Ionic Liquid Biorefining of Lignocellulose to Sustainable Polymers

Lead Research Organisation: Imperial College London
Department Name: Dept of Chemistry

Abstract

We currently make more than just fuel from petroleum refining. Many of the plastics, solvents and other products that are used in everyday life are derived from these non-renewable resources. Our research programme aims to replace many of the common materials used as plastics with alternatives created from plants. This will enable us to tie together the UK's desire to move to non-petroleum fuel sources (e.g. biofuels) with our ability to produce renewable polymers and related products.

Plant cell walls are made up of two main components: carbohydrate polymers (long chains of sugars) and lignin, which is the glue holding plants together. We will first develop methods of separating these two components using sustainable solvents called ionic liquids. Ionic liquids are salts which are liquids at room temperature, enabling a variety of chemical transformations to be carried out under consitions not normally available to traditional organic solvents. These ionic liquids also reduce pollution as they have no vapours and can be made from non-toxic, non-petroleum based resources.

We will take the isolated carbohydrate polymers and break them down into simple sugars using enzymes and then further convert those sugars into building blocks for plastics using a variety of novel catalytic materials specifically designed for this process. The lignin stream will also be broken down and rebuilt into new plastics that can replace common materials. All of these renewable polymers will be used in a wide range of consumer products, including packaging materials, plastic containers and construction materials. The chemical feedstocks that we are creating will be flexible (used for chemical, material and fuel synthesis), safe (these feedstocks are predominantly non-toxic) and sustainable (most of the developed products are biodegradable). This will help reduce the overall environmental impact of the material economy in the UK.

The chemistry that we will use focusses on creating highly energy efficient and low-cost ways of making these materials without producing large amounts of waste. We are committed to only developing future manufacturing routes that are benign to the environment in which we all live. In addition, natural material sources often have properties that are superior to those created using artificial means. We plan to exploit these advantages of natural resources in order to produce both replacements for current products and new products with improved performance. This will make our synthetic routes both environmentally responsible and economically advantageous. The UK has an opportunity to take an international lead in this area due to the accumulation of expertise within this country.

The overall goal of this project is to develop sustainable manufacturing routes that will stimulate new UK businesses and environmentally responsible means of making common, high value materials. We will bring together scientific experts in designing processes, manufacturing plastics, growing raw biomass resources and developing new chemistries. The flexibility of resources is vital to the success of this endeavour, as no single plant biomass can be used for manufacturing on a year-round basis. Together with experienced leaders of responsible manufacturing industries, we will develop new ways of making everyday materials in a sustainable and economically beneficial way.

The result of this research will be a fundamental philosophical shift to our material, chemical, and energy economy. The technologies proposed in this work will help break our dependence on rapidly depleting fossil resources and enable us to become both sustainable and self-sufficient. This will result in greater security, less pollution, and a much more reliable and responsible UK economy.

Planned Impact

We anticipate our work will benefit a wide range of stakeholders including: biomass growers and processors, chemical and energy companies, polymer manufacturers and compositors and the broader chemical industries, as well as consumers interested in new products developed through the exploitation of sustainable feedstocks. Our proposed project will demonstrate to this broad base of stakeholders the opportunities and benefits of novel fractionation and conversion processes, and compute performance benchmarks by which novel processes can be compared against existing process chains.

In order to ensure this impact, we have already involved several industrial (Shell, BASF, Plaxica, Biocatalysts, Johnson Matthey), institutional (IBERS, JBEI, FuBio) and policy (Climate-KIC, Grantham Institute) stakeholders in our research programme. Representatives from each of these groups will be closely involved in our research efforts, advising us on pathways to commercialisation and ensuring we maximise the impact of our research efforts.

We shall work with our stakeholders to determine the economic, institutional and technical obstacles that currently prevent a shift to renewable resource based manufacturing. This will help us overcome these obstacles and ensure smooth implementation and exploitation of the fundamental principles developed and discovered during the course of this research programme.

Public engagement on such a major social issue is crucial. In order to ensure engagement with the general public, we will use the outreach providers at our home universities and also the professional public institutes with which we are associated. These include the Porter Alliance (biorenewable resource development), Energy Futures Laboratory (bioenergy), Grantham Institute for Climate Change, Manufacturing Futures Lab (sustainable manufacturing practices) and the BSBEC Outreach Group (bioenergy crop and land-use policy). We will also engage directly with the public by building a project website containing information on renewable manufacturing and by taking advantage of Imperial College's proximity to the National Science and Natural History museums, which provide a unique opportunity to show-case research on biorefining.

