Study of Novel Biofuels from Biomass - Methyl-Furans (MF)

Lead Research Organisation: University of Birmingham
Department Name: Mechanical Engineering

Abstract

Since a fundamental approach to identify and determine the reaction mechanisms in making furanics using fructose as the starting material has been reported by both Nature and Science as the breakthroughs in future biofuel production technology, in the real world, the fructose will come from biomass such as crop residues, forest waste, municipal waste and energy crops. The capability to work on sustainable feedstock and address those which have little or no cellulose within their structure is critically important in order to utilise a wide range of biomass sources for biofuel production.

This project will expand the previous work on 2,5-Dimethylfuran (DMF), to cover the research on production technology converting biomass to furan series as well as characterisation of a more attractive furanic family member 2-Methylfuran (MF). Biomass derived fuels like MF is not the only product formed from the biomass conversion. Bio MF is produced as a mixture with other compounds, referred to henceforth as MF-c (MF compounds), resulting from the degradation of the original biomass. The present project aims to investigate systematically a whole technological pathway for the use and production of furanics (MF and MF compounds) as novel engine fuels via biomass conversion. The research will involve bioenergy and engine combustion technological areas and it will target the following specific objectives:
1) To investigate the behaviours and combustion characteristics of MF and real-world MF-c based bio-oil in engines using experimental and numerical approaches
2) To improve understanding of mechanisms for production of bio-oils with MF and MF-c starting with lignocellulosic biomass
3) To develop practical technology and process for efficient production of biofuels containing MF and MF-c
4) To investigate the impact of MF (MF-c) (including non-conventional emissions) involving health issues of users and CO2 footprint in the production and application of MF based biofuels

The research programme will consist of 3 main Work Packages (WP): WP1 concerns the assessment of MF/MF-c performance in engines as fuels. Fundamental theoretical studies will be carried out to investigate the fuel properties of MF and MF-c bio-oils and expanded knowledge will be obtained about the fuel in terms of ignition and combustion chemistry compared with main components of gasoline and diesel. Advanced optical diagnostics will be applied to study the spray and combustion processes of MF and MF blends. WP2 concerns advancement of MF production methodology. A variety of lignocellulosic biomass residues will be characterised for their elemental, physical and chemical properties and by using TG-MS techniques the optimal biomass type and biomass degradation conditions which produces optimal yields of furfural and furfural alcohol as intermediate pyrolysis products will be determined. WP3 is for assessment of the toxicity of MF and impact on the environment. It will involve experimental study to determine whether MF is genotoxic at low concentrations. The results, in combination with information about predicted levels of human exposure to MF would then be used to form the basis of a more rational risk-assessment of the toxicity of MF in humans and the safety of MF as an alternative fuel source.

Planned Impact

The growing transport sector represents a significant proportion of the energy consumption and it has been reported that it contributed to over 20% of UK CO2 emissions. The technology roadmap is to shift to increase substantially the production of biofuels by using innovative commercially viable processes and technologies. The knowledge of the biomass derived Methyl-Furans (MF) as biofuels to be developed by this project will be not only to answer the questions from the automotive industry with respect to their interest in furan fuels due to their advantages in making the combustion engines more efficient and clean but also to explore the technology pathways for a low CO2 foot print using novel catalytic technology in biofuel production. At the same time, the research will assess the toxicity of MF and its furan family and respond to the concerns of the public on this issue. The outcome will have a significant impact on the current movement to new biofuels with a great contribution to the reduction of global energy consumption and CO2 emissions and thus contribute to the environmental protection.

This project will be a cross-disciplinary collaborative research involving Mechanical Engineering, Chemical Engineering and Bioscience. It will also be supported by the best relevant international partners for collaboration in this field. The collaboration will include Fraunhofer, National University of Ireland Galway, Tsinghua University and will be supported by JLR, Green Fuels and Shell Global Solutions (UK) as local industry partners. It has great potential to develop international collaboration beyond the community of automotive engineering in the field of biofuel research and development, across the boundaries of the academic and industry. It will provide evidence in advancement of application of fuel chemistry and production technology in biomass utilisation and understanding of combustion of MF family as candidates of biofuels for IC engines. This systematic research will provide a large and comprehensive data base for the biofuels MF family and contribute to the expansion of the knowledge on MF production and application as biofuel candidates. The project will maintain the R&D of furan series biofuel technology in the UK at an international leading level, on top of the completed world leading work on DMF.

