Progression towards Online Tar Detection Systems

ScienceDirect ScienceDirect Energy Procedia 00 (2017) 000–000 ScienceDirect ScienceDirect Energy Procedia 00 (2017) 000–000

Available online at www.sciencedirect.com Available online at www.sciencedirect.com

Energy Procedia 00 (2017) 000–000 Availableonline onlineat atwww.sciencedirect.com www.sciencedirect.com Available Energy Procedia 00 (2017) 000–000

ScienceDirect ScienceDirect

www.elsevier.com/locate/procedia www.elsevier.com/locate/procedia www.elsevier.com/locate/procedia www.elsevier.com/locate/procedia

(2017) 000–000 892–897 EnergyProcedia Procedia142 00 (2017) 9th International Conference Energy on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK www.elsevier.com/locate/procedia 9th International Conference on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK 9th International Conference on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK Progression Tar Detection Systems 9th International Conferencetowards on AppliedOnline Energy, ICAE2017, 21-24 August 2017, Cardiff, UK

Progression towards Online TaraDetection Systems a a,b a towards Online Tar SeanProgression Capper , Zakir Khan , Prashant Kamble ,Detection James SharpSystems , Ian Watsona* Progression towards Online Tar a a,b a Detection Systems a Sean Capper , Zakir Khan , Prashant Kamble , James Sharp , Ian Watsona* Systems Power International and Energy, School Symposium of Engineering, University of Glasgow, Glasgow,and G12 Cooling 8LL, UK The 15th on District Heating

a

a a,b a a a Sean Capper , Zakir KhanSchool Kamble JamesGlasgow, SharpG12 Watson * aPower a,b, Prashant aof, Glasgow, a, Ian Systems and Energy, of Engineering, University 8LL, UK Sean Capper , Zakir Khan , Prashant Kamble , James Sharp , Ian Watsona* a

Systems Energy, School of Engineering, University of Glasgow, Glasgow, G1254000, 8LL, UK Department ofPower Chemical Engineering, COMSATS of Information Technology, Lahore, Pakistan Assessing theandfeasibility ofInstitute using the heat demand-outdoor Systems Power and Energy, School of Engineering, University of Glasgow, Glasgow, G12 8LL, UK Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, 54000, Pakistan temperature function for a long-term district heat demand forecast Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, 54000, Pakistan a

b

a

b b

Abstract

Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, 54000, Pakistan

b

I. Andrića,b,c*, A. Pinaa, P. Ferrãoa, J. Fournierb., B. Lacarrièrec, O. Le Correc

Abstract The a most prohibitive aspect with the commercialisation of biomass gasification technology is tar fouling of the IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal Abstract b product The presence ofwith tar the impacts the efficiency ofbiomass gasification systems and France compromises gas quality, Abstract Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, The mostgas. prohibitive aspect commercialisation of gasification technology is tar fouling of the

cit less useful for some downstream applications sensitive to gas quality. Various tar detection methods rendering Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 ruesystems Alfred Kastler, 44300 Nantes, France product The presence tar the impacts the efficiency ofbiomass gasification and compromises gas quality, The mostgas. prohibitive aspectofwith commercialisation of gasification technology is tar fouling of the are reported in the literature which can be differentiated into offline and online techniques. However, offline The most prohibitive aspect with the commercialisation of biomass gasification technology is tar fouling of the rendering it less useful for some downstream applications sensitive to gas quality. Various tar detection product gas. The presence of tar impacts the efficiency of gasification systems and compromises gas methods quality, techniques are found to be time consuming, expansive and require sufficient instrumentation and knowledge to product gas. The presence of tar impacts the efficiency of gasification systems and compromises gas quality, are reported in the literature which can be differentiated into offline and online techniques. However, offline rendering it less useful for some downstream applications sensitive to gas quality. Various tar detection methods achieve reliable results. Recent advances in online tar detection based on spectral information of individual tar rendering it less useful for some downstream applications sensitive to gas quality. Various tar detection methods techniques to be time consuming, expansive andinto require sufficient instrumentation knowledge to are reportedare infound the literature which can be differentiated offline and online techniques. and However, offline Abstract component have attracted much research Among fluorescence spectroscopy is aand highly promising are reported infound the literature which can attention. be into offline and online techniques. However, offline achieve reliable results. Recent advances in differentiated online tar detection based on spectral information of knowledge individual tar techniques are to be time consuming, expansive andthese, require sufficient instrumentation to technique for the provision of distinctive, non-invasive andthese, real time data collection for tarislevels which can tar be techniques are found to be time consuming, expansive and require sufficient instrumentation and knowledge to component have attracted much research attention. Among fluorescence spectroscopy a highly promising achieve reliable results. Recent advances in online tar detection based on spectral information of individual District heating networks are commonly addressed in theThis literature as one of the the initial most effective solutions for adecreasing the easily installed on gasification product gas streams. paper presents work on developing low cost achieve reliable results. Recent advances in online tar detection based on spectral information of individual tar technique for theattracted provision of non-invasive andthese, real time collection for tar which canthebeheat componentgas have much researchsector. attention. fluorescence spectroscopy a highly promising greenhouse emissions from thedistinctive, building TheseAmong systems require highdata investments which areislevels returned through tar detection system based LEDgas induced fluorescence. The data detection system mainly consists of component have attracted much research attention. Among these, fluorescence spectroscopy islevels a highly promising easily installed on gasification product streams. Thisrenovation paper the collection initial work a low cost technique for the provision of on distinctive, non-invasive and realpresents time foron can bea sales. Due to the changed climate conditions and building policies, heat demand intardeveloping the futurewhich could decrease, photomultiplier tube (PMT), LED (emission wavelength of 280 nm) and 300 nm longpass colour glass filter. technique for the provision of distinctive, non-invasive and real time data collection for tar levels which can bea tar detection system based on LED induced fluorescence. The detection system mainly consists of easily installed on gasification product gas streams. This paper presents the initial work on developing a low cost prolonging the investment return period. Initial experiments have been carried out with different concentrations (0 to 100 wt%) of phenol (used as a model easily installed on gasification product gas streams. This paper presents the initial work on developing a low cost photomultiplier tube (PMT), LED (emission wavelength of 280 nm) and 300 nm longpass colour glass filter. tar main detection based on LED induced offluorescence. The detection mainly consists a The scope ofsystem this paper is to assess the feasibility using the heat demand – outdoor system temperature function for heatof demand tar compound) and bio-oil samples from an in-house, downdraft (throated) fixed bed system. detection system based onlocated LED fluorescence. The detection system mainly ofThe Initial experiments have been carried outininduced with different concentrations (0 100 wt%) ofgasification phenol (used as a model forecast. The district of (PMT), Alvalade, Lisbon (Portugal), as atocase study. The district isconsists consisted of a665 photomultiplier tube LED (emission wavelength ofwas 280used nm) and 300 nm longpass colour glass filter. results show a linear increase of fluorescence with phenol and the gasifier atbed different concentrations. photomultiplier tube (PMT), LED (emission wavelength of 280 nm) and 300 nm longpass colour glass filter. tar compound) and bio-oil samples from an in-house, downdraft (throated) fixed system. The buildings that vary in have both construction period and typology. Three weather scenarios (low, medium, high) and district Initial experiments been carried out with different concentrations (0 tobio-oil 100 wt%) ofgasification phenol (used as three a model Initial experiments have been carried out with different concentrations (0 to 100 wt%) of phenol (used as a model results show a linear increase of fluorescence with phenol and To the estimate gasifier bio-oil atbed different concentrations. renovation scenarios developed (shallow, intermediate, deep). the error, obtained heat demand values tar compound) andwere bio-oil samples from an in-house, downdraft (throated) fixed gasification system. Thewere © The Published by Elsevier Ltd. tar2017 compound) and from bio-oil samples from an in-house, downdraft (throated) fixedatbed system. The compared withAuthors. a dynamic heat demand model, previously developed and validated by gasification the authors. results show aresults linear increase of fluorescence with phenol and the gasifier bio-oil different concentrations. Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy. results show a linear increase of fluorescence with phenol and the gasifier bio-oil at different concentrations. The results thatPublished when only © 2017 Theshowed Authors. by weather Elsevier change Ltd. is considered, the margin of error could be acceptable for some applications

(the errorThe in annual demand wasby lower than Ltd. 20%committee for all weather considered). However, after introducing Peer-review under responsibility of the scientific of thescenarios 9th International Conference on Applied Energy. renovation © 2017 Authors. Published Elsevier Biomass; gasification; tar;Elsevier fluorescence spectroscopy; online measurement; tarrenovation detection scenarios combination considered). Keywords: © 2017 The Authors. Published by Ltd. scenarios, the error value increased up to 59.5% (depending on the weather and Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy. Peer-review of the scientific committee therange 9th International Conference Applied The value of under slope responsibility coefficient increased on average within of the of 3.8%tar updetection to 8% per on decade, thatEnergy. corresponds to the Biomass; gasification; tar; fluorescence spectroscopy; online measurement; Keywords: 1. Introduction decrease in the numbergasification; of heatingtar;hours of 22-139h during the heating season tar (depending Biomass; fluorescence spectroscopy; online measurement; detection on the combination of weather and Keywords: Biomass;considered). gasification; tar; spectroscopy; online measurement; tar detection Keywords: renovation scenarios Onfluorescence the other hand, function intercept increased for 7.8-12.7% per decade (depending on the 1. Introduction coupled scenarios). The values suggested could be used to modify the function parameters forformation the scenarios Global progression of gasification technology is, at least in part, hindered by tar andconsidered, costly tarand 1. Introduction improve the accuracy of heat demand estimations. 1. Introduction removal strategies. Excessive tar fouling diminishes gasification efficiency and without expensive scrubbing Global progression of gasification technology is, at least in part, hindered by tar formation and costly tar

equipment to eliminate problem ittechnology candiminishes lead tois,downstream complications such choking and scrubbing damaged removal Excessive tar fouling efficiency without expensive Globalstrategies. progression ofthe gasification atgasification least in part, hinderedand by tar as formation and costly tar

©components, 2017 The Authors. Published by Elsevier Ltd. Global progression ofthe gasification atgasification least in part, hindered by tar formation and costly periodic cleaning ordiminishes replacement. Tar detection is a complex and expensive taskscrubbing due totara equipment torequiring eliminate problem ittechnology can lead tois,downstream complications such as choking and damaged removal strategies. Excessive tar fouling efficiency and without expensive Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and removal strategies. Excessive tar fouling diminishes gasification efficiency and without expensive scrubbing variety of biomass feedstocks operating under different process conditions and in different gasification systems. components,torequiring cleaning or replacement. Tar detection is a complex taskdamaged due to a equipment eliminateperiodic the problem it can lead to downstream complications suchand as expensive choking and Cooling.

equipment torequiring eliminate the problem can lead to protocols) downstream complications as expensive choking and damaged Typical offline detection methods (e.g.itEuropean tar are veryistime consuming, unwieldy variety of biomass feedstocks operating under different process conditions insuch different gasification systems. components, periodic cleaning or replacement. Tar detection a and complex and taskrestricted due to a components, requiring periodic cleaning or replacement. Tar detection is a complex and expensive task due to a Typicalof offline detection methods (e.g. tar protocols) very timeand consuming, unwieldy and restricted variety biomass feedstocks operating under different processare conditions in different gasification systems. Keywords: Heat demand; Forecast; Climate changeEuropean variety of biomass feedstocks operating under different process conditions and in different gasification systems. Typical offline detection methods (e.g. European tar protocols) are very time consuming, unwieldy and restricted Typical offline detection methods (e.g. European tar protocols) are very time consuming, unwieldy and restricted

* Corresponding author. E-mail©address: [email protected] 1876-6102 2017 The Authors. Published by Elsevier Ltd. * Corresponding author. Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling. address:author. [email protected] * E-mail Corresponding 1876-6102 © 2017The TheAuthors. Authors. Published Published by 1876-6102 ©address: 2017 byElsevier ElsevierLtd. Ltd. * E-mail Corresponding author. [email protected] Peer-review underresponsibility responsibility thescientific scientificcommittee committee of of the the 9th Peer-review under ofofthe 9th International InternationalConference ConferenceononApplied AppliedEnergy. Energy . E-mail address: [email protected] 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. 10.1016/j.egypro.2017.12.143 Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy. 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. 1876-6102 2017responsibility The Authors. of Published by Elsevier Ltd. of the 9th International Conference on Applied Energy. Peer-review©under the scientific committee Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.

