Title: Simultaneous Dehydration of Glucose and Xylose Present in a Process-Relevant Biorefinery Hydrolysate to Furfurals Using Heterogeneous Solid Acid Catalysts

Abstract

In this work, we report the simultaneous dehydration of glucose and xylose present in a process-relevant biorefinery hydrolysate to furfural and 5-hydroxymethylfurfural (HMF) using heterogeneous solid acid catalysts in a microwave reactor. Initially, several solid acid catalysts with varied Bronsted and Lewis acidity were screened to evaluate their activity and selectivity in dehydration of pure glucose to HMF. A noticeable improvement in HMF yield from dehydration of 8 wt% glucose was obtained by combining an acidic ion-exchange resin (Purolite CT-275DR) with an amorphous silica-alumina catalyst (Davicat-3115) resulting in HMF yields of 27-33% using a homogeneous solvent system of aqueous dioxane (dioxane/water, 2:1 v/v) at 195 °C in 5 min. Under the same reaction conditions, catalysts, and solvent system but with the addition of NaCl in catalytic amounts (33-100 mM), a more than 2-fold increase in HMF yields (66-70%) was achieved for the dehydration of 8 wt% glucose, whereas furfural yields approaching 95% were achieved for the dehydration of 6 wt% xylose, when conducted separately. Notably, using the same catalyst and solvent system while slightly modifying the reaction conditions to 197 °C and 5 min, simultaneous dehydration of 4 wt% xylose and 9 wt% glucose present in a process-relevant corn stovermore » hydrolysate resulted in furfural and HMF yields of 96 and 74%, respectively, resulting in a combined furfural yield of 80%. The results further showed that the pH of the reaction solution played an important role in maximizing product yields. A pH < 2 resulted in low HMF yields due to the increased formation of HMF degradation products, whereas a pH 2-3 gave high HMF yields by possibly stabilizing the reaction intermediates and product, suppressing the occurrence of side reactions.« less

Authors:

Mittal, Ashutosh  ^[1];

• Search DOE PAGES for author "Mittal, Ashutosh"
• Search DOE PAGES for ORCID "0000-0002-0434-0745"

Ruddy, Daniel A.  ^[2];

• Search DOE PAGES for author "Ruddy, Daniel A."
• Search DOE PAGES for ORCID "0000-0003-2654-3778"

Chen, Xiaowen  ^[3];

• Search DOE PAGES for author "Chen, Xiaowen"
• Search DOE PAGES for ORCID "0000-0001-8041-5852"

Johnson, David K.  ^[1]

• Search DOE PAGES for author "Johnson, David K."
• Search DOE PAGES for ORCID "0000-0003-4815-8782"

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+ Show Author Affiliations

1. Renewable Resources and Enabling Sciences Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
2. Catalytic Carbon Transformation & Scale-up Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
3. Biochemical Process Integration Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States

Publication Date:

Tue Aug 22 00:00:00 EDT 2023

Research Org.:

National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Org.:

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

OSTI Identifier:

1996288

Alternate Identifier(s):

OSTI ID: 2005577

Report Number(s):

NREL/JA-2800-80807
Journal ID: ISSN 0887-0624

Grant/Contract Number:  

AC36-08GO28308

Resource Type:

Published Article

Journal Name:

Energy and Fuels

Additional Journal Information:

Journal Name: Energy and Fuels Journal Volume: 37 Journal Issue: 17; Journal ID: ISSN 0887-0624

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Aldehydes; Carbohydrates; Catalysts; Dehydration; Oxides; catalyst; dehydration; furfural; glucose; heterogeneous; HMF; hydrolysate; xylose