The progress will be closely monitored by industrial partners with the outcome at every step targeting the benefit in its application. This project will generate a considerable amount of knowledge to advance the biofuel research and development. The new knowledge will be exploited and used by industry partners. The benefits of the project will be passed to the public, providing a knowledge base in all the researched areas and contributing to the global strategy study for the sustainable production and use of biofuels. The know-how acquired in this project will be of direct benefit to the UK and European motor industries because any changes in future fuels will apply a significant influence to their business strategy and plan-making for future products. The project outcome may also help to increase the market size of the UK and Europe's biofuel industries. The project will put the UK's research on MF as a new generation biofuel in a leading position. The research results, however, will not be limited to the products of the industrial partners and shall be available for exploitation by all members of the consortium within the agreed distribution of IP. As the results of the research are published, it will be possible for all the other researchers to share the information about the new developments. Clearly, the beneficiaries of this first attempt to research the applications of MF and its family in direct injection engines will not only be the UK and Europe but also the international community and push forward the development of biomass derived biofuels.
 
Description This project examines for first-time in world the combustion characteristics of the multi-component MF based compound family and their impact on the performance and emissions of internal combustion engines as well as the environment and effect on human health. The work is carried out in close collaboration between Dept. of Mechanical Engineering, Chemical Engineering and Biosciences at University of Birmingham. The key findings of the ongoing award are listed below :
1. Methylfuran (2-MF) showed superior spray formation capability with respect to ethanol and isooctane which represent bioethanol and conventional gasoline, respectively. better spray characteristics will aid in rapid vaporization of the liquid phase-fuel and formation of air-fuel mixture. This deters the formation of locally rich mixtures or piston wetting and thus reducing overall soot emissions.

2. Flame speeds of the chemicals in the MF families are shown to have higher values than alcoholic fuels and they also have higher resistance to abnormal combustion so that they all the use of higher compression ratio engines fro improved fuel economy. Engine tests have demonstrated 2-MTHF (Methyltetrahydrofuran) to result in superior performance compared to MF and gasoline at intermediate and low loads. Although the specific THC emissions for MTHF were significantly lower than gasoline and MF, NOx emissions were higher compared to ULG. SI Engine load tests with another furan-based fuel, Cyclopentanone (CP), has shown higher indicated efficiency compared to ULG but lower than ethanol. A major setback for CP is the higher NOx emissions across the entire load range conditions.

3. In vitro toxicological and geno-toxicological assessment of the fuel main constituent 2-methylfuran and the bio-oil intermediate of the finished bio-fuel product.
MF, the proposed biofuel main constituent, did not show any significant toxicity or genetic toxicity on hepatic cell line. However, using a set of hamster fibroblast cell lines overexpressing specific members of the metabolic enzymes family P450 we found evidence of a possible involvement of this protein family in the metabolism of 2-methylfuran. Investigating further in this should help clarify the mechanism of action of 2-methylfuran possibly identifying putative risk factors associated with this compound. The bio-oil intermediate exhibited low toxic potential on hepatic cultured cells, inducing death in 50% of the cell population at a concentration of 1mg/mL. However, the compound proved to be able to induce stable mutations both in bacterial and mammalian systems down to a concentration of 0.1µg/mL underlying a potential occupational risk associated with the manufacturing of the final product.
Exploitation Route Recent work on combustion properties and emissions of Methylfuran in engines as well as combustion vessel provide benchmark information which is of tremendous interest to industries as well as other researchers. The findings will encourage further optimization of the MF/MF-c production process as well as interests from automotive industries which would push the compounds towards the best candidate for gasoline/diesel substitute.

The data obtained from the intermediate production product is of value because there is the potential for occupational exposure to this mixture during the production of the biofuel.

Research investigations that have resulted in journal publications have been listed in the corresponding sections.
Sectors Energy,Environment,Manufacturing, including Industrial Biotechology,Transport

 
Description Greenfuels is a UK SME engaged in making biomass derived fuels. They have been closely following our research. Hongming Xu is invited to SAE Powertrain Fuels and Lubricants Meeting Injector Deposits Workshop which includes the research outcome of this project. The effect of MF on injector deposits are also included in a major project sponsored by JLR and Shell.
First Year Of Impact 2016
Sector Energy,Environment,Manufacturing, including Industrial Biotechology,Transport
Impact Types Societal

 
Description Jaguar new high performance engine
Amount £214,000 (GBP)
Organisation Jaguar Land Rover 
Sector Private
Country United Kingdom
Start 10/2016 
End 11/2017
 
Description Study of Novel Biofuels from Biomass - Methyl-Furans (MF)
Amount £931,604 (GBP)
Funding ID EP/N021746/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 02/2016 
End 01/2019
 