As this research is primarily aimed at developing sustainable manufacturing, we anticipate a substantial impact on the future landscape of the UK manufacturing sector. The material routes and practices developed in this type of research represent potential economic impact by developing secure routes of material and chemical manufacturing within the UK. Breaking our dependence on fossil reserves will necessarily create new manufacturing industries and also reduce our dependence on imported goods.

A shift from fossil resources to renewable ones will have a positive impact on the environment, improving quality of life for everyone in the UK. This objective is concurrent with the positive economic impact; the linking of these goals is vital to the realization of either.

There is great training potential within this project. As we will be employing nine full-time researchers in the programme, we will be furthering the dissemination of sustainable manufacturing principles into the employment sector. This will influence future manufacturing directions as the propagation of these future research and development leaders into the chemical industry is inevitable.

The extensive timeline of this programme (five years) will enable us to have a sustained impact on manufacturing practices and policies, as we will be able to extend our vision into industry (through our project partners) and public policy (through our advisory institutes). Thes value of these goals cannot be overstated - the impact of academic research can only be realized if the support of government agencies and the UK public is evident. This requires long-term committments to the research principles we have outlined within this programme.

Publications

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F. De Gregorio G (2016) Oxidative Depolymerization of Lignin Using a Novel Polyoxometalate-Protic Ionic Liquid System in ACS Sustainable Chemistry & Engineering

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Giarola S (2016) Techno-economic assessment of the production of phthalic anhydride from corn stover in Chemical Engineering Research and Design

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Gschwend FJ (2016) Pretreatment of Lignocellulosic Biomass with Low-cost Ionic Liquids. in Journal of visualized experiments : JoVE

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Kontturi KS (2017) Noncovalent Surface Modification of Cellulose Nanopapers by Adsorption of Polymers from Aprotic Solvents. in Langmuir : the ACS journal of surfaces and colloids

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Myers D (2016) Polymer synthesis: To react the impossible ring. in Nature chemistry

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Myers D (2017) Phosphasalen Indium Complexes Showing High Rates and Isoselectivities in rac-Lactide Polymerizations. in Angewandte Chemie (International ed. in English)

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Prado R (2016) Lignin oxidation and depolymerisation in ionic liquids in Green Chemistry

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Prado R (2016) Willow Lignin Oxidation and Depolymerization under Low Cost Ionic Liquid in ACS Sustainable Chemistry & Engineering

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Romain C (2017) Di-Zinc-Aryl Complexes: CO Insertions and Applications in Polymerisation Catalysis. in Chemistry (Weinheim an der Bergstrasse, Germany)

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Romain DC (2014) Chemoselective polymerization control: from mixed-monomer feedstock to copolymers. in Angewandte Chemie (International ed. in English)

 
Description We currently make more than just fuel from petroleum refining. Many of the plastics that are used in everyday life are derived from these non-renewable resources. The purpose of our research programme was to move us closer to being able to replace these non-renewable, non-biodegradable plastics with alternatives created from plants. The preparation of materials and products such as plastics from biomass requires the development of new chemistry and processes. To do this, we needed to work on the whole process from the first breakdown of wood into its component parts, through the processing of these into the key components of potential new bio-derived plastics to the final production of new polymers themselves.

Before we embarked upon this project, we had discovered a method to break up wood into its component parts, cellulose, hemicellulose and lignin, using ionic liquids. However, this method had only been demonstrated on a very small scale. In this project we have increased the scale of the process by over 100 times and optimised this process by conducting it at higher temperatures to decrease the processing time (a key requirement for commercial application) without compromising the product quality or yield. We have also shown that the process can use a wide variety of biomass inputs, with particular emphasis on the large number of variety of Willows that are available.

Having separated the wood into its components, we have also shown that we can further process these into valuable building blocks for chemicals production. We can do this in a number of different ways, each with different products in mind. We have found commercially available enzymes that can convert cellulose from the process to sugar after the ionic liquid processing without the ionic liquid harming the enzymes. The tolerance of the enzymes to the ionic liquids was very much a concern before the project that we have been able to allay. We have also show that it is possible to produce other products, such as hydroxymethylfurfural, from the biomass components with physicochemical methods.