2 2 2 2 2 to 2 to

Sean Capper/ Energy Procedia 00 (2017) 000–000 Sean Capper/ Energy Procedia 00 (2017) 000–000 Sean Capper/ Energy Procedia 00 (2017) 000–000 Sean Capper/ Energy Procedia 00 (2017) 000–000 Sean Capper/ Energy Procedia 00 (2017) 000–000 the intricate nature tar involving aa vast SeanCapper/ Capper et al. /of Procedia 142 (2017) 892–897 Energy Procedia 00 (2017) 000–000 the Sean intricate nature ofEnergy tar mixtures, mixtures, involving vast

offline number offline use use only only [1]. [1]. Moreover, Moreover, number of of species species with with893 to offline use only [1]. Moreover, the intricate nature of tar mixtures, involving a vast number of species with To avoid differing polarity, structure and molecular mass, means that aged samples tend to re-polymerise [2]. To avoid differing and molecular mass,nature means aged samples tend to re-polymerise to offline polarity, use onlystructure [1]. Moreover, the intricate ofthat tar mixtures, involving a vast number of[2]. species with To avoid differing polarity, structure and molecular mass, means that aged samples tend to re-polymerise [2]. some of the drawbacks of the offline methods, some efforts have been made to develop online tar detection to offline use only [1]. Moreover, the intricate nature of tar mixtures, involving a vast number of species with some of the of the methods, some efforts havesamples been made online tar detection To avoid differing polarity, andoffline molecular mass,nature means that aged tend to to re-polymerise to offline usedrawbacks onlystructure [1]. Moreover, the intricate of tar mixtures, involving a develop vast number of[2]. species with some of the drawbacks of the offline methods, some efforts have been made to develop online tar detection systems. These methods are mainly based on Photo Ionization Detection (PID) [3], Ion-Molecule Reactions Mass To avoid differing polarity, structure and molecular mass, means that aged samples tend to re-polymerise [2]. systems. methods are mainly based onmass, Photo Ionization Detection [3], Reactions Mass some of These the drawbacks of the methods, some efforts havesamples been(PID) made to develop online tar detection To avoid differing polarity, structure andoffline molecular means that aged tend toIon-Molecule re-polymerise [2]. systems. methods are mainly based on Photo Ionization [3], Ion-Molecule Reactions Mass Spectrometry (IMR-MS) [4], Time-Of-Flight Mass Spectrometry (TOF-MS) with ionization [5], some of These the drawbacks of offline methods, some effortsDetection have been(PID) made tolaser develop online tarMolecular detection Spectrometry (IMR-MS) [4],the Time-Of-Flight Mass Spectrometry (TOF-MS) with ionization [5], systems. methods are mainly based on Photo Ionization [3], Ion-Molecule Reactions Mass some of These the drawbacks of the offline methods, some effortsDetection have been(PID) made tolaser develop online tarMolecular detection Spectrometry (IMR-MS) [4], Time-Of-Flight Mass Spectrometry (TOF-MS) with laser ionization [5], Molecular Beam Mass Spectrometry [6], Laser Induced Fluorescence Measurement (LIF) [7] and LED Induced Fluorescence systems. These methods are mainly based on Photo Ionization Detection (PID) [3], Ion-Molecule Reactions Mass Beam Mass Spectrometry [6],mainly Laser based Induced Measurement (LIF) [7] LED Induced Fluorescence Spectrometry (IMR-MS) [4], Time-Of-Flight Mass Ionization Spectrometry (TOF-MS) laser ionization [5], Molecular systems. These methods are onFluorescence Photo Detection (PID)with [3],and Ion-Molecule Reactions Mass Beam Mass Spectrometry [6], Laser Induced Fluorescence Measurement (LIF) [7] and LED Induced Fluorescence [8]. However, these systems are still underdeveloped and a lot of research is still needed to make reliable, accurate Spectrometry (IMR-MS) [4], Time-Of-Flight Mass Spectrometry (TOF-MS) with laser ionization [5], Molecular [8]. However, these systems still Induced underdeveloped and a Measurement lot of research is still needed to make reliable, accurate Beam Mass Spectrometry [6],are Laser Fluorescence (LIF) [7] and LED Induced Fluorescence Spectrometry (IMR-MS) [4], Time-Of-Flight Mass Spectrometry (TOF-MS) with laser ionization [5], Molecular [8]. However, thesemeasurements systems still underdeveloped and a Measurement lot of research isdetection still[7] needed to make reliable, accurate and cost effective when compared to (offline) Beam Mass Spectrometry [6],are Laser Induced Fluorescence (LIF) andsystems. LED Induced Fluorescence and cost effective when compared to conventional conventional (offline) [8]. However, thesemeasurements systems still underdeveloped and a Measurement lot of research isdetection still[7] needed to make reliable, accurate Beam Mass Spectrometry [6],are Laser Induced Fluorescence (LIF) andsystems. LED Induced Fluorescence and cost effective measurements when compared to conventional (offline)isdetection systems. [8]. However, these systems are still underdeveloped and a lot of research still needed to make reliable, accurate and cost effective when compared to conventional (offline)isdetection systems. [8]. However, thesemeasurements systems are still underdeveloped and a lot of research still needed to make reliable, accurate research work focuses on the development of low cost tar detection system based on LED andThis cost effective measurements when compared to conventional (offline) detection systems. focuses on the compared development of low cost(offline) tar detection system based on LED induced induced andThis cost research effective work measurements when to conventional detection systems. This research work focuses on the development of low cost tar detection system based induced fluorescence with subsequent instrumentation and control to collect and process the data to alter the state of fluorescence with work subsequent instrumentation and control to collect anddetection process the data to alter on theLED state value value of This research focuses on the development of low cost tar system based on LED induced fluorescence with subsequent instrumentation and control to collect and process the data to alter the state value of the gasifier e.g. equivalence ratio. This paper reports on the initial steps to develop an online tar detection system This research work focuses on the development of low cost tar detection system based on LED induced theThis gasifier e.g. equivalence ratio. reports on to develop an online taron detection system fluorescence with subsequent instrumentation and control to initial collect anddetection process the data to alter the state value of research work focuses onThis the paper development of the low cost steps tar system based LED induced the gasifier e.g. equivalence ratio. This paper reports on the initial steps to develop an online tar detection system that can measure the tar concentration within the product gas at high temperature (>350 °C) and in real time. For fluorescence with subsequent instrumentation and control to collect and process the data to alter the state value of thatgasifier can measure the tar concentration gas at high temperature (>350 °C) and in real For the e.g. equivalence ratio. Thiswithin paper the reports on the steps to develop an online tar the detection system fluorescence with subsequent instrumentation andproduct control to initial collect and process the data to alter statetime. value of thatgasifier can measure the and tar concentration the product gasinitial at high temperature (>350 °C)tar and in real time. sake of easiness simplification, the was tested offline using in the the equivalence ratio. Thiswithin paper reports on initially the steps to develop anmodel online tarcompounds detection system sake of e.g. easiness simplification, the system system was tested offline using in For the thatgasifier can measure the and tar concentration the product gasinitial at high temperature (>350 °C)tar and in real time. For the e.g. equivalence ratio. Thiswithin paper reports on initially the steps to develop anmodel online tarcompounds detection system the sake of easiness and simplification, the system was initially tested offline using model tar compounds in the liquid phase. The system for online tar measurements in the product gas has been fabricated and is currently being that can measure the tar concentration within the product gas at high temperature (>350 °C) and in real time. For liquid phase. The the system for online tar within measurements in the product gas has been fabricated isincurrently being the sake of easiness and simplification, the system was initially tested offline using model tar in the that can measure tar concentration the product gas at high temperature (>350 °C)and andcompounds real time. For liquid phase. The system for online tar measurements in the product gas has been fabricated and is currently being installed within an in-house, downdraft, fixed-bed gasification system. The design of the fluorescence system is the sake of easiness and simplification, the system was initially tested offline using model tar compounds in the installed within in-house, downdraft, fixed-bed system. Thebeen design ofmodel the fluorescence system is liquid phase. Theansystem for online tar measurements in the product gasoffline has fabricated and is currently being the sake of easiness and simplification, the system gasification was initially tested using tar compounds in the installed within an in-house, downdraft, fixed-bed gasification system. The design of the fluorescence system is discussed, followed by some results on using the system on liquid tar samples. liquid phase. The system for online tar measurements in the product gas has been fabricated and is currently being discussed, followed by some resultstar onmeasurements using the system on product liquid tar samples. installed within in-house, downdraft, fixed-bed gasification system. Thebeen design of the fluorescence system is liquid phase. Theansystem for online in the gas has fabricated and is currently being discussed, followed by some downdraft, results on using the system on liquid tar samples. installed within an in-house, fixed-bed gasification system. The design of the fluorescence system is discussed, followed by some downdraft, results on using the system on liquid tar samples. installed within an in-house, fixed-bed gasification system. The design of the fluorescence system is 1.1. gasification tar products discussed, followed by some on using the system on liquid tar samples. 1.1. Biomass Biomass gasification tar results products discussed, followed by some results on using the system on liquid tar samples. 1.1. Biomass gasification tar products 1.1. Biomass gasification tar products produced from gasification 1.1.Tars Biomass gasification tar products produced from biomass biomass gasification are are characteristically characteristically complex, complex, rendering rendering detection detection and and measurement measurement 1.1.Tars Biomass gasification tar products Tars produced from biomass gasification are characteristically complex, rendering detection and literature. measurement within the gas phase a complicated challenge. The definition of tar varies throughout industry and Tar within gas phase a complicated challenge. definition of tar varies throughout industry and Tar Tarsthe produced from biomass gasification areThe characteristically complex, rendering detection and literature. measurement within the gas phase a complicated challenge. The definition of tar varies throughout industry and literature. Tar can be regarded as thermal or partial oxidation products which are assumed to be chiefly aromatic compounds Tars produced from biomass gasification are characteristically complex, rendering detection and measurement canTars be the regarded asfrom thermal or partial oxidation products which are assumed to be chiefly aromatic compounds within gas phase a complicated challenge. definition of tar varies throughout industry and Tar produced biomass gasification areThe characteristically complex, rendering detection and literature. measurement can be regarded as thermal or partial oxidation products which are assumed to be chiefly aromatic compounds with a higher molecular weight greater than Benzene [1]. Lower molecular weight compounds such as Ethylene within the gas phase a complicated challenge. The definition of tar varies throughout industry and literature. Tar withbe a higher weight greater than Benzene [1]. which Lower molecular weight such as Ethylene can regarded as thermal or partial oxidation products are assumed to be compounds chiefly aromatic compounds within the gasmolecular phase a complicated challenge. The definition of tar varies throughout industry and literature. Tar with a higher molecular weight greater than Benzene [1]. Lower molecular weight compounds such as Ethylene and Benzene can similarly prove disruptive so shall be classified as tars for the purposes of this research [1, can be regarded as thermal or partial oxidation products which are assumed to be chiefly aromatic compounds and be Benzene can prove disruptive shall be classified as assumed tars forweight the thissuch research [1, 9]. 9]. with a higher molecular weight greater than so Benzene [1]. Lower are molecular as Ethylene can regarded assimilarly thermal or partial oxidation products which to purposes be compounds chieflyofaromatic compounds and Benzene can similarly prove disruptive so shall be classified as tars for the purposes of this research [1,and 9]. Tars carried by a product gas stream may choke up pipework leading to blockages and system failures with a higher molecular weight greater than Benzene [1]. Lower molecular weight compounds such as Ethylene TarsBenzene asimilarly product gas stream may choke pipework leading to weight blockages andof system failures and can prove disruptive shallup be classified as tars for the purposes thissuch research [1,and 9]. with acarried higher by molecular weight greater than so Benzene [1]. Lower molecular compounds as Ethylene Tars carried by a product gas stream may choke up pipework leading to blockages and system failures component damage. Moreover, tars are generally oxygenated and cannot be converted into valuable products and and Benzene can similarly prove disruptive so shall be classified as tars for the purposes of this research [1, 9]. component Moreover, are generally oxygenated and cannot into valuable products Tars carrieddamage. by product gas tars stream may so choke up leading toconverted blockages andof system failures and Benzene canasimilarly prove disruptive shall bepipework classified as tars be for the purposes this research [1,and 9]. component damage. Moreover, tars are generally oxygenated and cannot be converted into valuable products the presence of tars and impurities reduces the useable output syngas, diminishing gasification efficiency and Tars carried by a product gas stream may choke up pipework leading to blockages and system failures the presence of tars and impurities reduces the useable output gasification efficiency component Moreover, are generally oxygenated andsyngas, cannot betoconverted into products Tars carrieddamage. by a product gas tars stream may choke up pipework leadingdiminishing blockages andvaluable system failures and the presence of tars and impurities reduces the of useable output diminishing gasification efficiency and energy potential. Ultimately, the aa gasification system, terms tar production level, is component damage. Moreover, tarsperformance are generally oxygenated andsyngas, cannot be in converted into valuable products energy potential. Ultimately, the gasification system, terms of of tarvaluable production level,and is the presence of tars and impurities reduces the of useable output diminishing gasification efficiency component damage. Moreover, tarsperformance are generally oxygenated andsyngas, cannot be in converted into products energy potential. Ultimately, the performance of a gasification system, in terms of tar production level, is influenced by the acceptable tar limits of any intended downstream application. Table 1 details typical tar the presence of tars and impurities reduces the useable output syngas, diminishing gasification efficiency and influenced byofthe acceptable tar limits of any intended downstream application. details typical tar energy potential. Ultimately, the performance a gasification system, in terms Table of tar 1production level,and is the presence tars and impurities reduces the of useable output syngas, diminishing gasification efficiency influenced by the acceptable tar limits of any intended downstream application. Table 1 details typical acceptance limits of various syngas run applications, demonstrating the severe sensitivity of most systems to tar energy potential. Ultimately, the performance of a gasification system, in terms of tar production level, is acceptance limits various syngas run applications, the severe sensitivity most systems to tar influenced by theof acceptable tar limits of any of intended downstream application. Table details typical energy potential. Ultimately, the performance a demonstrating gasification system, in terms of tarof1production level, is acceptance limits of various syngas run applications, demonstrating the severe sensitivity of most systems to tar fouling. influenced limits by the acceptable tar limits of any intended downstream application. Table 1 details typical fouling. acceptance various syngas run applications, demonstrating the severe sensitivity systems to tar influenced by theofacceptable tar limits of any intended downstream application. Tableof1most details typical fouling. acceptance limits of various syngas run applications, demonstrating the severe sensitivity of most systems to tar fouling. acceptance limitsTable of various syngas run applications, demonstrating the severe sensitivity of most systems to tar 1. Tar limitations for syngas applications [1, 10] fouling. Table 1. Tar limitations for syngas applications [1, 10] fouling. Table 1. Tar limitations for syngas applications [1, 10] Application Table 1. Tar limitations for syngas applications [1, 10] Application Table 1. Tar limitations for syngas applications [1, 10] Application Table 1. Tar limitations for syngas applications [1, 10] Application Application Direct combustion Direct combustion Application Direct combustion Gas turbine Direct combustion Gas turbine Direct combustion Gas turbine IC engine Direct combustion Gasengine turbine IC Gas turbine IC enginetransport Pipeline Gas turbine IC engine Pipeline transport IC engine Pipeline transport Fuel cells IC engine Pipeline Fuel cellstransport Pipeline Fuel cellstransport Pipeline Fuel cellstransport Fuel cells Fluorescence spectroscopy Fuel cells Fluorescence spectroscopy