Title 2-methylfuran compounds toxicological assessment 
Description The objective of the work carried out by the group is to investigate the impact of MF (MF-c) involving health issues of users and CO2 footprint in the production and application of MF-based biofuels. The detailed assessment of potential genotoxicity of MF at low concentrations will be involve a panel of in vitro endpoints to establish concentration-response curves. Mechanistic studies would be carried out to identify specific isoforms of cytochrome P450 that metabolically activate MF. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? No  
Impact We identified a possible occupational hazard in the biofuel manufacturing as one of the bio-oil intermediate showed mutagenic potential in in vitro assay systems at low concentrations that could be relevant in vivo. 
 
Title Engine performance and emissions of MF/MTHF/MF-c compounds in compression ignition research engine. 
Description The EU has created an incentive for 10% of automotive fuels to be sourced from biofuels by 2020 with this increasing to 27% by 2030. Significant amount of research is required to investigate the suitable alternative fuels to ensure the accomplishment of this target. There have been advances in the mass-production methods of a wide variety of biofuels at a suitable price, one of these promising fuels is MF. This has acquired a large amount of research interest for its use within a spark ignition engine. However, there is still limited understanding about this fuel's performance and feasibility in a compression ignition engine. The main aim of this research is to investigate the performance of different MF/MF-c fuels blends within the engine. This research will be assessing the performance of both emissions and combustion behaviour. MF has characteristics that are much more similar to gasoline rather than diesel and because of which it is not practicable to use pure MF within a compression ignition engine. The test engine that will be used is a 2.2 litre turbo diesel engine that has been manufactured by Ford, however, it is unknown how the fuel will behave. Therefore, it has been proposed to separate out a cylinder to run the MF-diesel blends while the running the other 3 cylinders with pure diesel. 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? No  
Impact The majority of the time has been allocated to the commissioning modifications to the engine set up, which will be the major equipment used to review the feasibility of using MF within a compression ignition engine. The purpose for this research is to assess whether MF could be used as an additive fuel with diesel in compression ignition engine. So, before the engine was converted to suit MF, screening tests have been completed with a blend of 10% MF and 90% diesel (by volume). The most notable impact will be a better understanding of whether it will be suitable for MF/diesel blends to be used within the automotive sector. 
 
Title Engine performance and emissions using MF/MF-c biofuels in DISI research engine 
Description Our group is one of the first groups to investigate DMF as a potential engine-fuel. Combustion, emission characteristics of DMF fuelled DISI engines and effect of spark timing and load was investigated extensively. Results of such experiments provide valuable information about the usability of novel fuels in an engine under practical conditions. Investigations currently carried out are extended beyond DMF towards MF, MTHF, Cyclopentanone(CP) and their blends with gasoline. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? No  
Impact A detailed investigation of the combustion characteristics of MTHF and cyclopentanone (CP) fuels is being carried out in a single cylinder DISI research engine. The load-scan tests for MTHF indicate superior performance compared to MF and gasoline at intermediate and low loads, however the limited knock resistance of MTHF necessitates retarded spark timings at high loads. ISHC emissions for MTHF were significantly lower than ULG and MF, whereas the NOx emissions were higher compared to ULG. CP exhibits a higher resistance to knock promoting advanced spark timing at high load running conditions. The CP indicated efficiency is observed to be about equal to that of MF, higher than ULG but lower than ethanol. A major setback for CP is the higher NOx emissions across the entire loads range. 
 
Title Investigation of spray characteristics of 2-MF and MF-c fuels 
Description Combustion performance and emissions from automotive engines are greatly affected by the in-cylinder spray characteristics. Inferior spray formation results in large droplet sizes, piston and cylinder wall wetting deteriorating the fuel consumption economy, soot and THC emissions. Very limited research has been carried out in this regard for MF/MF-c fuels and thus needs immediate attention to investigate the spray characteristics and understand the mixture formation properties. This knowledge would enable researchers and industries to optimize the fuel injection strategy for enhancing the engine performance and emissions. High-speed shadowgraphy macroscopic and microscopic imaging of the spray in a constant volume chamber reveals important qualities about the fuel spray formation characteristics such as penetration length, cone angle and droplet size. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
Impact High-speed shadowgraphy imaging was carried out for 2-Methylfuran (MF), ethanol (ETH) and isooctane (ISO) sprays under various test conditions from non-flash boiling to flare-flash boiling conditions in a constant volume chamber. Results showed that under flash boiling conditions, near-nozzle spray patterns changed significantly and clear radial expansion was observed due to bubble formation and explosion. MF showed better primary break-up behaviour compared to ETH and ISO due to its much higher vapour pressure while it also showed the lowest spray velocity compared to ETH and ISO owing to its high density. At flare-flash boiling conditions, the atomization of MF was almost mature as soon as it left the nozzle exit and the formation of the liquid core was retarded. Among the three fuels, MF showed the most intense flash boiling behaviour due to its high vapour pressure. 
 