We have been particularly interested in the preparation of new polymers using monomers extracted from biomass. This has proven to be highly prescient of current concerns regarding plastics in the environment. Our bio-derived polymers include materials that are biodegradable and/or recyclable. We have worked to improve understanding and to use that insight to make better catalysts and processes to prepare these polymers. In addition, there is a feedback between polymer properties and how to make them, for example in this work we targeted making biodegradable polymers with improved temperature resistance. We also invented a new type of catalysis that allows mixtures of raw materials to be selectively reacted to make completely new polymers. The properties of these polymers are currently under-investigation but they show promise as elastomers, coatings and rigid plastics, which are vital properties for a number of real-world applications.

Finally, we have been looking at whether these lab scale discoveries can be turned into real process in a biomass based chemicals industry. Our multiscale modelling has shown that through a series of conversion stages, it is possible to take low value materials such as agricultural residues and turn them into renewable chemical feedstocks such as renewable polymers.
Exploitation Route Future developments will be to upscale these processes to enable their use in the real world.
Sectors Agriculture, Food and Drink,Chemicals

 
Description Biodegradable Polymers 
Organisation Polymateria Ltd
Country United Kingdom 
Sector Private 
PI Contribution PhD research project student: Mr. Richard von Goetze
Collaborator Contribution PhD research project student: Mr. Richard von Goetze
Impact None as yet
Start Year 2016
 
Company Name Chrysalix Technologies Limited 
Description Chrysalix Technologies (http://www.chrysalixtechnologies.com/) is an Imperial College spin-out company developing an innovative biomass fractionation process using low-cost ionic liquids. Currently, our society is heavily relying on the use of crude oil while products are discarded at the end of their lives. We want to change that, which is why we are developing novel chemical processes that enable us to live more sustainably in a clean world. Our first product is the BioFlex process that uses waste wood and agricultural by-products as well as sustainably grown biomass to produce a greener alternative to today's petrochemical industry while providing unwanted waste materials with a new purpose. 
Year Established 2017 
Impact Chrysalix currently operates at pilot scale, and is not yet receiving direct income. We have raised funds for process development and have won many international prizes, including second place at the Slush CLimate Impact Battle, the EIT Change Award and third place at the Climate Launchpad.
Website http://www.chrysalixtechnologies.com/
 
Description 250th American Chemical Society and Meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Three lectures were given at the ACS meeting in Boston by the Williams group
Year(s) Of Engagement Activity 2015
 
Description 8th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact keynote lecture at the meeting in Karlsruhe Germany
Year(s) Of Engagement Activity 2015
 
Description Bio-Environmental Polymer Society BEPS 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited keynote lecture at the BEPS 2015 in Karlsruhe
Year(s) Of Engagement Activity 2015
 
Description Dalton Young Researchers Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Dr Pike lectured on his research at the conference
Year(s) Of Engagement Activity 2015
 
Description Demonstration 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Policymakers/politicians
Results and Impact Presentation at the UK Ministry for Transportation
Year(s) Of Engagement Activity 2014
 
Description Frontiers in Green Materials Symposium 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact 2 lectures at the symposium in London and posters to present our findings
Year(s) Of Engagement Activity 2015
 
Description Gordon Research Conference: Organometallic Chemistry 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Two posters presented at the GRC and GRS (lecture) in USA in 2015
Year(s) Of Engagement Activity 2015
 
Description Imperial College Festival 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Schools
Results and Impact The Williams group ran an interactive 'stall' at the imperial college festival. We demonstrated how carbon dioxide can be transformed into products using a series of show-case examples, experiments and hands-on demonstrations for the general public. The total participation at the festival was 15,000 people.
we also participated in a special 'schools' event just before the festival opened where we demonstrated our science to primary school children
Year(s) Of Engagement Activity 2015
 
Description Imperial Fringe 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Public/other audiences
Results and Impact Participation at Imperial Festival
Year(s) Of Engagement Activity 2015,2016
 
Description Invited and keynote lecture at 21 st Bioenvironmental Polymer Society Conference (Warwick) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Discussions with academics and industrialists

New collaboration formed with Michael Meier which resulted in a research exchange of Dr Mathias Winkler to Imperial College in 2014
Year(s) Of Engagement Activity 2013
URL http://www.beps.org/warwick.html
 
Description Invited lecture at 10th IUPAC International Conference on Advanced Polymers via Macromolecular Engineering (Durham); 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact New collaborations with academics in Sweden
discussions

see above
Year(s) Of Engagement Activity 2013
URL http://www.iupac.org/publications/ci/2012/3405/ca4_18.08.13.html
 