Tar acceptance Tar acceptance limit (g/Nm33) Tar acceptance limit (g/Nm ) Tar acceptance limit (g/Nm33) Tar acceptance No limit limit (g/Nm ) No limit Tar acceptance limit (g/Nm33) No limit 0.05-5 limit (g/Nm ) No limit 0.05-5 No limit 0.05-5 50-100 No limit 0.05-5 50-100 0.05-5 50-100 50-500 0.05-5 50-100 50-500 50-100 50-500 <1 50-100 50-500 <1 50-500 <1 50-500 <1 <1 <1

1.2. 1.2. 1.2. Fluorescence spectroscopy 1.2. Fluorescence spectroscopy 1.2.Fluorescence Fluorescencespectroscopy spectroscopyis Fluorescence spectroscopy is an an effective, effective, non-intrusive, non-intrusive, and and online online analytical analytical strategy strategy which which can can be be exploited exploited 1.2.Fluorescence Fluorescencespectroscopy spectroscopyis an effective, non-intrusive, and online analytical strategy which can be exploited for tar detection in biomass gasification. Many aromatic molecules are fluorescent, and fluorescence has forFluorescence tar detection spectroscopy in biomass gasification. Many aromatic molecules fluorescent, and which fluorescence has been been is an effective, non-intrusive, and onlineare analytical strategy can be exploited for tar detection in biomass gasification. Many aromatic molecules are fluorescent, and fluorescence has been used for numerous disciplines including biological and chemical analysis, combustion techniques and medical Fluorescence spectroscopy is an effective, non-intrusive, and online analytical strategy which can be exploited used numerous including biological and chemical analysis, combustion and medical forFluorescence tarfordetection in disciplines biomass gasification. Many aromatic molecules are fluorescent, andtechniques fluorescence has been spectroscopy is an effective, non-intrusive, and online analytical strategy which can be exploited used numerous disciplines including biological and chemical combustion andis medical applications [8]. Following absorption, intensity of re-emitted fluorescence radiation directly for tarfor detection biomass energy gasification. Manythe aromatic molecules are fluorescent, andtechniques fluorescence been applications [8]. in Following energy absorption, the intensity of the theanalysis, re-emitted fluorescence radiation directly used numerous disciplines including biological and chemical analysis, combustion andishas medical for tarfordetection in biomass gasification. Many aromatic molecules are fluorescent, andtechniques fluorescence has been applications [8]. Following energy absorption, the intensity of the re-emitted fluorescence radiation is directly proportional to the concentration of the excited species and excitation radiation irradiance. Therefore, used for numerous disciplines including biological and chemical analysis, combustion techniques and medical proportional to the concentration of the excited species and excitation radiation irradiance. Therefore, applications [8]. Following energy absorption, the intensity of theanalysis, re-emitted fluorescence radiation is medical directly used for numerous disciplines including biological and chemical combustion techniques and proportional to thespectral concentration ofof the excited species radiation irradiance. Therefore, measurement of emission fluorescence radiation provides an accurate representation of applications [8]. Following energy absorption, the intensity ofand the excitation re-emitted fluorescence radiation is directly measurement of the the emission fluorescence radiation provides an extremely extremely accurate representation of proportional to thespectral concentration ofof the excited species radiation irradiance. Therefore, applications [8]. Following energy absorption, the intensity ofand the excitation re-emitted fluorescence radiation is phase directly measurement of the spectral emission of fluorescence radiation provides an extremely accurate representation of the quantity of a fluorescing species. Efficiently detecting fluorescence radiation from tar within the gas is proportional to the concentration of the excited species and excitation radiation irradiance. Therefore, the quantity of a fluorescing species. Efficiently detecting fluorescence radiation from tar within the gas phase is measurement of the spectral emission of fluorescence radiation provides an extremely accurate representation of proportional to the concentration of the excited species andtheexcitation radiation irradiance. Therefore, the quantity of a fluorescing species. Efficiently detecting fluorescence radiation from tar within the gas phase is dependent on numerous parameters including the tar load within gas stream, the optical power output of the measurement of the spectral emission of fluorescence radiation provides an extremely accurate representation of dependent on numerous parameters including the tar load within the gas stream, the optical power output of the the quantity of a fluorescing species. Efficiently detecting fluorescence radiation from tar within the gas phase is measurement of the spectral emission of fluorescence radiation provides an extremely accurate representation of dependent onofthe numerous theexposed tar load the gasradiation stream, the optical power of and the light source, amount of the detector is towithin the molecule distributions the a fluorescing species. Efficiently detecting fluorescence from tarspatial within theoutput gas phase is lightquantity source, amountparameters of time time theincluding detector is the fluorescence, fluorescence, molecule spatial distributions dependent onofthe numerous parameters including theexposed tar loadtowithin the gasradiation stream, the optical power output of and the the quantity a fluorescing species. Efficiently detecting fluorescence from tar within the gas phase isa light source, the amount of time the detector is exposed to the fluorescence, molecule spatial distributions and efficiencies of irradiation and collection optics. The intensity of fluorescence radiation can be expressed as dependent on numerous parameters including the tar load within the gas stream, the optical power output of the efficiencies ofthe irradiation collection optics. The intensity fluorescence radiation canpower bedistributions expressed as a light source, amountparameters ofand time theincluding detector is exposed towithin the of fluorescence, molecule spatial and dependent on numerous the tar load the gas stream, the optical output of the efficiencies oftheirradiation collection optics. The intensity fluorescence radiation can bedistributions expressed function of the absorbance and quantum yield of compound by equation derived from the light source, amount ofand time thethe detector is exposed the of fluorescence, molecule spatial and function of both both the absorbance and the quantum yield of aato compound by the the following following equation derived fromas theaa efficiencies oftheirradiation and collection optics. The intensity of fluorescence radiation can bedistributions expressed as light source, amount of time the detector is exposed to the fluorescence, molecule spatial and function of both the absorbance and[11]: the quantum of a compound by the following equation fromasthea Beer-Lambert of efficiencies of Laws irradiation and collection optics. yield The intensity of fluorescence radiation can bederived expressed Beer-Lambert Laws of absorption absorption function of both the absorbance and[11]: the quantum of a compound by the following equation fromasthea efficiencies of Laws irradiation and collection optics. yield The intensity of fluorescence radiation can bederived expressed Beer-Lambert of absorption [11]: function of both the absorbance and the quantum yield of a compound by the following equation derived from the Beer-Lambert Laws of absorption function of both the absorbance and[11]: the quantum yield of a compound by the following equation derived from the

894

Sean Capper/ Energy Procedia 00 (2017) 000–000 Sean Capper/ Energy Procedia 00 (2017) 000–000 −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐) (2017) 000–000 𝐼𝐼𝑓𝑓Sean = 𝑗𝑗Capper/ ∙ 𝑘𝑘 ∙ 𝐼𝐼𝑜𝑜Energy ∙ 𝛷𝛷𝑓𝑓 ∙Procedia [1 − 𝑒𝑒00 ] Sean Capper/ Energy Procedia 00 (2017) 000–000 −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐) 𝐼𝐼𝑓𝑓 = 𝑗𝑗 ∙ 𝑘𝑘 ∙ 𝐼𝐼𝑜𝑜 ∙ 𝛷𝛷𝑓𝑓 ∙ [1 − 𝑒𝑒 −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐) ] 𝐼𝐼𝑓𝑓Sean = 𝑗𝑗Capper/ ∙ 𝑘𝑘 ∙ 𝐼𝐼𝑜𝑜Energy ∙ 𝛷𝛷𝑓𝑓 ∙Procedia [1 − 𝑒𝑒00 ] (2017) 000–000 −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐)

