nolan, Dellorco, Stefano, Orton, Kellene A., Deutch, Stephen P., Yung, Matthew M., Starace, Anne K., Parent, Yves O., Chiaramonti, David, and Magrini, Kimberly A. Tue .  
"Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors".  United States.  https://doi.org/10.1021/acssuschemeng.9b03188.  https://www.osti.gov/servlets/purl/1559778.

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@article{osti_1559778,

  title        = {Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors},

  author       = {Peterson, Braden H. and Engtrakul, Chaiwat and Wilson, Nolan and Dellorco, Stefano and Orton, Kellene A. and Deutch, Stephen P. and Yung, Matthew M. and Starace, Anne K. and Parent, Yves O. and Chiaramonti, David and Magrini, Kimberly A.},

  abstractNote = {During ex situ catalytic fast pyrolysis (CFP) of biomass, the separation of reactive char and alkali/alkaline particulates from biomass pyrolysis vapors by hot-gas filtration (HGF) leads to improved vapor stability and quality. HGF in tandem with chemical tailoring (e.g., partial deoxygenation) of the clean pyrolysis vapors, denoted as catalytic hot-gas filtration (CHGF), has the potential to further improve vapor composition by removing reactive oxygen moieties and protect downstream upgrading catalysts from fouling. Downstream upgrading refers to both vapor phase upgrading (e.g., ex situ CFP) and condensed phase upgrading (e.g., hydrotreating). Consequently, CHGF (as a single unit operation) was evaluated for preconditioning pyrolysis vapors for downstream upgrading processes. In order to understand the effective operating conditions that successfully filter and partially deoxygenate pyrolysis vapors, a titania-supported molybdenum heteropolyacid (Mo-HPA/TiO2) catalyst was studied for use in CHGF. Here, pine pyrolysis vapors were generated in a small pilot-scale pyrolyzer and transferred to a CHGF unit via a continuous-flow slipstream. In the CHGF unit, the pyrolysis vapors were filtered and upgraded over a packed Mo-HPA/TiO2 catalyst bed. Real-time monitoring and identification of the products formed were achieved by molecular beam mass spectrometry. The results showed that under a hydrogen-rich environment, the pine vapors were partially deoxygenated and alkylated over the Mo-HPA/TiO2 catalyst. Reactivity studies revealed that an increase in hydrogen concentration and a reduction in weight-hourly space velocity enhanced deoxygenation and alkylation. Time-on-stream (TOS) studies showed stable product formation up to 1 h with little change in catalyst activity. Additionally, the liquid product was collected using a custom fractional condensation unit (built in-house) and analyzed by gas chromatography mass spectrometry to confirm that the product was partially deoxygenated and alkylated. The combination of CHGF and fractional condensation allowed for chemical and physical removal of both foulant and value-added compounds (e.g., phenols, alkylphenols, methoxyphenols, cyclopentenones) for additional enhancement of downstream upgrading processes. The pre- and postreaction catalysts were characterized using temperature-programmed desorption, N2 physisorption, and elemental analysis with results indicating some catalyst coking. A hydrogen-based catalyst regeneration procedure restored the reacted catalyst activity to that of fresh Mo-HPA/TiO2.},

  doi          = {10.1021/acssuschemeng.9b03188},

  journal      = {ACS Sustainable Chemistry & Engineering},

  number       = 17,

  volume       = 7,

  place        = {United States},

  year         = {Tue Aug 13 00:00:00 EDT 2019},

  month        = {Tue Aug 13 00:00:00 EDT 2019}

}

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https://doi.org/10.1021/acssuschemeng.9b03188

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Cited by: 9 works

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Figure 1: Catalytic hot-gas filter (CHGF) and Davison Circulating Riser (DCR) systems coupled to a small pilot-scale pyrolyzer reactor system. The pyrolyzer system includes a biomass feed system, fluidized bed pyrolyzer, char cyclones + catch-pots, hot-gas filter (HGF) unit, slipstreams to the CHGF and DCR systems, and a scrubber productmore »

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