earth natural sciences phd programme 2011 3 description document v7.pdf · relatively little is...

ENS PhD Strand 3 Project Descriptions v7

UCD Earth Sciences Institute

Earth & Natural Sciences PhD Programme 2011

Strand 3: Energy and Environmental Engineering

Project Descriptions (v7)

Earth and Natural Science PhD Programme 2011 Strand 3

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Please Note:

While every effort has been made to ensure that the information contained within this document is accurate, it is possible for errors and omissions to have occurred. It is strongly recommended that potential students make contact with the Principal Investigators directly, should they have any questions about the projects.

Energy and Environmental Engineering UCD Earth Sciences Institute

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Introduction 4

Information on the Application Process 5

List of Projects

1 The effects of two‐phase fault rock properties on CO2 sequestration risk 6

2 Enabling ICT and energy system technologies for Smart Grids 7

3 Evaluating the geothermal potential above buried high heat production granites, Co Meath, Ireland

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4 Improved dye‐sensitised photovoltaic solar cells for indoor diffuse lighting and BIPV applications

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5 Carbon emissions mitigation and storage: engineering gas and energy storage through membrane‐assisted gas capture

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6 Carbon emissions mitigation and storage: assessment of the potential of Irish on‐ and off‐shore carboniferous black shales and coal‐bearing sequences for CO2 sequestration

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7 Investigation of the geothermal energy potential of geological source rocks in the greater Dublin area

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8 The Combustion of Biofuels under Combustor Relevant Conditions (Bioenergy, biofuels, biomaterials, and Biochemicals)

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9 Use of functionalised mesoporous silicas for pyrolysis oil upgrading 14

10 Catalytic conversion of biomethane to methanol and higher alcohols 16

11 Tar mitigation in biosyngas production 18

12 The hydrogenation of furfural to furfuryl alcohol 20

13 Mixed culture biotechnology for conversion of Food waste and Sewage sludge to organic acids and biomethane

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Introduction

The ENS PhD Programme

The global change in climate and energy supplies will have a major impact on the island of Ireland, on how our economy evolves and the need for measures to protect our environment.

UCD is harnessing its considerable resources to address the challenges by developing an Earth Sciences Institute (ESI). The proposed ENS PhD programme building on the concept that energy and environment are co‐dependent, draws on the unique range of disciplines and technologies of UCD, ESI and its partners to create new programmes in Earth and Natural Sciences education. The proposed ESI PhD programme will create a cohort of graduates with a strong background in Energy and Environmental studies, imbued with the innovation and entrepreneurial skills to develop an emerging green technology sector. In addition to a core of postgraduate students specialised in key elements of earth sciences, the programme will impact across a wide range of undergraduate and graduate programmes. It is only by influencing the collective skills of future graduates emanating from a range of disciplines that we will as a society adapt to the national and global challenges and opportunities in agriculture, energy, food, forestry, green technology, land resources, nanoscience and water.

This Strand – Energy and Environmental Engineering – aims to equip PhD graduates with the training/skills for modeling, chemical/photochemical energy resources/usage and CO2 amelioration and, in association with the Engineering PhD Programme, to provide training towards an energy secure, low carbon emissions Ireland.

A total of 13 Projects are offered with 17 positions for PhD candidates within this Strand. Students in this Strand will be housed at UCD, TCD, DIAS, UL or NUIG.

Strand Keywords: Biosystems Engineering, Chemical Engineering, Civil Engineering, Electrical Engineering, Mechanical Engineering, Geoscience, Physics, Chemistry, Bioscience, Architecture, Economics, Geology, Geochemistry


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Information

The Application Process

Please read the following section very carefully. It is of the utmost importance that all the relevant documents are submitted as part of a single email application. Incomplete applications will not be reviewed.

If you have any specific questions about the project or the application, please contact the Principal Investigator directly (details are available in this booklet).

Applications should be emailed to both the Principal Investigator for the specific project and to [email protected]. The subject line should contain the word “Application” followed by the project number followed by the applicant’s name (e.g. Application EEE 4 Joe Bloggs).

Mislabeled applications may not be processed.

All applications must include the following documents:

1. A completed Application Cover Form (download) 2. A complete Curriculum Vitae 3. A Letter of Motivation outlining your interest in the specific project 4. Certified copies of academic transcripts

and, where appropriate,

5. Evidence of proficiency in English

All documents should be typeset or scanned, as appropriate. Please provide PDF format documents where possible.

Please note that all elements of the application must be included in one email. It will not be possible to process incomplete applications and we will not be in a position to collate applications sent in separate emails.

Failure to include all of the documentation listed above will result in your application being rejected.

Applications received before 13 May 2011 will receive full consideration, and the positions will remain open until filled.


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Project EEE 1

The effects of two‐phase fault rock properties on CO2 sequestration risk Principal Investigator: Dr Tom Manzocchi (TCD) – [email protected] Collaborators: Professor Chris bean (UCD); Dr Brian McConnell (GSI); Dr Gareth O Brien (UCD)

Sherwood sandstone sites comprise about half the higher certainty “Effective” sites for Irish CO2 storage in saline aquifers and the majority of lower certainty “Theoretical” sites. Faults are ubiquitous within the Sherwood sandstone, retard seawater incursion into this important groundwater aquifer in the UK and are recognised as significant production heterogeneities in Sherwood sandstone hydrocarbon reservoirs. Faults therefore are clearly a risk to Sherwood sandstone CCS projects.