3 3 (1) 3 (1) 3 (1) 3

(1) 𝐼𝐼𝑓𝑓 = 𝑗𝑗 ∙ 𝑘𝑘 ∙ 𝐼𝐼𝑜𝑜 ∙ 𝛷𝛷𝑓𝑓 ∙ [1 − 𝑒𝑒 ] Where 𝐼𝐼𝑓𝑓 represents the fluorescence intensity, j al. encompasses instrumental factors such as collection efficiency Sean Procedia 142 (2017) −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐) (2017) 000–000 (1) 3 𝐼𝐼𝑓𝑓Sean =Capper 𝑗𝑗Capper/ ∙ 𝑘𝑘 ∙ 𝐼𝐼et𝑜𝑜Energy ∙ 𝛷𝛷/ 𝑓𝑓Energy ∙Procedia [1 − 𝑒𝑒00 ] 892–897 andWhere system𝐼𝐼𝑓𝑓 geometry, considers the specific fraction of emissions occurring at thesuch excitation wavelength and −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐) representskthe fluorescence intensity, j encompasses instrumental factors as collection efficiency (1) 𝐼𝐼𝑓𝑓 = 𝑗𝑗 ∙ 𝑘𝑘 ∙ 𝐼𝐼𝑜𝑜j ∙encompasses 𝛷𝛷𝑓𝑓 ∙ [1 − 𝑒𝑒 instrumental ] factors such as collection efficiency Where 𝐼𝐼𝑓𝑓 represents the fluorescence intensity, is the intensity of the incident light from the excitation source at the the probability of reemission of energy, 𝐼𝐼 𝑜𝑜 andWhere system𝐼𝐼𝑓𝑓 geometry, considers the𝐼𝐼 specific fraction occurring at thesuch excitation wavelength and representskthe fluorescence intensity, instrumental as collection efficiency (1) = 𝑗𝑗 ∙ 𝑘𝑘 ∙𝜀𝜀(𝜆𝜆) 𝐼𝐼𝑜𝑜j ∙encompasses 𝛷𝛷 ∙of [1emissions − 𝑒𝑒 −(𝜀𝜀(𝜆𝜆)∙𝑏𝑏∙𝑐𝑐) ] factors 𝑓𝑓specific 𝑓𝑓the and system geometry, k considers the fraction of emissions occurring at the excitation wavelength and is the fluorescence quantum yield, is molar absorptivity of the molecule, b is the cell path sample, 𝛷𝛷 𝑓𝑓𝐼𝐼𝑓𝑓 geometry, represents fluorescence intensity, jintensity encompasses factors as collection efficiency of theinstrumental incident light from the excitation source at and the theWhere probability of reemission of energy, 𝐼𝐼𝑜𝑜 is the and system kthe considers the specific fraction of emissions occurring at thesuch excitation wavelength the 𝜀𝜀(𝜆𝜆) intensity of
Fig. 1. (a) Instrumentation arrangement schematic for liquid phase testing and (b) picture of system set up Fig. 1. (a) Instrumentation arrangement schematic for liquid phase testing and (b) picture of system set up

Fig.from 1. (a) Instrumentation schematic for liquid phaseoperating testing and (b) picture of system set up strength, and The cell is made stainless steelarrangement (grade 316) to allow for high material Fig. 1. (a) Instrumentation arrangement schematic for liquid phase testing and temperatures, (b) picture of system set up hardness asFig. notfrom beInstrumentation affectedsteel by creep loads and fromand anytemperatures, particles the product 1.to(a) arrangement schematic for liquid phaseoperating testing (b) picture oftransported system set up in The cell issomade stainless (grade 316) toabrasive allow forwearing high material strength, and The cell is made from stainless steelarrangement (grade 316) to allow for high operating temperatures, material strength, and Fig. 1. (a) Instrumentation schematic for liquid phase testing and (b) picture of system set up hardness so as not to be affected by creep loads and abrasive wearing from any particles transported in the product The cell is made from stainless steel (grade 316) to allow for high operating temperatures, material strength, and hardness so as not to be affected by creep loads and abrasive wearing from any particles transported in the product The cell issomade stainless (grade 316) toabrasive allow forwearing high material strength, and hardness asFig. notfrom beInstrumentation affectedsteel by creep loads and fromand anytemperatures, particles the product 1.to(a) arrangement schematic for liquid phaseoperating testing (b) picture oftransported system set up in hardness as notfrom to bestainless affectedsteel by creep loads and from anytemperatures, particles transported the product The cell issomade (grade 316) toabrasive allow forwearing high operating materialinstrength, and

4 Sean Capper/ Energy Procedia 00 (2017) 000–000 4 Sean Capper/ Energy Procedia 00 (2017) 000–000 4 Sean Capper/ Energy Procedia 00 (2017) 000–000 gas. On each side of the block there isSean a 12Capper/ mm bored the(2017) centre of the block to provide optical access 4 Energy through Procedia 00 000–000 4gas. On each side of the block there isSean Energy through Procedia 00 (2017) 000–000 a as 12Capper/ bored the25 centre of the block provide opticalwindow access from each sideside to the cellblock centre, as well amm shallow 3mm deep, mm000–000 diameter boreto seat a quartz 4 Energy Procedia 00 gas. On each of the there isSean a 12Capper/ mm bored through the(2017) centre of the block totoprovide optical access from each side to the cellwindows centre, as well as awith shallow 3mm deep, 25 mm000–000 diameter bore toprovide seat a quartz window gas. On each side of block there is a 12 mm bored through the centre of the block to optical access on each side. Each the is flanged a high temperature gasket material and four separately machined 4from Sean Capper/ Energy Procedia 00 (2017) each sideside to the the cellblock centre, as well amm shallow deep, mm diameter boretotoprovide seat a quartz window On each there isSean a as 12Capper/ the25 centre of the892–897 block optical access895 gas. Sean Capper et al.3mm /through Energy Procedia 142000–000 (2017) 4 each Energy Procedia 00 (2017) on side. Each of of the windows is flanged with abored high temperature gasket material and four separately machined

from each side to the cell centre, as well awith shallow 3mm mm diameter bore toexcitation seat a quartz window gas. On each side of the block a as 12 mm through the25centre of the to block provide optical access square filleted flanges (each 50there mm xis50 mm x 15 mm). Thedeep, design is intended allow from the top on each side. Each of the windows is flanged abored high temperature gasket material and to four separately machined from each side to the cell centre, as well amm shallow 3mm deep, mm diameter bore toexcitation seat a quartz window gas. On each side of the block there is50 a as 12 bored through the25centre of the to block to provide optical access square filleted flanges (each 50 mm xbe mm xFigure 15 mm). The design is intended allow from the top on each side. Each of the windows is flanged with a high temperature gasket material and four separately machined from each side to the cell centre, as well as a shallow 3mm deep, 25 mm diameter bore to seat a quartz window window via a mounted LED. As can seen in 2(a) a small metallic mount is mechanically fastened to the square filleted flanges (each 50there mm xis50 mm x 15 mm). Thedeep, design is intended allow excitation from the top on each side. Each windows is flanged with abored high temperature gasket material and four separately machined gas. On each side of the block aseen 12 mm through the25 centre of the to block to provide optical access from each side to the cell centre, as well as a shallow 3mm mm diameter bore to seat a quartz window window via a mounted LED. As can be in Figure 2(a) a small metallic mount is mechanically fastened to the square filleted flanges (each 50 mm x 50 mm x 15 mm). The design is intended to allow excitation from the top gas. On each side of block there is a 12 mm bored through the centre of the block to provide optical access on each side. Each the windows is flanged with a high temperature gasket material and four separately machined top of the sell to securely and precisely align and hold the LED in place and the output radiation is directed through window viaside aEach mounted LED. Asmm can seen inshallow 2(a) a deep, small metallic mounttoisbore mechanically fastened to top the square filleted flanges (each 50 xbe50 mm xFigure 15 mm). The design is intended allow from the from each tosecurely the cell centre, as well as awith 3mm 25 mm diameter toexcitation seat adirected quartz window on each side. of the windows is flanged a high temperature gasket material and four separately machined top of the sell to and precisely align and hold the LED in place and the output radiation is through window via athe mounted LED. Asmm can seen inshallow 2(a) a deep, small metallic mount mechanically fastened to top the from each side tosecurely thesealed cell centre, aswindow. well as aThe 3mm 25 mm diameter to seatisadirected quartz square filleted flanges (each 50 xbe50 mm xFigure 15 mm). The design is intended toisbore allow from the the centre of gas quartz bottom side of cell will incorporate aexcitation beam dump towindow absorb top of the sell to and precisely align and hold the LED in the place and the output radiation through window via a mounted LED. As can be seen in Figure 2(a) a small metallic mount is mechanically fastened to the on each side. Each of the windows is flanged with a high temperature gasket material and four separately machined square filleted flanges (each 50 mm x 50 mm x 15 mm). The design is intended to allow excitation from the top the centre ofaEach the gas sealed The bottom side of the cell will incorporate a beam dump tothrough absorb top of the sell to securely andquartz precisely hold the LED insystem, place and the output radiation is directed on each side. ofand theLED. windows iswindow. flanged with atar high temperature gasket material and four separately machined window via mounted As can bealign seenand in Figure 2(a) a small metallic mount isan mechanically fastened to and the the LED radiation mitigate scattering. The detection housed in aluminium enclosure the centre of the gas sealed quartz window. The bottom side of the cell will incorporate a beam dump to absorb top of the sell to securely and precisely align and hold the LED in place and the output radiation is directed through square filleted flanges (each 50 mm x 50 mm x 15 mm). The design is intended to allow excitation from the top window via a mounted LED. As can be seen in Figure 2(a) a small metallic mount is mechanically fastened to the LED radiation mitigate scattering. The tarmm). detection housed in an aluminium enclosure and the centre ofathe gasand sealed quartz window. The bottom side of the cell will aexcitation beam dump tocell absorb square filleted flanges (each 50 mm x 50 mm x 15 The design isand intended tothe allow from the top top of the sell to securely and precisely align and hold the LED insystem, place theincorporate output radiation is directed through mounted on removable aluminium plate is attached via a mechanical coupling to side of the optical wall the LED radiation and mitigate scattering. The tar detection system, housed in an aluminium enclosure and centre of the gas sealed quartz window. The bottom side of the cell will incorporate a beam dump to absorb window via a mounted LED. As can be seen in Figure 2(a) a small metallic mount is mechanically fastened to the top of the sell to securely and precisely align and hold the LED in place and the output radiation is directed through mounted on removable aluminium plate is attached athe mechanical coupling to the side thefor optical LED radiation and mitigate scattering. The tar detection housed inis an aluminium enclosure and window via mounted LED. As can be seen in Figure 2(a) a small metallic mechanically fastened towall the the centre ofaaathe gasfasteners sealed quartz window. The bottom of system, the cell willmount incorporate a of beam dump tocell absorb using threaded bolt which screw into the facevia ofside cell. The opposite side is then free optical access mounted on removable aluminium plate is attached via a mechanical coupling to the side of the optical cell wall LED radiation and mitigate scattering. The tar detection system, housed in an aluminium enclosure and top of the sell to securely and precisely align and hold the LED in place and the output radiation is directed through the centre of the gas sealed quartz window. The bottom side of the cell will incorporate a beam dump to absorb using threaded bolt fasteners which screw into the facevia ofLED the cell. The opposite side isradiation then free for optical access mounted on a removable aluminium plate is attached a mechanical coupling to the side of the optical cell wall top of the sell to securely and precisely align and hold the in place and the output is directed through the LED radiation and mitigate scattering. The tar detection system, housed in an aluminium enclosure and for another spectral detection device such as a spectrometer or CCD camera. Figure 2(b) displays the CAD design using threaded bolt which screw into thebottom facevia ofside cell. The opposite side is side then free optical access mounted on athe removable aluminium plate is attached athe mechanical coupling to thefor optical wall the another centre ofspectral gasfasteners sealed quartz window. of the cell willFigure incorporate a of beam dump tocell absorb LED radiation and mitigate scattering. The tar detection system, housed inthe an aluminium enclosure and for detection device such as aThe spectrometer orcell. CCD camera. 2(b) displays the CAD design using threaded bolt which screw into thebottom facevia ofside The opposite side is side then free optical access the another centre ofspectral gasfasteners sealed quartz window. The of the cell willFigure incorporate a of beam dump tocell absorb mounted on athe removable aluminium plate is attached athe mechanical coupling to the thefor optical wall for tar detection system connected to the gasifier. for detection device such as a spectrometer or CCD camera. 2(b) displays the CAD design using threaded bolt fasteners which screw into the face of the cell. The opposite side is then free for optical access the LED radiation and mitigate scattering. The tar detection system, housed in an aluminium enclosure and mounted on a removable aluminium plate is attached via a mechanical coupling to the side of the optical cell wall for tar detection system connected to the gasifier. spectral detection device such as aThe spectrometer CCD camera. Figure 2(b) displays theenclosure CAD design the another LED radiation and mitigate scattering. system, housed in an aluminium and using threaded bolt fasteners which screw into the tar facedetection of theorcell. The opposite side is then free for optical access tar detection system connected to the gasifier. for another spectral detection device such as a spectrometer or CCD camera. Figure 2(b) displays the CAD design mounted on a removable aluminium plate is attached via a mechanical coupling to the side of the optical cell wall using bolt fasteners whichtoscrew into the facevia ofathe cell. The opposite side is side thenof free optical access tarthreaded detection system connected the gasifier. mounted onspectral a removable aluminium is attached mechanical coupling to the thefor optical cell wall for another detection device plate such as a spectrometer or CCD camera. Figure 2(b) displays the CAD design tarthreaded detection system connected the gasifier. using bolt fasteners which into the face of theorcell. The opposite side2(b) is then free for access for another spectral detection devicetoscrew such as a spectrometer CCD camera. Figure displays theoptical CAD design (b) using fasteners which into the face of the cell. The opposite side is then free for optical access for tarthreaded detectionbolt system connected toscrew the gasifier. for another spectral detection devicetosuch as a spectrometer or(b) CCD camera. Figure 2(b) displays the CAD design tar detection system connected the gasifier. for another spectral detection device such as a spectrometer or(b) CCD camera. Figure 2(b) displays the CAD design for tar detection system connected to the gasifier. (b) for tar detection system connected to the gasifier. (b) (b) (b) (b) (b)

