Title: Hybrid Catalytic Biorefining of Hardwood Biomass to Methylated Furans and Depolymerized Technical Lignin

Abstract

A robust method is needed to achieve high yield all-catalytic conversion of recalcitrant lignocellulosic biomass to transportation fuels while maximizing carbon utilization from raw substrates. To accomplish this, we developed an integrated strategy that combines homogeneous and heterogeneous reactions with a treatment-extraction step to co-produce 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) directly from hardwood poplar while maintaining high catalyst activity. In the first step, poplar wood chips were treated with dilute FeCl3 in THF-water at sub-pyrolytic temperature to yield 93.5% furfural (FF) from xylan and 66.0% 5- hydroxymethylfurfural (HMF) from glucan. Concurrently, a highly pure lignin powder was obtained from the liquor by precipitation upon room temperature vacuum recovery of THF from the water. Afterwards, FF and HMF were extracted from water into an organic phase consisting of toluene and 1,4-dioxane treated with Ca(OH)2. A second hydrodeoxygenation reaction using Cu-Ni/TiO2 catalyst yielded 87.8% MF from FF and 85.6% DMF from HMF. Characterization of the lignin product showed its molecular weight to be reduced by an order of magnitude from its native state as well as complete removal of its native β-aryl ether linkages without hydrogen input or further heterogeneous catalytic processing. A 60% cumulative yield of MF, DMF, and lignin productsmore » from the available carbon (xylan+glucan+lignin) in poplar was achieved, rivaling more mature cellulosic ethanol strategies.« less

Authors:

Seemala, Bhogeswararao ^[1]; Meng, Xianzhi  ^[2];

• Search DOE PAGES for author "Meng, Xianzhi"
• Search DOE PAGES for ORCID "0000-0003-4303-3403"

Parikh, Aakash ^[1]; Nagane, Nikhil ^[1]; Kumar, Rajeev ^[3]; Wyman, Charles E. ^[1]; Ragauskas, Arthur  ^[4];

• Search DOE PAGES for author "Ragauskas, Arthur"
• Search DOE PAGES for ORCID "0000-0002-3536-554X"

Christopher, Phillip  ^[5];

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• Search DOE PAGES for ORCID "0000-0002-4898-5510"

Cai, Charles M.  ^[1]

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• Search DOE PAGES for ORCID "0000-0002-5047-0815"

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+ Show Author Affiliations

1. Univ. of California, Riverside, CA (United States). Bourns College of Engineering. Center for Environmental and Research Technology (CE-CERT). Dept. of Chemical and Environmental Engineering
2. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical & Biomolecular Engineering
3. Univ. of California, Riverside, CA (United States). Bourns College of Engineering. Center for Environmental and Research Technology (CE-CERT)
4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical & Biomolecular Engineering. Inst. Agriculture. Dept. of Forestry, Wildlife and Fisheries. Center for Renewable Carbon; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division
5. Univ. of California, Riverside, CA (United States). Bourns College of Engineering. Dept. of Chemical and Environmental Engineering; Univ. of California, Santa Barbara, CA (United States). Dept. of Chemical Engineering

Publication Date:

Thu Jun 28 00:00:00 EDT 2018

Research Org.:

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office

OSTI Identifier:

1471887

Alternate Identifier(s):

OSTI ID: 1581905

Grant/Contract Number:  

AC05-00OR22725; EE0007006

Resource Type:

Accepted Manuscript

Journal Name:

ACS Sustainable Chemistry & Engineering

Additional Journal Information:

Journal Volume: 6; Journal Issue: 8; Journal ID: ISSN 2168-0485

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

09 BIOMASS FUELS; biofuels; biomass; fractionation; hydrodeoxygenation; lignin