There are two principal fault‐related risks. The first is the extent to which intra‐reservoir faults impede flow of CO2 across them and therefore to the practical management of a sequestration programme (number of wells required, sustainable injection rates). Conventional reservoir engineering flow simulation is used to model CO2 sequestration into saline aquifers but the treatment of faults with respect to two‐phase fluid flow in these simulators is over‐simplistic5.

Recent research has highlighted that these simplifications can lead to over‐optimistic conclusions about the number of wells required to sequester CO2 in faulted aquifers6. This PhD will use twophase fault property upscaling methods to model the influence of faults on sequestration processes in idealised Sherwood sandstone aquifers covering the range of conditions likely to be encountered in Irish sites (sandstone permeabilities, fault densities and properties, aquifer pressures and temperatures, reservoir dips and sizes).

The second risk relates to seal integrity and therefore to CO2 leakage. The majority of sites are bounded by faults which must be robust seals throughout and after a successful sequestration programme. An injection induced pressure increase adjacent to a fault will promote flow of the wetting fluid (water) across it. This can lead to changes in capillary pressure which can result, in theory, in seal breakdown for the non‐wetting fluid (supercritical CO2). This leakage mechanism is understood in principal, but cannot be replicated in conventional flow simulation models because of assumptions made during the discretisation of the flow equations into the finite difference scheme used8. Analytical solutions to the problem will be developed to examine the likelihood of capillary seal failure in fluid‐rock‐pressure environments relevant to CO2 injection.

The two topics covered by this PhD are important, but seldom recognised, fault‐related risks associated with CO2 sequestration. Though focused on Irish sites, the numerical modelling results will be of general relevance. The research is highly cross‐disciplinary between geology and reservoir engineering, and is a logical application of our long‐term research on improving the inclusion of fault properties in flow models.

There is one studentship available in this Project and will be based at UCD


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Project EEE 2

Enabling ICT and energy system technologies for Smart Grids Principal Investigator: Professor Chen‐Ching Liu (UCD) – [email protected] Collaborators: Professor Stephen McArthur (University of Strathclyde); Professor John Murphy

(UCD); Professor Liam Murphy (UCD)

Smart grid is a global priority that requires new technologies to meet our energy needs while achieving environmental sustainability. In transmission, a smart grid enhances system security and reliability through self‐healing capabilities and large scale integration of renewable energy devices. In distribution, the smart grid incorporates customers’ participation through smart meters. Information and communications technology (ICT) is critical for development of the smart grid. Given the wide scope of smart grid, we focus our effort on the transmission level.

Power grid control relies on real time data acquisition and computation to determine vulnerabilities and remedial actions. In a smart grid environment, Phasor Measurement Units (PMUs) provide a massive amount of data, which, together with data from supervisory control and data acquisition systems, are the basis for monitoring and control. Applications for this high volume of data are emerging; an example is to develop fast and reliable methods to determine when the grid becomes vulnerable with respect to cascading events that are causes for catastrophic outages. High‐performance algorithms are needed to enable real time recognition of vulnerable patterns and self‐healing capabilities. The communication and computational challenges become more complex as numerous renewables, primarily wind and solar, are integrated. These interconnections lead to dynamic behaviours unknown to date and hence require extensive computation to identify vulnerable patterns. Self‐healing is essential for a smart grid. The state‐of‐the‐art is to perform grid partitioning or controlled islanding; however, islanding is an extreme response with likely unintended consequences. We propose a distributed, multi‐agent approach that uses autonomous, coordinated controls to achieve the same goal.

This interdisciplinary project has two threads (1) real‐time computational algorithms to recognise vulnerable patterns for a grid with large scale integration of renewables, (2) self‐healing of a smart grid and supporting ICTs. The first thread requires a computer science foundation; the second thread is built on energy system engineering. The proposed team has internationally leading researchers in energy systems, high performance real time computation, and smart grid. Co‐funding has been committed for one PhD student at Strathclyde to participate in the research. We will seek collaborations in biologically inspired computation and environmental sciences to identify important issues (e.g., CO2 cap‐and‐trade) to be incorporated. This research will produce innovations in computational and energy system technologies for Irish industry. We have strong relationships with EirGrid, Intel, and IBM Ireland and power grids in Scotland, France, and Italy. Collaborations will be pursued through these relationships.