Fig. 2. Online tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. Fig. 2. Online tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. Fig. 2. Online tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. Fig.Design 2. OnlineValidation tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. 3. Fig. 2. Online tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. 3. Design Validation Fig. 2. Online tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. 3. Fig.Design 2. OnlineValidation tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. 3. Design Validationof the fluorescence system was evaluated off-line to prove that the specified instrumentation The performance Fig.Design 2. OnlineValidation tar detection system (a) custom optical cell design and (b) integration with gasification system and instrumentation housing. 3. The performance ofsystem the fluorescence system was evaluated off-line togasification prove that theperformance specified instrumentation Fig.Design 2.optics Online tar detection (a)for custom cell design and integration with system and instrumentation 3. Validation and were appropriate the optical measurement of (b) fluorescence and to evaluate and housing. identify

The performance of the fluorescence system was evaluated off-line to prove that the specified instrumentation 3. Design Validation and optics wereconnecting appropriate forthe the measurement of fluorescence and to evaluate performance andfollowing identify The performance of the fluorescence system was evaluated off-line to prove that the specified problems before it to gasifier. Preliminary, testing was conducted in the liquid phase.instrumentation The and optics were appropriate for the measurement of fluorescence and to evaluate performance and identify 3. Design Validation The performance of the fluorescence system was evaluated off-line to prove that the specified instrumentation problems before connecting it to the gasifier. Preliminary, testing was conducted in the liquid phase. The following 3. Design Validation and optics were appropriate for the measurement of fluorescence and to evaluate performance and identify The performance of the fluorescence system was evaluated off-line to prove that the specified instrumentation results shows theconnecting testing solutions of known concentration of andevaluate samples of bio-oil/tar which were problems before it to the gasifier. Preliminary, testing wasphenol conducted in the liquid phase.instrumentation The following andThe optics were appropriate for the measurement of fluorescence and to performance and identify performance of thewith fluorescence system was evaluated off-line to prove that the specified results shows the testing with solutions of known concentration of phenol and samples of bio-oil/tar which were problems before connecting it to the gasifier. Preliminary, testing was conducted in the liquid phase. The following and optics were appropriate for the measurement of fluorescence and to evaluate performance and identify collected from the gasifier and their fluorescence signature investigated. results shows the testing with solutions of known concentration of phenol and samples of bio-oil/tar which were The performance of the fluorescence system was evaluated off-line to prove that the specified instrumentation problems before connecting it to the gasifier. Preliminary, testing was conducted in the liquid phase. The following and optics were appropriate for thefluorescence measurement of fluorescence and to evaluate performance and identify collected from the gasifier and their signature investigated. The performance of thewith fluorescence system was evaluated off-line to prove that the specified instrumentation results shows the testing solutions of known concentration of phenol and samples of bio-oil/tar which were problems before connecting it to the gasifier. Preliminary, testing was conducted in the liquid phase. The following collected from the gasifier and their fluorescence signature investigated. and optics were appropriate for the measurement of fluorescence and to evaluate performance and identify results shows the testing with solutions of known concentration of phenol and samples of bio-oil/tar which were problems before connecting it to the gasifier. Preliminary, testing was conducted in the liquid phase. The following and optics were appropriate for the measurement of fluorescence and to evaluate performance and identify collected from the gasifier and their fluorescence signature investigated. results shows the testing with solutions of known concentration of phenol and samples of bio-oil/tar which were 3.1 Methods problems before connecting it to the gasifier. Preliminary, testing was conducted in the liquid phase. The following collected from the gasifier and their fluorescence signature investigated. results shows theconnecting testing with solutions of known concentration of and samples of bio-oil/tar which were 3.1 Methods problems before it to the gasifier. Preliminary, testing wasphenol conducted in the liquid phase. The following collected from the gasifier and their fluorescence signature investigated. 3.1 Methods results shows the testing with solutions of knownsignature concentration of phenol and samples of bio-oil/tar which were collected from the gasifier and their fluorescence investigated. results shows the testing withwere solutions of known concentration of phenol andphenol samples of bio-oil/tar which were 3.1Various Methods phenol solutions using signature water as ainvestigated. solvent. For the tests, a total of 10 solutions collected from the gasifier and theirprepared fluorescence 3.1 Methods phenol solutions were prepared using water as ainvestigated. solvent.concentration For the phenol tests, a total of 10 solutions collected from the gasifier and their fluorescence signature 3.1 Methods of Various increasing concentration were prepared from 8% w/w phenol up to the purchased solution solutions were prepared using water as a solvent. For the phenol tests, a total of 10 solutions 3.1Various Methodsphenol of increasing concentration were prepared preparedThe from 8% solutions w/w to the purchased solution phenol solutions water as a phenol solvent. For the phenol a total of 10 solutions concentration of 80% w/w concentration. phenol wereconcentration transferred toup UV quartz cuvette using a of Various increasing concentration prepared using from 8% w/w concentration upatests, to the purchased solution Various phenol solutions were prepared using water as a phenol solvent. For the phenol tests, a total of 10 solutions 3.1 Methods concentration of 80% w/w concentration. The phenol solutions were transferred to a UV quartz cuvette using 3.1 Methods of increasing concentration prepared from 8% w/w phenol concentration up to the purchased solution Various phenol solutions were prepared using water as a solvent. For the phenol tests, a total of 10 solutions pipette (100 1000 µL Finn Pipette, Thermoscientific, United States). Once filled and sealed, the cuvette wasaa concentration of 80% w/w concentration. The phenol wereconcentration transferred toupatests, UV quartz cuvette using of increasing concentration prepared from 8% solutions w/w phenol to sealed, the purchased solution Various phenol solutions were prepared using water as a solvent. For the phenol a total of 10 solutions pipette (100 1000 µL Finn Pipette, Thermoscientific, United States). Once filled and the cuvette wasa concentration concentration. The phenol wereconcentration transferred aand UV quartz cuvette using of increasing concentration were prepared from 8% solutions w/w phenol up to sealed, the purchased solution gently shaken to 80% ensure mixing. For calibration purposes, sample of water wasto tested to establish the output pipette (100phenol - of 1000 µLw/w Finn Pipette, Thermoscientific, United States). Once filled the cuvette wasa concentration of 80% w/w concentration. The phenol solutions wereconcentration transferred toup atests, UV quartz cuvette using Various solutions were prepared using water as aaaphenol solvent. For the phenol a total of 10 solutions of increasing concentration prepared from 8% w/w to the purchased solution gently shaken to ensure mixing. For calibration purposes, sample of water was tested to establish the output pipette (100 1000 µL Finn Pipette, Thermoscientific, United States). Once filled and sealed, the cuvette was Various phenol solutions wereFor prepared using water as aa solvent. the phenol a total of 10the solutions concentration of 80% w/w concentration. phenol solutions were transferred atests, UV to quartz cuvette using observed from system with no tar orThe aromatic compounds in For the cuvette. Measurements were taken ina gently shaken tothe ensure mixing. calibration purposes, sample of water wasto tested establish output pipette (100 1000 µL Finn Pipette, Thermoscientific, United States). Once filled and sealed, the cuvette was of increasing concentration were prepared from 8% w/w phenol concentration up to the purchased solution concentration of 80% w/w concentration. The phenol solutions were transferred to a UV quartz cuvette using observed from system with no tar ortararomatic in thewater cuvette. Measurements were taken ina gently shaken tothe ensure mixing. For calibration purposes, aphenol sample of wasthe tested to establish the output of increasing concentration were prepared from 8%compounds w/w concentration up to sealed, the purchased solution pipette (100 - separate 1000 µLsamples Finn Pipette, Thermoscientific, United States). Once filled and the cuvette was triplicate. Six of varying concentrations were produced from samples collected from the observed from the system with no tar or aromatic compounds in the cuvette. Measurements were taken ina gently shaken to ensure mixing. For calibration purposes, a sample of water was tested to establish the output concentration of 80% w/w concentration. The phenol solutions were transferred to a UV quartz cuvette using pipette (100 1000 µL Finn Pipette, Thermoscientific, United States). Once filled and sealed, the cuvette was triplicate. Six separate samples ofFor varying tar concentrations produced from the collected from the observed from system with no tar orThe aromatic compounds in the cuvette. Measurements werethe taken ina concentration of 80% w/w concentration. phenol solutions were transferred a samples UV quartz cuvette using gently shaken tothe ensure mixing. calibration purposes, a were sample of water wasto tested to establish output gasifier, ranging from 1:5, 2:4, 1:1, 4:2, 5:1 (oil:water). Similarly, the fluorescence was measured after the gentle triplicate. Six separate samples of varying tar concentrations were produced from the samples collected from the observed from system with no4:2, tar or (oil:water). aromatic compounds in of the cuvette. Measurements were taken in pipette (100 - 1000 µL1:5, Finn Pipette, Thermoscientific, United States). Once filled andmeasured sealed, the cuvette was gently shaken tothe ensure mixing. calibration purposes, a were sample water wasthe tested to establish the output gasifier, ranging from 2:4, 1:1, 5:1 Similarly, the fluorescence was after the gentle triplicate. Six- separate samples ofFor varying tar concentrations produced from samples collected from the pipette 1000 µL1:5, Finn Pipette, Thermoscientific, United States). Once filled and sealed, the cuvette was observed from the system with no tar ortriplicate aromatic in the cuvette. Measurements were taken in shaking(100 procedure, which was repeated in forcompounds each sample. gasifier, ranging from 2:4, 1:1, 4:2, 5:1 (oil:water). Similarly, the fluorescence was measured after the gentle triplicate. Six separate samples ofFor varying tar concentrations were produced from samples collected from the gently shaken tothe ensure mixing. calibration purposes, asample. sample of water wasthe tested to establish the output observed from system with no tar or aromatic compounds in the cuvette. Measurements were taken in shaking procedure, which was repeated in triplicate for each gasifier, ranging 1:5, 2:4, repeated 1:1, 4:2, 5:1triplicate (oil:water). Similarly, the fluorescence was measured after the the gentle gently to from ensure mixing. calibration purposes, asample. sample of water wasthe tested to establish output triplicate. Six separate samples ofFor varying tar concentrations were produced from samples collected from the shakingshaken procedure, which was forcompounds each gasifier, ranging from 1:5, 2:4, 1:1, 4:2, 5:1 (oil:water). Similarly, fluorescence wassamples measured after gentle observed from the system with tarin ortar aromatic in the cuvette. Measurements werethe taken in triplicate. Six separate samples ofno varying concentrations were the produced from the collected from the shaking procedure, which repeated forcompounds each sample. observed from the system with no tarin ortriplicate aromatic in the cuvette. Measurements werethe taken in gasifier, ranging from 1:5, was 2:4, 1:1, 4:2, 5:1 (oil:water). Similarly, the fluorescence was measured after gentle 4. Results and Discussions shaking procedure, which was repeated in triplicate for each sample. triplicate. Six separate samples of varying tar concentrations were produced from the samples collected from the gasifier, ranging from 1:5, 2:4, 1:1, 4:2, 5:1tar (oil:water). Similarly, the fluorescence wassamples measured after the gentle 4. Results andseparate Discussions triplicate. Six samples of varying concentrations were produced from the collected from the shaking procedure, which was repeated in triplicate for each sample. 4. Results and Discussions gasifier, ranging from 1:5, was 2:4, repeated 1:1, 4:2, in 5:1triplicate (oil:water). Similarly, the fluorescence was measured after the gentle shaking procedure, which for each sample. gasifier, ranging from 1:5, 2:4, 1:1, 4:2, 5:1 (oil:water). Similarly, the fluorescence was measured the gentle 4. Results andare Discussions The results shown Figure 3 and show that the fluorescence increased (i.e. more after negative) with shaking procedure, which in was repeated in clearly triplicate for each sample. 4. Results and Discussions The concentration, results are shown in Figure 3 and show thatthe the fluorescence increased (i.e. more negative) with shaking procedure, which was repeated in clearly triplicate for for each sample. 4. Results and Discussions phenol and the light detected was lowest water only sample. The results presented an almost The results are shown in Figure 3 and clearly show that the fluorescence increased (i.e. more negative) with 4. Results and Discussions phenol concentration, and the light detected was lowest for the water only sample. The results presented an almost Theincrease results are shown 3phenol and clearly show for that thewater fluorescence increased (i.e. more negative) with linear of fluorescence withdetected concentration. These results indicative the linearly proportional phenol concentration, and in theFigure light was lowest the onlyare sample. The of results presented an almost Theincrease results shown in Figure 3phenol and clearly show that the fluorescence increased (i.e. more negative) with 4. Results andare Discussions linear of fluorescence with concentration. These results are indicative of theItlinearly proportional 4. Results and Discussions phenol concentration, and the light detected was lowest for the water only sample. The results presented an almost The results are shown in Figure 3 and clearly show that the fluorescence increased (i.e. more negative) with relationship previously identified for fluorescence analysis of phenol within a gas stream. is worth noting that linear increase of fluorescence withdetected phenol concentration. These results are indicative of the linearly proportional phenol concentration, and the light was lowest for the water only sample. The results presented an almost The results are shown in Figure 3 and clearly show that the fluorescence increased (i.e. more negative) with relationship previously identified for fluorescence analysis ofoutput phenol within a gas stream. Itlinearly is worth noting that linear increase of fluorescence with phenol concentration. These results are indicative of the proportional phenol concentration, and the of light detected was lowest forthe the water only sample. The results presented anfor almost at the highest concentrations phenol (64 to 80% w/w) was higher (i.e. less negative) than 56% relationship previously identified for fluorescence analysis of phenol within a gas stream. It is worth noting that linear of fluorescence with concentration. These results are indicative of the linearly proportional Theincrease results concentrations are shown in 3phenol and clearly show that the fluorescence increased (i.e. more negative) with phenol concentration, and theFigure light detected was lowest for the water only sample. The results presented anfor almost at the highest of phenol (64 to 80% w/w) the output was higher (i.e. less negative) than 56% relationship previously identified for fluorescence analysis of phenol within a gas stream. It is worth noting that The results are shown in Figure 3 and clearly show that the fluorescence increased (i.e. more negative) with linear increase of fluorescence with phenol concentration. These results are indicative of the linearly proportional w/w was the most negative output observed during the atests). This isIt is most likely due to at the(which highest concentrations of phenol (64 concentration. tointensity 80% w/w) the was higher (i.e. less negative) than 56% relationship previously identified for fluorescence analysis ofoutput phenol within gas stream. worth noting that phenol concentration, and thenegative light detected was lowest for the water only sample. The results presented anfor almost linear increase of fluorescence with phenol These results are indicative of the linearly proportional w/w (which was the most output intensity observed during the tests). This is most likely due to at the highest concentrations of phenol (64 to 80% w/w) the output was higher (i.e. less negative) than for 56% phenol concentration, and the light detected was lowest for the water only sample. The results presented an almost relationship previously identified for fluorescence analysis of phenol within a gas stream. It is worth noting that inconsistencies with alignment during the setup. The process required removing the cuvette, filling with the w/w (which was the most negative output intensity observed during the tests). This is most likely due to at the increase highestpreviously concentrations ofwith phenol (64 to 80%analysis w/w)process the was higher (i.e. less negative) than for 56% linear ofwith fluorescence These results are indicative of cuvette, the proportional relationship identified forphenol fluorescence ofoutput phenol within atests). gas stream. Itlinearly is worth noting that inconsistencies alignment during the concentration. setup. The required removing the filling with the w/w (which was the most negative output intensity observed during the This is most likely due to linear increase of fluorescence with phenol concentration. These results are indicative of the linearly proportional at the highest concentrations of phenol (64 to 80% w/w) the output was higher (i.e. less negative) than for 56% inconsistencies with during the to setup. The process required removing the filling with the w/w was thealignment most negative output intensity observed during the This isIt is most likely due to relationship identified for fluorescence phenol within atests). gas stream. worth noting that at the(which highestpreviously concentrations of phenol (64 80%analysis w/w) theof was higher (i.e. lesscuvette, negative) than for 56% inconsistencies with during the setup. The process required removing the filling with the relationship identified for fluorescence analysis ofoutput phenol within atests). gas stream. worth noting w/w (which previously was thealignment most negative output intensity observed during the Thiscuvette, isIt is most likely duethat to inconsistencies with alignment duringoutput the to setup. process required removing filling the at the(which highestwas concentrations of phenol (64 80%The w/w) the output was higher (i.e.the lesscuvette, negative) than with for 56% w/w the most negative intensity observed during the tests). This is most likely due to at the highest concentrations of phenol 80%The w/w)process the output was higher (i.e.the lesscuvette, negative) than with for 56% inconsistencies with alignment during (64 the to setup. required removing filling the