Title Laminar combustion characteristics of MF/MF-c 
Description Fundamental properties of a fuel combustion such as the laminar flame speed is critical for characterizing a fuel, developing models for the kinetic mechanisms and for the optimized design of future engines by the industry. In addition, the impact of diluents in the form of N2 and CO2 on flame propagation and stability is important to investigate for any potential fuel since the introduction of EGR in engines is an effective way of reducing NOx emissions. The diluents can affect the combustion process though physical and chemical kinetic pathway. No investigation has been reported till now focusing on the effect of diluents on laminar burning characteristics of MF and MF-c fuels in a well-controlled environment. Therefore, the aim of this research model is to explore this area of research. The investigation will be carried out using high-speed Schlieren flame imaging technique in a constant volume chamber for various levels of dilution at preheated conditions for MF and MF-c fuels. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
Impact Laminar burning characteristics for MF and blends have been investigated in the past and were compared with properties of DMF resulting in multiple international journal publications. In the last term, the laminar combustion studies were carried out using 2-methyltetrahydrofuran (2-MTHF) which is a promising second-generation novel-biofuel candidate produced from furfurals, a common MF based compound. The results were compared with ethanol and isooctane, a representative component in gasoline. The measurements show that for most tests, the ranking of unstretched flame propagation speed is ethanol, 2-MTHF followed by isooctane. The Markstein length calculations indicate that isooctane has a more diffusion-thermal stable flame than 2-MTHF and ethanol when F < 1.2 at 393 K. The laminar burning velocity of 2-MTHF is much faster than isooctane and is comparative with ethanol, indicating its fast-burning property and potential of improving engine thermal efficiency. The laminar flame speed measurements have been carried out for MF, MTHF and isooctane with different levels of CO2 and N2 dilution under preheated conditions through high-speed Schlieren imaging (non-intrusive technique). This research database would be critical to (a) assess the detailed and reduced chemical kinetic mechanisms developed for MF and MTHF, (b) Provide validation targets for numerical modelling researchers. (c) Analysis of experimental results is ongoing and should result in potential publications 
URL http://www.sciencedirect.com/science/article/pii/S0016236116311371
 
Title Thermo-Catalytic Reformer (TCR) 
Description Production of a bio-oil rich in Methyl-furans through TCR, using lignocellulosic wastes. In this research, a Thermo-Catalytic Reforming (TCR) process is proposed to combine intermediate pyrolysis with post catalytic reforming in the complete absence of oxygen. The process converts lignocellulosic biomass into bio-oils, which contain furfural, furfural alcohols, and a range of other oxygenated aromatic compounds as intermediate liquid products. Reaction conditions, temperature, solid residence times and pellet compression ratios will be optimised to achieve maximum yields of liquid intermediates containing furfural and furfural alcohols. The bio-oils produced will be characterised to determine their fuel physical and chemical compositions. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? No  
Impact Waste valorisation and green fuels production. No one has tested MF as mixtures with other compounds which are also present from the degradation of biomass for combustion engine use. This will be the first time to examine combustion characteristics and emissions of Furanic bio-oil (different from the pyrolysis product) in automotive engines. As for its production, the novelty of the TCR process is the utilisation of char as the catalyst for upgrading pyrolysis liquids and feedstocks which have little or no cellulose within their structure. Producing MF and its compounds using this process is new, because internally produced hydrogen can be used for the upgrading hydro treatment step, without the need of externally sourced hydrogen. Furthermore, the production and utilisation of 2-MF from biomass offers a unique approach compared to other studies using model based chemicals. 
 