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Project EEE 3

Evaluating the geothermal potential above buried high heat production granites, Co Meath, Ireland Principal Investigator: Professor Stephen Daly (UCD) – [email protected] Collaborators: Dr David Chew (TCD); Dr Brian McConnell (GSI); Dr Mark Muller (DIAS)

Relatively little is known of Ireland’s geothermal resources1 and yet geothermal power is particularly attractive as a renewable energy source because it can be used as predictable base‐load source in a way that wind and solar power cannot be2. This goal of this project is to characterize and model the thermal state and thermal evolution of the North Meath geothermal exploration target identified by the IRETHERM project. Here preliminary geochemical analyses of the buried Kentstown and Drogheda granites indicate high heat production values4 ~3.64 μWm‐3. These granites lie at depths of 500 – 700 m beneath an insulating cover of Carboniferous sedimentary rocks, which provide a potential seal to conductive heat transfer. Hence the region is an attractive target for shallow heat extraction through stimulated hydrofracturing. The project is closely linked with Dr David Chew’s (TCD) application in Strand 1 (Earth and Computational Climate Modelling). It contributes to three interdisciplinary research themes: monitoring/modelling surface/sub‐surface heat & fluid flow; modelling geothermal power; sub‐surface energy extraction. There will be close collaboration between this project, which characterizes a key target area for geothermal exploration (strand 3) and the TCD group working on regional‐scale thermal history modelling (strand 1).

This project will involve a geochemical investigation of rock samples from surface exposures and boreholes (with co‐applicant Dr Brian McConnell, Geological Survey of Ireland) to provide a detailed 3D model of heat production combined with thermal conductivity measurements. Selected samples will be evaluated for their thermal history using low‐temperature thermochronology methods including fission track and U‐He dating overseen by co‐applicant Dr David Chew (TCD). These data will be integrated to provide a 3D temperature distribution model (co‐applicant Dr M. Muller, DIAS) for the upper crust, who is concurrently supervising a magnetotelluric investigation of the same target region.

The results will be used to assess the present‐day thermal equilibration of the upper crust in particular to determine the nature and magnitude of the geothermal gradients (depth‐dependence of temperature), traditionally used in thermal modelling. A 3D thermal model for the north Meath region will assess its geothermal energy potential and guide further exploration by reducing the risk associated with future exploration drilling.



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Project EEE 4

Improved dye‐sensitised photovoltaic solar cells for indoor diffuse lighting and BIPV applications Principal Investigator: Professor Ravi Thampi (UCD) – [email protected] Collaborators: Dr Donal Finn (UCD); Mr Paul Kenny (UCD); Professor Don MacElroy (UCD); Dr

Simeon Oxizidis (UCD)

The focus of this project is on the development of diffuse light active photovoltaic power delivery systems for indoor use and for deployment as building integrated photovoltaics suitable for solar irradiation conditions prevalent in countries like Ireland. The new PhD student will be engaged in developing dye‐sensitised solar cells (DSSC) using specifically designed novel dyes. The selected sensitisers should absorb light over the entire visible range into the near‐infrared (NIR) and ensure other molecular requirements identified for DSSC sensitisers, inexpensive, environmentally friendly and stable. New dyes will include porphyrins and phthalocyanines. These dyes will be tested in a variety of DSSC configurations for optimisation. The work will involve the development and fabrication of flexible solar cells. For this, novel semiconductor layer processing routes will be followed. Further, formulation of suitable electrolytes, DSSC fabrication, testing, and evaluation of stability under various light conditions will follow.

The host team is multidisciplinary and works on the various aspects of solar energy conversion, artificial photosynthesis and carbon capture. The topic is directly relevant to the ESI research priorities and will be instrumental in developing further capacity in UCD and in Ireland to pursue this important and emerging area of research on an international scale.

The applicant should have a Masters in Physical Chemistry, General Chemistry, Chemical Physics, Surface Science, Materials Science or equivalent. Some research/project experience in a similar field will be required. Exposure to electrochemical methods and impedance spectroscopy will be an added advantage. Knowledge or experience in photovoltaics or mesoporous materials will be a bonus.



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Project EEE 5

Carbon emissions mitigation and storage: engineering gas and energy storage through membrane‐assisted gas capture Principal Investigator: Professor Don MacElroy (UCD) – [email protected] Collaborators: Dr David Chew (TCD); Professor Geoff Clayton (TCD); Dr Denis Dowling (UCD); Dr

Robbie Goodhue (TCD); Dr Damian Mooney (UCD); Dr Gareth O Brien (UCD)

The project work will focus on two primary pathways towards carbon capture: post‐combustion capture from flue gases and pre‐combustion capture from syngas. We propose to utilise recent theoretical and experimental results to design and optimise ultra‐thin (nanometer) membranes, synthesised using APPLD and ALD techniques, for the separation of two key, high temperature gas mixtures, namely CO2/N2 (exhaust gases) and H2/CO (syngas). These mixtures are of particular interest as they will play a major role in future technologies in both the fossil fuel (CO2 sequestration) and hydrogen (H2 production) economy. A specially constructed membrane permeation apparatus will be employed in this work.

The topic of this project is central to the PhD strand “Energy and Environmental Engineering,” linked to the prioritized interdisciplinary research topics “CO2 subsurface/ocean sequestration/carbon capture ”, “ Sub‐surface energy storage/extraction”, “Enhanced/clean sub‐surface oil/gas recovery”, “Smart Grid” and “Photo‐electrochemical (solar) energy storage”

This project is aligned directly with the core principles of the ENS Doctoral Studies Programme, through the development of a close interaction between those working in carbon capture (UCD) and those in sequestration (TCD/UCD) and the exposure to, and appreciation of, the difficulties which need to be overcome to meet the full requirements for CCS. The PhD student involved will develop this appreciation as they approach the issues from both the upstream (capture) and downstream (sequestration) perspectives and undertake a programme of study entailing this broader picture seeking to develop a low cost technology for CO2 sequestration – critical for Ireland’s long term commitments to CO2 reduction. It will also, for the first time, investigate the opportunities for large scale H2 capture and storage.