Sean Capper/ Energy Procedia 00 (2017) 000–000

5

solution and shaking before placing Sean backCapper/ withinEnergy the system. This may have led to inconsistencies and any5 Procedia 00 (2017) 000–000 solution shaking before back within the system. This may have inconsistencies and Capper/ Procedia 00 (2017) 000–000 deviations from linearity with placing the exactSean positioning of samples to be measured andto explain the change in5 solution and and shaking before placing back withinEnergy thethe system. This may have led led tomay inconsistencies and any any deviations from linearity with the exact positioning of the samples to be measured and may explain the change in solution and shaking before placing back within the system. This may have led to inconsistencies and any the trend. The test results for the gasifier bio-oil experiments shown in Figure 3, similarly show that when a higher deviationsand from linearity with placing the exactback positioning of samples to be measured andtomay explain the change in solution shaking before within thethe system. This may have led inconsistencies and any the trend. The test results for the gasifier bio-oil experiments shown in Figure 3, similarly show that when a higher deviations from linearity with the exact positioning of the samples to be measured and may explain the change in5 percentage ofshaking bio-oil is present within abio-oil sample the output from thebe PMT decreases, signifying more intense Sean Capper/ Energy Procedia 00 (2017) 000–000 the trend. The test results for the gasifier experiments shown in Figure 3, similarly show that when a higher solution and before placing back within the system. This may have led to inconsistencies and any deviations from linearity with the exact positioning of the samples to measured and may explain the change 896 Sean Capper etProcedia al.output / Energy Procedia 142 (2017) 892–897 Sean Capper/ Sean Capper/ Energy Energy Procedia 00shown (2017) 00 (2017) 000–000 000–000 5 in5 percentage of bio-oil is present within a sample the from the PMT decreases, signifying more intense the trend. The test results for the gasifier bio-oil experiments in Figure 3, similarly show that when a higher fluorescence percentage ofsignal. bio-oil is present within a sample the from to thebe PMT decreases, signifying more intense deviations from linearity with thegasifier exact positioning of output the samples measured and may explain the change in the trend. The test results for the experiments similarly show that when higher fluorescence percentage ofsignal. bio-oil is present within abio-oil sample the outputshown from in theFigure PMT 3, decreases, signifying moreaintense fluorescence signal. the trend.and The test results for the gasifier bio-oil experiments shown in Figure 3, similarly show that when aintense higher percentage of bio-oil is present within a sample the output from the PMT decreases, signifying more solution shaking before placing back within the system. This may have led to inconsistencies and any fluorescence solution solution and shaking andofsignal. shaking before before placing placing backback within within the the system. the system. This This may may have have led to ledinconsistencies to inconsistencies and any and any percentage bio-oil is present a sample from decreases, signifying more intense fluorescence signal. deviations from linearity with thewithin exact positioning of output the samples tothebePMT measured and may explain the change in deviations deviations fromfrom linearity linearity with with the exact the exact positioning positioning of theofsamples the samples to betomeasured be measured and may and may explain explain the change the change in in fluorescence signal. the trend. The test results for the gasifier bio-oil experiments shown in Figure 3, similarly show that when a higher the trend. the trend. The test Theresults test results for the forgasifier the gasifier bio-oil bio-oil experiments experiments shown shown in Figure in Figure 3, similarly 3, similarly showshow that when that when a higher a higher percentage of bio-oil is present within a sample the output from the PMT decreases, signifying more intense percentage percentage of bio-oil of bio-oil is present is present within within a sample a sample the output the output fromfrom the PMT the PMT decreases, decreases, signifying signifying moremore intense intense fluorescence signal. fluorescence fluorescence signal. signal.

Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples

5. Conclusions 5. 5. Conclusions Conclusions Fig. 3. Spectral response from PMT for varying concentrations of Phenol (left) and bio-oil samples 5. Conclusions Fig. of 3.Fig. Spectral 3. Spectral response response from PMT from for PMT varying for LEDs varying concentrations concentrations of Phenol of (left)content and (left)bio-oil andseems bio-oil samples samples The utilization fluorescence strategies using for analysis ofPhenol tar to be a very promising 5. Conclusions The utilization of fluorescence strategies using LEDs for analysis of tar content seems to be very route for biomass to the potential for real-time, non-intrusive monitoring. of promising LEDs has The utilization of gasification fluorescencedue strategies using LEDs for analysis of tar content seems to The be aause very promising 5. Conclusions route for biomass gasification due to the potential for real-time, non-intrusive monitoring. The use of LEDs has The utilization of fluorescence strategies using LEDs for analysis of tar content seems to be a very promising been proven to be effective for the stimulation of measurable fluorescence signals in the liquid phase both with route for biomass gasification due to the potential for real-time, non-intrusive monitoring. The use of LEDs hasa The utilization of gasification fluorescence strategies usingofLEDs for analysis of tar content seems to The be phase ause very promising been proven to be effective for the stimulation measurable fluorescence signals in the liquid both with route for biomass due to the potential for real-time, non-intrusive monitoring. of LEDs hasaa standard tar compound (phenol) of known concentrations and for bio-oil samples derived from a gasifier test using been proven to be effective for the stimulation of measurable fluorescence signals in the liquid phase both with The utilization of fluorescence strategies using LEDs for analysis of tar content seems to be a very promising 5. Conclusions route for tar biomass gasification due to the potential for real-time, non-intrusive monitoring. The use ofboth LEDs hasa standard compound (phenol) of known concentrations and for bio-oil samples derived from a gasifier test using been proven to be effective for the stimulation of measurable fluorescence signals in the liquid phase with 5. Conclusions 5. Conclusions Miscanthus biomass. Although exact information regarding thebio-oil species of tars presents within bio-oils isa standard compound (phenol) of known concentrations and for samples derived from a phase gasifier testwith using route for tar biomass gasification due to the potential for real-time, non-intrusive monitoring. The usethe ofboth LEDs has been proven to be effective for the stimulation of measurable fluorescence signals in the liquid Miscanthus biomass. Although exact information regarding the species of tars presents within the bio-oils is standard tarthis compound (phenol) of known concentrations and for bio-oil samples derived from a gasifier test using unknown, method demonstrates the components selected could effectively be utilized a tar detection Miscanthus biomass. Although exact information regarding the species of tars presents within the bio-oils isa been proven to be effective for the stimulation of measurable fluorescence signals in the liquid phase both with The utilization of fluorescence strategies using LEDs forand analysis of tar content seems towithin bea gasifier a very promising standard tarthis compound (phenol) of known concentrations for bio-oil samples derived from test using unknown, method demonstrates the components selected could effectively be utilized a tar detection Miscanthus biomass. Although exact information regarding the species of tars presents the bio-oils is The utilization The utilization of fluorescence of fluorescence strategies strategies using using LEDs LEDs for analysis for analysis of tar of content tar content seems seems to be to a be very a very promising promising system for quantitative evaluation of tar loading on a gas stream if coupled with a suitable offline technique, such unknown, this method demonstrates the components selected could effectively be utilized within a tar detection standard tar compound (phenol) of known concentrations and for bio-oil samples derived from a gasifier test using route forforbiomass gasification due tothe the potential for real-time, non-intrusive monitoring. The use of LEDs has Miscanthus biomass. Although exact information regarding the species of tars presents within the bio-oils is system quantitative evaluation of tar loading on a gas stream if coupled with a suitable offline technique, such unknown, this method demonstrates components selected could effectively be utilized within a tar detection routeMiscanthus route for biomass for biomass gasification gasification due to due the to potential the potential for real-time, for real-time, non-intrusive non-intrusive monitoring. monitoring. The use The of use LEDs of LEDs has has as theproven European Tar Protocol, for calibration. The design presented couldof be effectively developed to provide system for this quantitative evaluation of tarinformation loading onmeasurable aregarding gas stream if species coupled with abesuitable offline technique, such biomass. Although exact the tars presents within the bio-oils isa been to be effective for the stimulation of fluorescence signals in the liquid phase both with unknown, method demonstrates the components selected could effectively utilized within a tar detection as the European Protocol, for calibration. The could be developed to provide system for quantitative evaluation of tar loading on adesign gas stream if coupled with athe suitable offline technique, beenbeen proven to this be toeffective beTar effective for the for stimulation the stimulation of any measurable of measurable fluorescence signals signals in liquid the liquid phase phase both both with with a sucha quantitative data concerning tar quantity on scale offluorescence thepresented gasifier. Ultimately, the system will require testing as theproven European Tar Protocol, for calibration. The presented could beineffectively effectively developed totest provide unknown, method demonstrates the components selected could effectively utilized within a tar detection standard tarquantitative compound (phenol) of known concentrations and for samples derived from a gasifier using system for evaluation of tar loading on adesign gas stream ifbio-oil coupled with abe suitable offline technique, such quantitative data concerning tar quantity on any scale of the gasifier. Ultimately, the system will require testing as the European Tar Protocol, for calibration. The design presented could be effectively developed to provide standard standard tar compound tar compound (phenol) (phenol) of known of known concentrations concentrations and for and bio-oil for bio-oil samples samples derived derived from from a gasifier a gasifier test using test using in the gas evaluate whether the detector isaregarding sufficiently to detect tarsystem loading concentrations in quantitative data to concerning tarfor quantity on anyThe scale of stream thepresented gasifier. Ultimately, the will require testing system for phase quantitative evaluation ofcalibration. tar loading on gas ifsensitive coupled with a suitable offline technique, such Miscanthus biomass. Although exact information the species of tars presents within the bio-oils is as the European Tar Protocol, design could be effectively developed to provide in the gas phase evaluate whether the detector is sufficiently to detect tar loading concentrations quantitative data to concerning tar quantity on any scale of the gasifier. Ultimately, the system will require testing Miscanthus Miscanthus biomass. biomass. Although Although exact exact information information regarding regarding species thesensitive species of tars ofbe presents tars presents within within the bio-oils the to bio-oils is in is the gas. in the gas phase to evaluate whether the detector is sufficiently sensitive to detect tar loading concentrations in as European Tar Protocol, for calibration. The design presented could effectively developed provide unknown, this method demonstrates the components selected could effectively be utilized within a tar detection quantitative data concerning tar quantity on any scale of the gasifier. Ultimately, the system will require testing the gas. in the gas phase to evaluate whether the detector is sufficiently sensitive to detect tar loading concentrations in unknown, unknown, this method this method demonstrates demonstrates the components the components selected selected could could effectively effectively be utilized be utilized within within a tar a detection tar detection the gas.gas quantitative data to concerning tar quantity on anyon scale of stream the gasifier. Ultimately, the will require testing system for phase quantitative evaluation of tar gas ifsensitive coupled with a suitable offline technique, such in the evaluate whether theloading detector isa sufficiently to detect tarsystem loading concentrations in the gas. system system for quantitative for phase quantitative evaluation evaluation of tarofloading tar loading on a on gas astream gas stream if coupled ifsensitive coupled withto with a suitable a suitable offline offline technique, technique, such such Acknowledgements in the gas to evaluate whether the detector is sufficiently detect tar loading concentrations in as the European Tar Protocol, for calibration. The design presented could be effectively developed to provide the gas. Acknowledgements as theas European the Tar Protocol, Tar Protocol, for calibration. for calibration. The design The design presented presented couldcould be effectively be effectively developed developed to provide to provide Acknowledgements the gas.European quantitative data concerning tar quantity on any scale of the gasifier. Ultimately, the system will require testing Acknowledgements quantitative quantitative data data concerning concerning tar quantity tar quantity on any on scale any scale of the of gasifier. the gasifier. Ultimately, Ultimately, the system the system will require will require testing Thegas authors like to whether thank EPSRC and theisSUPERGEN (UK) funding support testing for the in the phasewould to evaluate the detector sufficiently Bioenergy sensitive toHub detect tarfor loading concentrations in Acknowledgements The authors would like to thank EPSRC and the SUPERGEN Bioenergy Hub (UK) for funding support for in thein gas the phase gas phase to evaluate to evaluate whether whether the detector the detector is sufficiently is sufficiently sensitive sensitive to detect to detect tar loading tar loading concentrations concentrations in in research project (EP/M01343X/1). Kamble was kindly supported by a Government of Maharashtra scholarship The authors would like to thank EPSRC and the SUPERGEN Bioenergy Hub (UK) for funding support for the the Acknowledgements the gas. research project (EP/M01343X/1). Kamble was kindly supported by a Government of Maharashtra scholarship The authors would like to thank EPSRC and the SUPERGEN Bioenergy Hub (UK) for funding support for the the gas. the gas. (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported byby anaEPSRC research project (EP/M01343X/1). Kamble was kindly supported Government offorMaharashtra scholarship The authors like to thank EPSRC and SUPERGEN Bioenergy HubScholarship (UK)of funding support for the (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported by an Scholarship research projectwould (EP/M01343X/1). Kamble wasthe kindly supported by aEPSRC Government Maharashtra scholarship (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported by an EPSRC Scholarship The authors would like to thank EPSRC and the SUPERGEN Bioenergy Hub (UK) for funding support for the Acknowledgements research project (EP/M01343X/1). Kamble was kindly supported by a Government of Maharashtra scholarship (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported by an EPSRC Scholarship Acknowledgements Acknowledgements References research project (EP/M01343X/1). Kamble was kindly supportedbyby Government of Maharashtra scholarship (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported anaEPSRC Scholarship References References (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported by an EPSRC Scholarship The authors would like to thank EPSRC and the SUPERGEN Bioenergy Hub (UK) for funding support for the References The TheAhmadi, authors would like K. to like thank to thank EPSRC EPSRC andH.the and SUPERGEN theB.SUPERGEN Bioenergy Bioenergy HubofHub (UK) (UK) for funding formeasurement funding support support for the for the [1] authors M. C. would Brage, Sjöström, K. Engvall, Knoef, Van de Beld, Development an on-line tar method based on research project (EP/M01343X/1). Kamble was kindly by a Government of scholarship References [1] M. Ahmadi, C. Brage, K.Catalysis Sjöström, K. Engvall, H. Knoef, B.supported Van supported de Beld,by Development of an on-line tar Maharashtra measurement method based on photo ionization technique, Today, 176 was (2011) 250-252. research research project project (EP/M01343X/1). (EP/M01343X/1). Kamble Kamble kindly was kindly supported a by Government a Government of Maharashtra of Maharashtra scholarship scholarship [1] M. Ahmadi, C. Brage, K. Sjöström, K. Engvall, H. Knoef, B. Van de Beld, Development of an on-line tar measurement method based on References photo ionization technique, Catalysis Today, 176 (2011) 250-252. (DSW/EDU/F.S/15-16/D-IV/1762). Sean Capper was supported by an EPSRC [2] T.A. Milne C. and R.J. K. Evans, Biomass gasification "Tars": formation andofconversion, in,measurement National Renewable Energy [1] M. Ahmadi, Brage, Sjöström, K. Engvall, H. Knoef, B. Their Van denature, Beld, Development an Scholarship on-line tar method based on photo ionization technique, Catalysis Today, 176 (2011) 250-252. (DSW/EDU/F.S/15-16/D-IV/1762). (DSW/EDU/F.S/15-16/D-IV/1762). Sean Sean Capper Capper was supported was supported by an by EPSRC an EPSRC Scholarship Scholarship [2] T.A. Milne andBrage, R.J. Evans, gasification "Tars": formation andofconversion, in,measurement National Renewable Energy Laboratory, Colorado, USA,, 1998.Biomass [1] M. Ahmadi, C. K. Sjöström, K. Engvall, H. Knoef, B. Their Van denature, Beld, Development an on-line tar method based on photo ionization technique, Catalysis Today,gasification 176 (2011) "Tars": 250-252.Their nature, formation and conversion, in, National Renewable Energy [2] T.A. Milne and R.J. Evans, Biomass Laboratory, Colorado, USA,, 1998.

[1] M. C. Brage, K. Sjöström, K. Engvall, H. Knoef, B. Their VanDevelopment denature, Beld, Development ofconversion, anon-line on-linetar tar measurement method–based on [3] Ahmadi, H. Knoef, B.Catalysis Van de Beld, T. Liliedahl, K. Engvall, of a PIDand based measurement method Proof of photo ionization technique, Today, 176 (2011) 250-252. [2] T.A. Milne and R.J. Evans, gasification "Tars": formation in, National Renewable Energy Laboratory, Colorado, USA,, 1998.Biomass References [3] M. Ahmadi, H. Knoef, B.Catalysis Van de Beld, T. Liliedahl, K. Engvall, Development of a PIDand based on-line tarin, measurement method – Proof of photo ionization technique, Today, 176 (2011) 250-252. concept, Fuel, 113 (2013) 113-121. [2] T.A. Milne and R.J. Evans, Biomass gasification "Tars": Their nature, formation conversion, National Renewable Energy References References Laboratory, Colorado, USA,, 1998. [3] M. Ahmadi, H. Knoef, B. Van de Beld, T. Liliedahl, K. Engvall, Development of a PID based on-line tar measurement method – Proof of