Description Invited speaker at Industry and Parliament Trust, Parliamentary Programme on the diversification of energy sources and energy mix (Portcullis House, Westminster, 2015) ? 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Policymakers/politicians
Results and Impact Invited speaker at Industry and Parliament Trust, Parliamentary Programme on the diversification of energy sources and energy mix (Portcullis House, Westminster, 2015). Breakfast meeting with Industrialists, policy makers and politicians.
?
Year(s) Of Engagement Activity 2015
URL https://www.energy-uk.org.uk/publication.html?task=file.download&id=5488
 
Description Keynote lecture at Macro Group Young Researcher's Symposium, Nottingham 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Discussions with students

New applications to my research group
Year(s) Of Engagement Activity 2013
URL http://www.macrogroup.org.uk/meeting/
 
Description Lecture at HPRG Meeting in Pott Shrigley 
Form Of Engagement Activity Scientific meeting (conference/symposium etc.)
Part Of Official Scheme? No
Type Of Presentation keynote/invited speaker
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Discussions and new collaborations formed (sheffield)

new collaboration formed with academics at sheffield
Year(s) Of Engagement Activity 2014
URL http://www.highpolymer.org.uk/
 
Description Lecture at the graduate school professional skills course for Imperial College London and MIT PG students 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Discussions about an academic career and about entrepreneurship

see above
Year(s) Of Engagement Activity 2014
 
Description Oral presentation at the 18th International Zeolite Conference, 19-24 June 2016, Rio de Janeiro, Brazil. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral conference presentation by Wilson K: Hydrothermally stable, conformal sulfated zirconia monolayer catalysts for sustainable chemical processes", Amin Osatiashtiani, Adam F. Lee, Karen Wilson, 18th International Zeolite Conference, 19-24 June 2016, Rio de Janeiro, Brazil.
Year(s) Of Engagement Activity 2016
 
Description Oral presentation at the Workshop Biomass Resources for Renewable Energy Production, 2nd-3rd June, 2016 IMDEA Energy Institute Móstoles - Madrid 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Prof Karen Wilson, Catalyst design for biorefining - Workshop BIOMASS RESOURCES FOR RENEWABLE ENERGY PRODUCTION, 2nd-3rd June, 2016 IMDEA Energy Institute Móstoles - Madrid
Year(s) Of Engagement Activity 2016
 
Description Plenary Lecture 'Catalytic Technologies for the Production of Bioproducts and Biofuels' at CCESC 2016 'Catalysts for Clean Energy and Sustainable Chemistry', (Madrid 2016) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Plenary lecture at international conference
Year(s) Of Engagement Activity 2016
URL http://www.ccesc2016.net/
 
Description Policy Briefing Document 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Policymakers/politicians
Results and Impact Author of policy briefing document: Using Carbon Dioxide
Year(s) Of Engagement Activity 2017
 
Description Presentation at the American Chemical Society National Meeting special symposium on Green Polymer Chemistry: Biobased Materials and Biocatalysis 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Discussions with industrialists and academics

Book Chapter written in collaboration with other speakers - for the ACS symposium series
New collaborations likely
Invitations to collaborate
Year(s) Of Engagement Activity 2014
URL http://abstracts.acs.org/chem/248nm/meetingview.php?page=session&par_id=713
 
Description RSC Main Group Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Lecture at the conference
Year(s) Of Engagement Activity 2015
 
Description Smart Biorefinery: Outlook and Prospects (University of Warwick workshop) July 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Oral presentation vy Dr Amin Osatiashtiani entitled 'Designing heterogeneous catalysts for biorefining' at University of Warwick workshop on the 'Smart Biorefinery: Outlook and Prospects
Date: 7 July 2016

Led to increased interest in the potential of tailored catalysts in biorefinery applications.
Year(s) Of Engagement Activity 2016
 
Description UK Catalysis Conference 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Presentation at the Uk Catalysis Conference, 2016, Loughborough
Year(s) Of Engagement Activity 2016
 
Description UK Chemicals Stakeholder Forum. Presentation on measuring sustainability 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Policymakers/politicians
Results and Impact Presentation and discussion on sustainability metrics
Year(s) Of Engagement Activity 2016
 
Description Uk Catlaysis Conference 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Dr Garcia Trenco gave a lecture at the conference in 2015 in Loughborough
Year(s) Of Engagement Activity 2015