Providing a low cost route to CO2 and H2 capture will make the challenge of sequestration more realisable in the short‐term – both of which have global demand. Indeed, such technology satisfies two strategic goals for Ireland ‐ the development of high impact IP for industry growth and the reduction of CO2 emissions coupled with the development of H2 storage as an energy storage option. The ability to separate CO2 from other gases in high temperature gas systems (combustion exhausts, syngas, for example) is one of the great technological challenges of the 21st Century. The challenge centers around the, typically, low concentration of CO2 in such systems, the high temperature and corrosive environments present, and the similar molecular size of CO2 and the other constituent gas species.



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Project EEE 6

Carbon emissions mitigation and storage: assessment of the potential of Irish on‐ and offshore Carboniferous black shales and coal‐bearing sequences for CO2 sequestration Principal Investigator: Professor Geoff Clayton (TCD) – [email protected] Collaborators: Dr David Chew (TCD); Professor Don MacElroy (UCD); Dr Denis Dowling (UCD); Dr

Robbie Goodhue (TCD); Dr Damian Mooney (UCD); Dr Gareth O Brien (UCD)

Coals have the potential to store vast quantities of CO2. Published estimates of potential CO2 sequestration capacity in unminable coal reserves in the USA alone are 324 Gt of CO2. It has also been established that CO2 can not only be adsorbed by coals but is preferentially adsorbed in organic‐rich shales, displacing CH4 and facilitating enhanced natural gas recovery2. Ireland has considerable unminable coal reserves and extensive black shale deposits of Carboniferous age. However, these rocks have not yet been assessed in terms of either their relevant properties such as coal rank, thermal maturity, total organic carbon content (TOC) or their subsurface geological setting. The objectives of this project are:

• To establish the geological setting of selected Carboniferous rock units on‐ and offshore Ireland that appear to have potential for CO2 sequestration and enhanced coal bed methane production. These include the Pennsylvanian 'coal measures' in the Kish Bank Basin, offshore Dublin, and also the Mississippian Clare Shale onshore in County Clare together with its westward extension into the offshore Clare Basin.

• To characterise the basic physical and chemical properties of relevant lithologies, including coal rank, thermal maturity of organic‐rich shales, TOC, porosity and permeability.

• Using the above results, on‐ and offshore prospects that merit detailed exploration and commercialisation will be identified.

This PhD topic fits perfectly within the prioritized interdisciplinary research topic, “CO2 subsurface/ocean sequestration/carbon capture” and is also highly relevant to, "Enhanced/clean sub‐surface oil/gas recovery", both within the PhD strand, “Energy and Environmental Engineering.” This project will involve close collaboration between the TCD/UCD group working in carbon sequestration and the UCD team working in capture. The two PhD students will gain an understanding of both upstream (capture) and downstream (sequestration) perspectives. They will undertake a comprehensive programme of general study in these fields whilst undertaking their individual research projects. Development of a successful Irish CO2 sequestration programme will have a major impact in terms of the essential reduction of CO2 emissions whereas enhanced natural gas production will reduce Ireland's current dependence on imported energy.

There is one studentship available in this Project and will be based at TCD


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Project EEE 7

Investigation of the geothermal energy potential of geological source rocks in the greater Dublin area

Principal Investigator: Professor Alan Jones (DIAS) – [email protected] Collaborators: Dr Donal Finn (UCD); Dr Mark Muller (DIAS)

Of the available sustainable energy options, little is known of the potential of Ireland s geological formations to provide geothermal energy for district‐scale space‐heating and electricity generation. Both energy applications require identification and assessment of deep, permeable aquifers or large, hot, radiogenic granitic intrusions. Recent advances in utilizing medium‐temperature (<150°C) groundwaters provide real potential for electricity generation within the upper range of geothermal gradients observed in Ireland (~25°C/km), provided deep (2 5km) source rocks can be identified.

We aim to initiate such geological investigations and build geothermal skills and capacity in Ireland. Firstly by developing new, state‐of‐the‐art joint magnetotelluric‐gravity modelling software to provide a high‐resolution geophysical imaging capability applicable to geothermal targets. Secondly, by acquiring new magnetotelluric (MT) data, together with currently available gravity, temperature and granite radiogenic‐element composition data, assess the geothermal energy potential of two different, representative geological target types located close to Dublin where geothermal energy utilisation would contribute significantly in reducing fossil fuel consumption. MT and gravity data together are strongly sensitive to the geological properties that define geothermal energy potential.

• Dublin Basin Sediments. While a geothermal exploration borehole in Dublin s Newcastle area is encouraging (46.2°C at 1.4km depth), knowledge of the geological context and source of the warm waters is insufficient to predict whether higher‐temperature waters might be present at greater depth and whether similar geological potential may exist elsewhere in Ireland. Geothermal potential will be assessed based on sediment porosity, subsurface continuity and depth extent.