Description Collaboration with Chemical Engineering, University of Birmingham 
Organisation University of Birmingham
Department School of Chemical Engineering
Country United Kingdom 
Sector Academic/University 
PI Contribution combustion and emission characteristics of novel bio-fuels developed
Collaborator Contribution The first phase of this work package will consist of the building and commissioning of a TCR reactor at the University of Birmingham. In parallel to this, a variety of lignocellulosic biomass residues will be characterised for their elemental, physical and chemical properties and by using TG-MS techniques the optimal biomass type and biomass degradation conditions which produces optimal yields of furfural and furfural alcohol as intermediate pyrolysis products will be determined. This will establish a fundamental understanding of the thermal degradation behaviour of the feedstocks as well as an understanding of the chemical compounds produced during pyrolysis of the feedstock. Upon characterisation, these feedstocks will be tested in a pilot scale TCR reactor for production of bio-oils. Reaction conditions, temperature, solid residence times and pellet compression ratios will be optimised to achieve maximum yields of liquid intermediates containing furfural and furfural alcohols. The biooils produced will be characterised to determine their fuel physical and chemical compositions. This work package will establish the TCR process to deliver sufficient yields of bio-oil intermediate products for further upgrading to MF-c. The second phase is to study a catalytic upgrading of TCR bio-oil to maximise the yields of 2-methylfuran. This work package task will aim towards upgrading the intermediate liquids produced from the first phase to MF-c by the catalytic hydro treatment (hydrodeoxygenation) of intermediate bio-oils under a range of catalysts. Initially the process will be optimised for selectivity towards MF-c by using standard Cu catalysts. This work package task aims towards optimising the catalytic upgrading conditions for the economic production of MF-c from TCR intermediate liquids. Sufficient quantities will be produced for subsequent engine tests.
Impact collaboration is multi-disciplinary: combustion characteristics (energy ) novel production technology of biofuels (chemical engineering)
Start Year 2016
 
Description Collaboration with Dept. of Biosciences, University of Birmingham 
Organisation University of Birmingham
Department Institute of Biomedical Research
Country United Kingdom 
Sector Academic/University 
PI Contribution Provide technical information about the fuel samples and combustion characteristics
Collaborator Contribution The objective of the work carried out by the group is to investigate the impact of MF (MF-c) involving health issues of users and CO2 footprint in the production and application of MF-based biofuels. The detailed assessment of potential genotoxicity of MF at low concentrations will be involve a panel of in vitro endpoints to establish concentration-response curves. Mechanistic studies would be carried out to identify specific isoforms of cytochrome P450 that metabolically activate MF.
Impact this collaboration is multi-disciplinary - combustion and energy systems - toxicity and environmental effects (biosciences)
Start Year 2016
 
Description Link with Fraunhofer Germany 
Organisation Fraunhofer Society
Department Fraunhofer Institute for Environmental, Safety, and Energy Technology
Country Germany 
Sector Public 
PI Contribution We have shared research outcome and discussions during two of their visits and meetings. The discussions focussed on the production technology of MF/MF-c based bio-oil and characterizing the fuel properties.
Collaborator Contribution The Institute provides technical support
Impact this collaboration is multi-disciplinary
Start Year 2016
 
Description Partnership with Key State Lab of IC engines China 
Organisation Tianjin University
Country China 
Sector Academic/University 
PI Contribution Sino-British research fellowship. Royal Society Sponsored international fellow for research on furans as biofuel candidates.
Start Year 2010
 
Description Partnership with Tsinghua University 
Organisation Tsinghua University China
Country China 
Sector Academic/University 
PI Contribution Tsinghhua University is ranked as no 1 university in China. This project has led to a long term collaboration with Tsinghua. This an International Exchange Programme sponsored by Royal Society and NSFC for 2 years.
Start Year 2012
 
Description Fuel Cell & Hydrogen Technical Conference 2017 (Millenium Point - Birmingham) 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Technical poster presentation at the Fuel Cell & Hydrogen Technical Conference Conference 2017 (FCH2)
Year(s) Of Engagement Activity 2017
 
Description ICHEME ChemEng Day UK 2017 - Oral presentation. 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Oral presentation of the ongoing research at ICHEME ChemEng Day UK 2017 hosted by University of Birmingham
Year(s) Of Engagement Activity 2017
 
Description International Conference on Applied Energy 2017 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Involved in the panel meeting with experts at International Conference on Applied Energy, Cardiff to discuss the future of bio-fuel research and internal combustion engine technology.
Year(s) Of Engagement Activity 2017
 
Description SAE Engine Deposits Workshop 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact MF is a component widely used in fuels as additive. There is evidence that MF can cause deposits in engine combustion onto the injector especially direct injection engines and this makes the engine performance and emissions deteriorate with time. The problem has become a big challenge to motor and fuel industry, if MF is to be used as biofuel. We have carried out a lot of research work on the combustion of MF and deposits in engines. Clearly our publications have received good attention and thus I was invited to this workshop to give a talk on the subject, showing how we can identify the way to mitigate the problem.
Year(s) Of Engagement Activity 2016
URL http://www.sae.org