Evaluation of the technical and commercial feasibility of the manufacture of bio-based polyester from cellulose derived hydroxymethyl furfural

Lead Research Organisation: University of Liverpool
Department Name: Chemistry

Abstract

Aromatic chemicals are a crucial constituent of plastics and bioplastics, conveying functionality such as strength and flexibility. At present, these chemicals can only be sourced economically from fossil-oil. However, lignocellulose is a low-cost and renewable material available from plants from which aromatics can be obtained, both from lignin and indirectly from the cellulose portion. This project evaluates the commercial potential of novel work that has demonstrated high yielding and efficient conversion of a cellulose-derived chemical called HMF into a key novel building block (FDCA) for the synthesis of a biomass-derived bioplastic PBAF. The two- step enzyme process uses enzyme biocatalysts called oxidases which work at 37degC where water is the only by product. Hence the process has extremely green credentials. The project will evaluate sensitivity to the source and type of crude HMF used, improve reaction conditions and will be scaled up to produce gram quantities of FDCA. These will be converted into novel polymers and the properties of these materials tested. A techno-economic assessment of the holistic process will be carried out to evaluate the commercial potential in both the bioplastic and broader polyester markets.

Technical Summary

Aromatic chemicals are a crucial constituent of plastics and bioplastics, conveying strength and flexibility. At present, these chemicals can only be sourced economically from fossil-oil. However, lignocellulose is a potential low-cost and renewable alternative input. This project will evaluate the commercial potential of novel work that has demonstrated a tandem bioconversion giving high yields (74% isolated, unoptimised) of the aromatic diacid, furan-2, 5-dicarboxylic acid (FDCA), from cellulose derived hydroxymethyl furfural (HMF), using isolated oxidase enzymes galactose oxidase M3-5 and E. coli aldehyde oxidase PaoABC. Both enzymes will be immobilised to compare performance with soluble enzymes. Loading efficiency, activity, re-use efficiency and product recovery will be optimised. This work will also provide important preliminary data for potential application in flow reactors. Reaction parameters, including pH control for HMF to FDCA in a two-step, one-pot conversion will be optimised. We will produce gram quantities of bio-derived FDCA with a target reaction concentration of 50g/L. We will also investigate a single stage process where both enzymes can be combined. This will require new GOase mutants that can convert the PaoABC by-product hydroxymethyl acid (HMFCA) to FDCA more effectively. If a suitable enzyme can be found we will substitute this for GOase M3-5 and thus potentially develop a combined GOase-PaoABC process. Biome will identify different sources of crude HMF and a process from a crude feed will be investigated. The FDCA produced will be converted into novel block co-polyesters/amides by Biome and the properties of these materials tested and compared with material made from commercially available FDCA and petrochemically-derived terephthalate analogue polymer PBAT. A techno-economic assessment of the holistic process will be carried out to evaluate the commercial potential in both the bioplastic and broader polyester markets.

Planned Impact

As described in proposal submitted to INNOVATE UK
 
Description We have developed a biocatalytic route to a key intermediate (FDCA) monomer for bioplastics formation starting from HMF, which can be made from biomass. The award has allowed us to develop proof-of-principle for demonstration of feasibility for scale up of this multi-enzyme process. The bioconversion has advantages over other chemocatalytic and biocatalytic processes in that the conversion and product purity are very high and this is required for subsequent polymer formation. The collaborating company, Biome Technologies have patented the biopolymers that we will make. There is potential for new IP in the immobilisation and application of the biocatalysts we are developing.
Exploitation Route We have recently been funded by Innovate UK to scale up the process developed in this award. Title: "Scale-up and commercial evaluation of the manufacture of bio-based FDCA from HMF" 1/10/2017 - 30/9/2019. This is a collaboration with Biome Bioplastics and The University of Leeds. A.J. Carnell (academic PI), J. Blacker and Biome Bioplastics, Innovate UK, Liverpool £163,251 (total value £837,055).
Sectors Chemicals,Manufacturing, including Industrial Biotechology

 
Description BBSRC Biocatnet Proof of Concept-034 "Enzymatic methylation of bio-derived aromatic diacids as polyester precursors".
Amount £50,451 (GBP)
Funding ID Biocatnet PoC-034 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 11/2017 
End 04/2018
 
Description Development of oxidases for synthesis of bioplastics intermediates
Amount £252,663 (GBP)
Funding ID BB/V003100/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 09/2020 
End 09/2022
 
Description Innovate UK IB Catalyst Industrial Research
Amount £875,752 (GBP)
Funding ID BB/N023625/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 07/2016 
End 06/2019
 
Description Materials and Manufacturing round 2
Amount £837,055 (GBP)
Funding ID Co. No. RC000660 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 10/2017 
End 09/2019
 
Title PROCESS FOR OXIDISING A SUBSTRATE 
Description A process for oxidising a substrate selected from hydroxymethylfurfural (HMF), diformylfuran (DFF), hydroxymethylfurancarboxylic acid (HMFCA) and formylfurancarboxylic acid (FFCA). Said process comprises mixing said substrate with catalase, one or more further enzymes and hydrogen peroxide to form a reaction mixture. Said one or more further enzymes have the ability to catalyse oxidation of said substrate. Said hydrogen peroxide is provided at a total molar ratio of at least about 0.1:1 hydrogen peroxide to substrate. 
IP Reference US2021017556 
Protection Patent application published
Year Protection Granted 2021
Licensed No
Impact None yet. Too early.
 
Title PROCESSES FOR THE FORMATION OF FURANDICARBOXYLIC ACID (FDCA) VIA A MULTISTEP BIOCATALYTIC OXIDATION REACTION OF 5-HYDROXYMETHYLFURFURAL (HMF) 
Description The present invention relates to processes for the formation of furandicarboxylic acid (FDCA), in particular 2,5-furandicarboxylic acid (2,5-FDCA), and mono- and diester derivatives thereof, via a multistep biocatalytic oxidation reaction of 5-hydroxymethylfurfural (HMF) using, for example, an enzyme selected from the group consisting of xanthine oxidoreductase (XOR), galactose oxidase variant M3-5, aldehyde dehydrogenase, and/or ketoreductase. The invention also relates to copolymers that comprise the furandicarboxylic acid monomers and derivatives thereof, processes for the formation of the copolymers and uses for the copolymers. 
IP Reference WO2016202858 
Protection Patent application published
Year Protection Granted 2016
Licensed No
Impact None, yet.
 
Description Sixth Form College Visit 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact I (PI) visited Sir John Dean's Sixth Form College in Cheshire to give a Sixth Form Lecture to inspire students about research in Chemistry and to encourage students to apply to do chemistry. The talk contained slides directly related to this research project on conversion of Biomass to Bioplastics. I took along a box of samples of commercial products made from bioplastics supplied by our collaborators Biome Bioplastics to show the students. The outcome was well received and feedback at our Liverpool university Open Day was positive.
Year(s) Of Engagement Activity 2016