• Drogheda/Kentstown Granite. The depth and lateral extent of Ireland s many radiogenic granites favourable targets for EGS energy provision is poorly known, particularly buried granites benefiting from the thermal blanketing effect of sedimentary cover rocks. We plan to investigate the buried Drogheda Granite (600m burial depth and high heat‐production (~3.64μWm‐3) proven by drilling), to determine its depth extent, volume and heat generation potential.

There is one studentship available in this Project and will be based at DIAS


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Project EEE 8

The Combustion of Biofuels under Combustor Relevant Conditions (Bioenergy, biofuels, biomaterials, and Biochemicals)

Principal Investigator: Dr Henry Curran (NUIG) – [email protected] Collaborators: Professor Vincent O Flaherty (NUIG); Dr Kevin O Connor (UCD); Dr Eoin Casey (UCD);

Dr Cormac Murphy (UCD); Dr JJ Leahy (UL)

The production of energy as a gas (methane) or liquid fuel (methanol/ethanol) from waste helps address the issue of sustainable energy. The manipulation of biological (NUIG) and chemical (UL) reactor design and the mathematical modelling of bioprocesses (UCD) matches the environmental engineering aspect of the strand. Mathematical modelling is an interdisciplinary tool that allows mechanistic understanding for process optimisation and predicting scale‐up effects. The integration of multiple disciplines across energy, materials, and biochemicals from waste is in keeping with the energy and environmental engineering theme and the subtheme of biorefining and bioenergy.

In order to improve energy efficiency and develop renewable energy sources we need to better understand the fundamental chemical processes controlling fuel combustion. Herein we focus on chemical kinetics studies, particularly on the following key areas:

• Fundamental chemical kinetic studies of fossil and bio‐fuels • Applications to gas turbines and internal combustion engines • Applications to a wide range of combustion systems

One experimental programme will be carried out on the oxidation of oxygenated compounds including specifically the alcohols methanol and ethanol and their mixtures with surrogate petrol and diesel fuels under combustor‐relevant conditions of temperature, pressure and fuel/air composition.

A second study will focus on the study of synthesis gas (syngas) and natural gas with high concentrations of water will be studied under at high pressures (up to 50 atm) and at low, intermediate and high temperatures in order to increase efficiency and fuel flexibility of fuel combustion in gas turbines.

Food waste is a major waste and a major underutilised resource. Compost is one of the targeted products from food waste but new technologies that will diversity products from food waste are unexplored and needed. The integration of biological and chemical technologies to maximise the outputs from a single waste resource is of strong relevance to the waste, energy, environmental industry sectors. It also reduces dependence on terrestrial crops for energy, materials and chemical production.

The integration of activities across a broad set of disciplines (Microbiology, Chemistry, Biochemistry, and Chemical Engineering, across three universities will allow PhD students to be educated and exposed to thinking and approaches outside of their area of expertise, enhance their learning experience, generate an interinstituional network, produce a higher quality graduate with a broader knowledge of the areas of energy, environmental engineering, and biorefining. The creation of this network of graduates will impact positively on the emerging green technologies sector.

There are two studentship available in this Project and will be based at NUIG


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Project EEE 9

Use of functionalised mesoporous silicas for pyrolysis oil upgrading

Principal Investigator: Dr Witold Kwapinski (UL) – [email protected] Collaborators: Dr JJ Leahy (UL); Dr Henry Curran (NUIG); Dr Kevin McDonnell (UCD)

Thermal processing of lignocellulosic non‐food biomass under fast pyrolysis conditions to produce liquid bio‐oils offer significant promise for second generation biofuels since the resulting bio‐oils can more easily fit into the existing transportation fuel infrastructure than can many other biofuels . The bio‐oil is a low viscosity liquid with a large number (over 400) of organic compounds and a high moisture content (10–30 wt% ). However, bio‐oil itself is very unstable due to the reactive species present, which gives rise to high viscosity during storage and poor combustion when used as a fuel. Reducing the concentration of organic acids present in the as‐prepared bio‐oil (UL) will slow down the acid catalyzed reactions thereby enhancing the bio‐oil storage and will also simplify subsequent upgrading of the bio‐oil to fuels giving rise to improved combustion behaviour (NUIG).

Esterification is a potential route to remove the organic acids in bio‐oil by reacting them with alcohol present in bio‐oil or with added alcohol. The application of a heterogeneous solid acid catalyst would be advantageous in the esterification. In the proposed work program we will investigate mesoporous silicas functionalized with organic acid groups as active heterogeneous acidic catalysts. Due to the presence of abundant silanol groups on the surface of mesoporous silica, modifications of the material can be achieved through condensation reactions with the surface silanol groups so as to tune the surface properties. Another potential advantage of the application of these materials is that the support matrix has been reported to lower the solvation of the acidic protons by water and improve the reactivity. The work proposed will examine the use of solid acid catalysts for the esterification of model biomass pyrolysis acids. Acetic acid is a common chemical species in bio‐oil (up to 10%) and will be used as the model compound. The catalysts will be propylsulfonic acid functionalized MCM 41 materials as these catalysts allow for a systematic investigation of the impact of surface properties on the reaction kinetics. The effect of waster on the esterification will also be investigated as water is a significant component in bio‐oil and it is known that the presence of water will lower the esterification activity over acid catalysts.

The focus of this project will be the energy aspect of the strand. The use of perennial biomass to produce a carbon neutral fuel suitable for combustion matches the environmental engineering aspect of the strand. Additionally the biosystems engineering capability of UCD will be used to develop suitable models for small scale bio‐oil scenarios for an Irish context. The integration of multiple disciplines across energy, materials and biosystems engineering is in keeping with the energy and environmental engineering themes.

Ireland has a commitment to 10% biofuels from 2010. This cannot be achieved from starch or oil based feedstocks. There is also a government backed energy crops scheme to encourage the planting of perennial non‐food energy crops. This work will address the production and upgrading of pyrolysis oils to fuel grade materials. The integration of chemical technologies and biosystems engineering is relevant to relevance to agriculture and energy sectors.


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The integration of activities across a set of disciplines (Chemistry, thermochemical processing Chemical Engineering, biosystems engineering,) across three universities will allow PhD students to be educated and exposed to thinking and approaches outside of their area of expertise, enhance their learning experience, generate an inter‐instituional network, produce a higher quality graduate with a broader knowledge of the areas of energy, environmental engineering, and biorefining. The creation of this network of graduates will impact positively on the emerging green technologies sector.

There is one studentship available in this Project and will be based at UL


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Project EEE 10

Catalytic conversion of biomethane to methanol and higher alcohols

Principal Investigator: Dr Teresa Curtin (UL) – [email protected] Collaborators: Dr Dmitri Bulushev (UL); Professor Vincent O Flaherty (NUIG); Gavin Collins (NUIG);

Dr JJ Leahy (UL); Dr Kevin O Connor (UCD); Dr Henry Curran (NUIG); Dr Eoin Casey (UCD); Dr Cormac Murphy (UCD)

Selective synthesis of alcohols from syngas is a well known commercial process, however there are no current commercial routes to alcohol synthesis from biomethane. This project will address two problems, the quantitative conversion of biomethane to syngas and the upgrading of syngas to alcohols. This project integrates the biological and chemical production of value added products from food waste (biorefining).

Food waste and Sewage sludge will be converted to fatty acids and then methane using anaerobic digestion. This PhD project will compliment the process‐based activities of the cluster and will investigate the catalytic synthesis of higher alcohols from the biomethane arising from anaerobic digestion. The research proposed here will support the efforts of collaborators in bioplastic production, combustion and anaerobic digestion.

This research will target two key problems and knowledge gaps, (1) selective conversion of biogas to syngas with a ratio a ratio of 2.1 (H2/CO), (2) catalytic upgrading to methanol and higher alcohols(HAS).

Methane can undergo partial oxidation with molecular oxygen to produce syngas, as the following equation shows: 2CH4 + O2 → 2CO + 4H2. This reaction is exothermic and the heat given off can be used in‐situ to drive the steam‐methane reforming reaction. When the two processes are combined, it is referred to as autothermal reforming. The ratio of CO and H2 can be adjusted to some extent by the water‐gas shift reaction, CO + H2O → CO2 + H2, to provide the appropriate stoichiometry for methanol synthesis.The carbon monoxide and hydrogen then react on a second catalyst to produce methanol. Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina but we will develop novel catalysts for both partial oxidation and alcohol synthesis. CO + 2H2 → CH3OH. The conversion of CH4 into value‐added products is a challenging task and the main reason for this is the high CH3–H(g) bond dissociation energy (439.3 kJ/mol). Heterogeneous catalysts have therefore been a key to the successful conversion of CH4 because once the molecule is adsorbed on a metal surface the bond dissociation energies CHx–H depends on the hosting surface metal. This project will focus on optimization of catalysts by providing nano‐sized embedded metal particles that are stabilized by the support, with metal particle sizes that are smaller than the ensembles typically required for carbon formation and growth.

The common route to HAS is directly using Fischer Tropsch–type processes to mixed higher alcohols using ZnO/Cr2O3 and MoS3 based catalysts. We propose an isosynthesis route via CO hydrogenation over modified zirconia (ZrO2) catalysts. The mechanism proceeds through oxygenated intermediates


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followed by chain growth and dehydration. The reaction conditions are known to influence product distribution with alcohols favoured at low temperatures. Our approach will be to modify the selectivity of ZrO2 using promoters and additives to enhance selectivity to ethanol and higher alcohols

The production of energy as a gas (methane) or liquid fuel from waste addresses the energy aspect of the strand. The recyling of waste material to produce a useful carbon neutral product through engineered biological (NUIG) and Chemical processing (UL) matches the environmental engineering aspect of the strand. Additionally we will use mathematical modelling (UCD) for process optimisation and predicting scale‐up effects. The integration of multiple disciplines across energy, materials, and biochemicals from waste is in keeping with the energy and environmental engineering theme and the subtheme of biorefining and bioenergy.

Food waste and sewage sludge are major underutilised resources. The integration of biological and chemical technologies to maximise the outputs from a single waste resource is of strong relevance to the waste, energy, environmental & industry sectors.

The integration of activities across a broad set of disciplines (Microbiology, Chemistry, Biochemistry, and Chemical Engineering, across three universities will allow PhD students to be educated and exposed to thinking and approaches outside of their area of expertise, enhance their learning experience, generate an interinstituional network, produce a higher quality graduate with a broader knowledge of the areas of energy, environmental engineering, and biorefining. The creation of this network of graduates will impact positively on the emerging green technologies sector.

There are two studentship available in this Project and will be based at UL


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Project EEE 11

Tar mitigation in biosyngas production

Principal Investigator: Dr JJ Leahy (UL) – [email protected] Collaborators: Dr Witold Kwapinski (UL); Dr Henry Curran (NUIG); Kevin McDonald (UCD)

Biomass has the potential to play a significant role in the future energy mix in Ireland and will contribute to the reduction of CO2 emissions, increase energy security and support sustainable development and regeneration of rural areas. The technical limitations are associated with biomass fuel properties compared to coal or oil, are lower energy density, it is a bulkier fuel (with poorer handling and transportation characteristics), more tenacious (difficult to reduce to small homogeneous particles) and ‐ in most cases ‐ a higher moisture content, resulting in storage issues such as degradation and self heating. These properties can have negative impacts during energy conversion such as lower combustion efficiencies and can impose limits on gasifier design. The thermal pre‐treatment of biomass known as torrefaction, improves the solid fuel properties through a mild temperature process that removes moisture and a proportion of the volatile content and leaves a dry, partially carbonised solid. The benefits include homogenisation of different biomass feedstocks, higher energy density and reduced transportation costs, increased carbon content and improved grindability of the fuel and storage stability. Gasification technology offers a versatile method of converting carbonaceous feedstock into valuable products such as hydrogen, transportation fuels and chemicals as well as heat/electricity. Biomass gasification is less mature than coal gasification. The main technological hurdles for biomass gasification are tar reduction and gas cleaning. Downstream processing of producer gas is necessary to eliminate this tar and increase the concentration of hydrogen. Prevention of tar formation by upgrading the feedstock prior to gasification offers an alternative approach. This project will look at the effect of torrifaction as well as a range of process variables on the quality (gas composition) and yield of biogas, particularly with respect to tar reduction. There will be two components to the project, torrifaction and in‐situ tar cracking.

Torrifaction: the objective of this component of the research is the conversion of biomass into a torrified material to improve throughput and conversion efficiencies in gasifying facilities. This component of the work will investigate the effects of torrification process variables on the proximate and ultimate fuel properties of feedstock. The variable to be investigated include temperature, residence time gas atmosphere and feedstock particle size. The main feedstock materials will be miscanthus, willow and agricultural residue. The ease of size reduction will also be determined. Tar‐cracking: the aim is to use existing laboratory and pilot scale processing facilities to test and optimise the yield of hydrogen fuel from native biomass feedstock by the sequential process of thermal pre‐treatment, gasification, stream reforming of tars and reacting carbon monoxide in the producer gas with steam to increase the concentration of hydrogen. We intend to optimise the route for increasing the concentration of hydrogen obtained by investigating the effects of bed material, bed temperature, equivalence ratio, steam to biomass ratio and biomass particle size.


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The focus of this project will be the energy aspect of the strand. The use of perennial biomass to produce a carbon neutral fuel suitable for combustion in IGCC plants matches the environmental engineering aspect of the strand. Additionally the biosystems engineering capability of UCD will be used to develop suitable models for integration of biogas into existing gas‐fired power plants. The integration of multiple disciplines across energy, chemical engineering and biosystems engineering is in keeping with the energy and environmental engineering themes.

Ireland has a commitment to 40% electricity from renewables from 2020. The majority will come from wind but because wind power is not dispatchable in the absence of storage, alternative fuel technologies for thermal plants such as gasification are required. This cannot be achieved from starch or oil based feedstocks. There is also a government backed energy crops scheme to encourage the planting of perennial non‐food energy crops. This work will address the production and upgrading of pyrolysis oils to fuel grade materials. The integration of chemical technologies and biosystems engineering is relevant to relevance to agriculture and energy sectors.

The integration of activities across a set of disciplines (Chemistry, thermochemical processing Chemical Engineering, biosystems engineering,) across three universities will allow PhD students to be educated and exposed to thinking and approaches outside of their area of expertise, enhance their learning experience, generate an inter‐institutional network, produce a higher quality graduate with a broader knowledge of the areas of energy, environmental engineering, and biorefining. The creation of this network of graduates will impact positively on the emerging green technologies sector.



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Project EEE 12

The hydrogenation of furfural to furfuryl alcohol

Principal Investigator: Dr JJ Leahy (UL) – [email protected] Collaborators: Dr Teresa Curtin (UL) Dr Witold Kwapinski (UL); Dr Maria Tuohy (NUIG); Gavin

Collins (NUIG)

The UL Dibanet process (FP7) aims to produce levulinic acid, formic acid and furfural from low‐value biomass in high yields. It will use a two‐reactor system that targets furfural production in the first reactor while conditioning the second reactor for the conversion of the degraded cellulose to levulinic acid and formic acid. The process will involve in the first reactor, the rapid hydrolysis of polysaccharides via dilute (2‐4%) H2SO4 in a linear plug‐flow reactor and a residence time of less than 2 seconds. Dehydration of the monosaccharides liberated from the hydrolysis of the biomass polysaccharides (i.e. from cellulose, hemicelluloses) can lead to the formation of hydroxymethylfurfual (a crucial intermediate for the synthesis of levulinic acid) from the hexoses (which mainly come from cellulose), and furfural from the pentoses (which result from the hemicelluloses). The pentoses typically yield approximately 50% by mass furfural. The furfural will be removed at this stage while the intermediate liquor will be introduced to the second reactor producing levulinic acid and formic acid with the Solid Residues (SR) containing any residual lignin as well as products from condensation reactions. Furfural is also a byproduct of enzymatic hydrolysis.

Furfural is an almond‐scented, oily, colorless liquid that is used in the production of furfuryl alcohol (2‐furan methanol) an important chemical in polymer industry, used mainly for the production of thermostatic resins, liquid resins used for strengthening ceramics. Furfuryl alcohol is also an important chemical intermediate for the manufacture of lysine and Vitamin C.

The hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) can be carried out either in the gas phase or in the liquid phase.

This project will investigate the catalytic hydrogenation of furfural in phase using mesoporus silica supported precious metal catalysts.

The production of ethyl levulinate as a diesel miscible liquid fuel from biomass addresses the energy aspect of the strand. The production of furfural from enzymatic hydrolysis (NUIG) matches the biochemical engineering while the two stage process developed in UL will match the chemical engineering and chemistry strands. The integration of multiple disciplines across energy, functional catalytic materials, and biochemistry is in keeping with the energy and environmental engineering theme and particularly biorefining and bioenergy.

Furfural is a byproduct of chemical or enzymatic hydrolysis of hemicellulose which are frequently an underutilised resource. The integration of biological and chemical technologies to add value to this product is very relevant to the concept of biorefining..

The integration of activities across a broad set of disciplines (Microbiology, Chemistry, Biochemistry, and Chemical Engineering, across three universities will allow PhD students to be educated and


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exposed to thinking and approaches outside of their area of expertise, enhance their learning experience, generate an interinstituional network, produce a higher quality graduate with a broader knowledge of the areas of energy, environmental engineering, and biorefining. The creation of this network of graduates will impact positively on the emerging green technologies sector.



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Project EEE 13

Mixed culture biotechnology for conversion of Food waste and Sewage sludge to organic acids and biomethane

Principal Investigator: Professor Vincent O Flaherty (NUIG) – [email protected]

Food waste and Sewage sludge will, respectively, be converted to building block chemicals and methane using anaerobic digestion (AD) during two PhD studies. A major technological disadvantage is apparent with AD approach as currently constituted ‐ the need to operate reactors at >25˚C to ensure good performance, which can result in 20‐30% of produced biogas being recycled into the process for energy recovery. Significant progress on low‐temperature AD has been made by the O’Flaherty group at NUIG. When high‐rate methanogenesis and bio‐film formation at low‐temperatures is combined, excellent organic conversion efficiency and biogas yields are achieved. Implementation requires further research, however, focused on phase seperation, biofilm formation and bioprocess control, which will be addressed during these projects. The research is integrated into a larger Irish biorefining initiative: the building block chemicals produced from the AD process will be used as a starting material for the production of the biodegradable plastic by collaborators in UCD, while other collaborators in UL will examine the chemical conversion of methane and other building blocks to liquid transport fuels.

A third PhD project will target key problems and knowledge gaps, which must be overcome before the process can be applied at a technical scale– namely the lack of basic information on the rates and limitation of anaerobic mixed‐culture microbial hydrolysis and fermentation. This project will compliment the process‐based activities of the cluster and will investigate the microbial commuity structure and ecology of the anaerobic processes to optimise the in‐reactor processes. A novel feature of the project will be the use of psychrophilic or psychrotrophic methanogenic consortia which can reduce the impact of temperature on hydrolysis and conversion of intermediate products to organic acids and methane, and increase the range of acceptable operating temperatures.

The production of energy as a gas (methane) or liquid fuel (methanol/ethanol) from waste addresses the energy aspect of the strand. The manipulation of biological (NUIG) and chemical (UL) reactor design and the mathematical modelling of bioprocesses (UCD) matches the environmental engineering aspect of the strand. Mathematical modelling is an interdisciplinary tool that allows mechanistic understanding for process optimisation and predicting scale‐up effects. The integration of multiple disciplines across energy, materials, and biochemicals from waste is in keeping with the energy and environmental engineering theme and the subtheme of biorefining and bioenergy.

Food waste and sewage sludge are major underutilised resources. The integration of biological and chemical technologies to maximise the outputs from waste resources is of strong relevance to the waste, energy, environmental & industry sectors.

The integration of activities across a broad set of disciplines (Microbiology, Chemistry, Biochemistry, and Chemical Engineering, across three universities will allow PhD students to be educated and exposed to thinking and approaches outside of their area of expertise, enhance their learning


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experience, generate an interinstituional network, produce a higher quality graduate with a broader knowledge of the areas of energy, environmental engineering, and biorefining. The creation of this network of graduates will impact positively on the emerging green technologies sector.

There are three studentship available in this Project and will be based at NUIG

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