concept, Fuel, 113 (2013) 113-121. [4] F. Defoort, S.H. Thiery, S. promising new on-line method ofnature, tar quantification mass spectrometry during steam gasification of Laboratory, Colorado, USA,, 1998.Biomass [2] T.A. Milne and R.J. Evans, gasification "Tars": Their formation and conversion, National Renewable Energy [3] M. Ahmadi, Knoef, B.Ravel, Van deABeld, T. Liliedahl, K. Engvall, Development of a PIDby based on-line tarin, measurement method – Proof concept, Fuel, 113 (2013) 113-121. [4] F. Defoort, S.H. S. ABeld, promising new method of quantification mass spectrometry during steam gasification of [1] M. C.Thiery, Brage, K. Sjöström, K. Engvall, H.on-line Knoef, B. VanDevelopment detar Beld, Development of anon-line on-line tarmeasurement measurement method biomass, Biomass and Bioenergy, 65 (2014) Laboratory, Colorado, USA,, 1998.de [3] Ahmadi, Knoef, B.Ravel, Van T.64-71. Liliedahl, K. Engvall, of a PIDby based tar method –based Proof on concept, Fuel, 113 (2013) 113-121. [4] F. Defoort, S.C.Thiery, S. Ravel, AEngvall, promising new on-line method of tar quantification by mass spectrometry during steam gasification of [1] M.biomass, [1] Ahmadi, M. Ahmadi, C. Brage, Brage, K. Sjöström, K. Sjöström, K. K. Engvall, H. Knoef, H. Knoef, B. Van B. de Van Beld, de Beld, Development Development of an on-line of an on-line tar measurement tar measurement method method based based on on Biomass and Bioenergy, 65 (2014) 64-71. photo ionization technique, Catalysis Today, 176 (2011) 250-252. [5] A. Fendt, T. Streibel, M. Sklorz, D. Richter, N. Dahmen, R. Zimmermann, On-Line Process Analysis of Biomass Flash Pyrolysis Gases [3] M. Ahmadi, H. Knoef, B. Van de Beld, T. Liliedahl, K. Engvall, Development of a PID based on-line tar measurement method – Proof concept, Fuel, 113 (2013) 113-121. [4] F. Defoort, S. Thiery, S. Ravel, A promising new on-line method of tar quantification by mass spectrometry during steam gasification of Biomass andCatalysis Bioenergy, 65 Today, (2014) 64-71. photo biomass, photo ionization ionization technique, technique, Catalysis Today, 176 (2011) 176 (2011) 250-252. 250-252. [5] A. Fendt, T.113 Streibel, M. Sklorz, Richter, N. R.Fuels, Zimmermann, On-Line Process Analysis ofin,Biomass Pyrolysis Gases [2] T.A. Milne and R.J. Evans, Biomass gasification "Tars": Theirof26 nature, formation andmass conversion, National Renewable Energy Enabled by Soft Photoionization Mass Spectrometry, Energy & 701-711. [4] F. Defoort, Thiery, S. Ravel, AD. promising newDahmen, on-line method tar(2012) quantification by spectrometry duringFlash steam gasification of concept, Fuel, (2013) 113-121. biomass, Biomass and Bioenergy, 65 (2014) 64-71. [5] A. Fendt, T.S. Streibel, M. Sklorz, D. Richter, N. Dahmen, R. Zimmermann, On-Line Process Analysis ofin,Biomass Flash Pyrolysis Gases [2] T.A. [2] Milne T.A. Milne and R.J. and Evans, R.J. Evans, Biomass Biomass gasification gasification "Tars": "Tars": Their Their nature, nature, formation formation and conversion, and conversion, in, National National Renewable Renewable Energy Energy Enabled by Soft Photoionization Mass Spectrometry, Energy (2012) 701-711. Laboratory, Colorado, USA,, 1998. [6] D.L. Carpenter, French, Quantitative Measurement of Biomass Tars ofUsing a Molecular-Beam Mass [4] F. Defoort, Thiery, S.Deutch, Ravel, AR.J. promising new on-line & method of26 quantification byGasifier massAnalysis spectrometry during steamPyrolysis gasification of biomass, Biomass andS.P. Bioenergy, 65 (2014) 64-71. [5] A. Fendt, T.S.Streibel, M. Sklorz, D. Richter, N. Dahmen, R.Fuels, Zimmermann, On-Line Process Biomass Flash Gases Enabled by Soft Photoionization Mass Spectrometry, Energy & Fuels, 26tar(2012) 701-711. Laboratory, Laboratory, Colorado, Colorado, USA,, USA,, 1998. 1998. [6] D.L. Carpenter, S.P. Deutch, French, Measurement of Biomass Gasifier Tarstar a Molecular-Beam Mass [3] M. Ahmadi, H. Knoef, B. VanTraditional de Beld, T.Impinger Liliedahl, K. Engvall, Development of a(2007) PID based on-line measurement method – Proof of Spectrometer:  with Sampling, Energy &(2012) Fuels, 21 3036-3043. biomass, Biomass and Bioenergy, 65R.J. (2014) 64-71. [5] A. Fendt, T.Comparison Streibel, M. Sklorz, D. Richter, N.Quantitative Dahmen, R.Fuels, Zimmermann, On-Line Process Analysis ofUsing Biomass Flash Pyrolysis Gases Enabled by Soft Photoionization Mass Spectrometry, Energy & 26 701-711. [6] D.L. Carpenter, S.P. Deutch, R.J. French, Quantitative Measurement of Biomass Gasifier Tars Using a Molecular-Beam Mass [3] M.Spectrometer:  [3] Ahmadi, M. Ahmadi, H. Knoef, H. (2013) Knoef, B. Van B.with deVan Beld, de Beld, T. Liliedahl, T.Impinger Liliedahl, K. Engvall, K. Engvall, Development Development of a PID of abased PID based on-line on-line tar measurement tar measurement method method – Proof – Proof of of Comparison Traditional Sampling, Energy &(2012) Fuels, 21 (2007) 3036-3043. concept, Fuel, 113 113-121. [7] R. Sun, N. Zobel, Y. Neubauer, C. Cardenas Chavez, F. Behrendt, Analysis of gas-phase polycyclic aromatic hydrocarbon mixtures by Enabled by Soft Photoionization Mass Spectrometry, Energy & Fuels, 26 701-711. [5] A. Fendt, T. Streibel, M. Sklorz, D. Richter, N. Dahmen, R. Zimmermann, On-Line Process Analysis of Biomass Flash Pyrolysis Gases [6] D.L. Carpenter, S.P. Deutch, R.J. French, Quantitative Measurement of Biomass Gasifier Tars Using a Molecular-Beam Mass Spectrometer:  Comparison with Traditional Impinger Sampling, Energy & Fuels, 21 (2007) 3036-3043. concept, concept, Fuel, 113 Fuel, (2013) 113 (2013) 113-121. 113-121. [7] R. Sun, N. Zobel, Y. Neubauer, C. Cardenas Chavez, F. Behrendt, Analysis of gas-phase polycyclic aromatic hydrocarbon mixtures by [4] F. Defoort, S. Thiery, S. Ravel, A promising new on-line method of tar quantification by mass spectrometry during steam gasification of laser-induced fluorescence, Optics and Lasers in Engineering, 48 (2010) 1231-1237. Enabled by Soft Photoionization Mass Spectrometry, Energy & Fuels, 26 (2012) 701-711. [6] D.L. Carpenter, S.P. Deutch, R.J. French, Quantitative Measurement of Biomass Gasifier Tars Using a Molecular-Beam Mass Spectrometer:  Comparison with Traditional Impinger Sampling, Energy & Fuels, (2007) [7] R. Defoort, Sun, N. Zobel, Neubauer, Cardenas Chavez, F. Behrendt, Analysis of21gas-phase polycyclic aromatic hydrocarbon mixtures [4] F. laser-induced [4] Defoort, F. S. Thiery, S. Thiery, S. Y. Ravel, S.Optics Ravel, A promising AC.(2014) promising new new on-line method method tar of quantification tar quantification by mass by3036-3043. spectrometry mass spectrometry duringduring steam steam gasification gasification of by of fluorescence, and Lasers inon-line Engineering, 48of (2010) 1231-1237. biomass, Biomass and Bioenergy, 65 64-71. [8] C. Baumhakl, S. Karellas, Tar analysis from biomass gasification of online Optics and Lasers in [6] D.L. Carpenter, S.P. Deutch, R.J. French, Quantitative of of Biomass Gasifier Tarsspectroscopy, Using ahydrocarbon Molecular-Beam Mass Spectrometer:  Comparison with Traditional Impinger Sampling, Energy &means Fuels, 21 (2007)fluorescence 3036-3043. [7] R. Sun, N. Zobel, Y. Neubauer, C.(2014) Cardenas Chavez, F. Behrendt, Analysis gas-phase polycyclic aromatic mixtures by laser-induced fluorescence, Optics and Lasers in Engineering, 48Measurement (2010)by 1231-1237. biomass, biomass, Biomass Biomass and Bioenergy, andKarellas, Bioenergy, 65 (2014) 65 64-71. 64-71. [8] C. Baumhakl, S. Tar analysis from biomass gasification by means of online fluorescence spectroscopy, Optics and Lasers in [5] A. Fendt, T. Streibel, M. Sklorz, D. Richter, N. Dahmen, R. Zimmermann, On-Line Process Analysis of Biomass Flash Pyrolysis Gases [7] R. Sun, N. Zobel, Y. Neubauer, C. Cardenas Chavez, F. Behrendt, Analysis of gas-phase polycyclic aromatic hydrocarbon mixtures by Spectrometer:  Comparison with Traditional Impinger Sampling, Energy & Fuels, 21 (2007) 3036-3043. laser-induced fluorescence, Optics and Lasers in Engineering, 48 (2010) 1231-1237. C. Fendt, Baumhakl, S.M.Karellas, Tar analysis biomass gasification byOn-Line means ofProcess online fluorescence spectroscopy, OpticsPyrolysis and Lasers in [5] A.[8] [5] Fendt, A. T.byStreibel, T. Streibel, Sklorz, M. Sklorz, D.Mass Richter, D. Richter, N.from Dahmen, N. Dahmen, R. Zimmermann, R.Fuels, Zimmermann, On-Line Process Analysis Analysis of Biomass of Biomass Flash Flash Pyrolysis Gases Gases Enabled Soft Photoionization Energy & 26 (2012) 701-711. [7] R. Sun, N.fluorescence, Zobel, Y. Neubauer, C. Spectrometry, Cardenas Chavez, F. Behrendt, Analysis of gas-phase polycyclicspectroscopy, aromatic hydrocarbon mixtures by laser-induced Optics and Lasers in Engineering, 48 (2010) 1231-1237. [8] C. Baumhakl, S. Karellas, Tar analysis from biomass gasification by means of online fluorescence Optics and Lasers in Enabled Enabled byD.L. Soft byCarpenter, Photoionization Soft Photoionization Spectrometry, Mass Spectrometry, Energy Energy & Fuels, & Fuels, 26 (2012) 26 (2012) 701-711. [6] S.P. Mass Deutch, R.J. French, Quantitative of701-711. Biomass Gasifier Tarsspectroscopy, Using a Molecular-Beam Mass laser-induced fluorescence, Optics Lasers in Engineering, 48Measurement (2010)by1231-1237. [8] C. Baumhakl, S. Karellas, Tar and analysis from biomass gasification means of online fluorescence Optics and Lasers in [6] D.L. [6] Carpenter, D.L. Carpenter, S.P. Deutch, S.P. Deutch, R.J. French, R.J. French, Quantitative Quantitative Measurement Measurement of Biomass of Biomass Gasifier Gasifier Tars Using Tars Using a Molecular-Beam a Molecular-Beam Mass Mass Spectrometer:  Comparison with Traditional Impinger Sampling, Energyby&means Fuels, of 21online (2007)fluorescence 3036-3043. spectroscopy, Optics and Lasers in [8] C. Baumhakl, S. Karellas, Tar analysis from biomass gasification Spectrometer:  Spectrometer:  Comparison Traditional with Traditional Impinger Sampling, Sampling, Energy & Fuels, & Fuels, 21 (2007) (2007) 3036-3043. 3036-3043. [7] R. Sun, N. Comparison Zobel, with Y. Neubauer, C.Impinger Cardenas Chavez, F.Energy Behrendt, Analysis of21gas-phase polycyclic aromatic hydrocarbon mixtures by

6

Sean Capper/ Capper Energy et al. / Energy Procedia 142000–000 (2017) 892–897 Sean Procedia 00 (2017)

897

Engineering, 49 (2011) 885-891. [9] P. Basu, Biomass gasification, pyrolysis and torrefaction: practical design and theory, 2nd ed., Amsterdam: Elsevier Inc., 2013. [10] K. Maniatis and A. Beenackers, “Tar Protocols: IEA Bioenergy Gasification Task,” Biomass and Bioenergy, vol. 1, no. 1, pp. 1-4, 1999. [11] L. J. Jandris and R. K. Forcé, “Determination of polynuclear aromatic hydrocarbons in vapor phases by laser-induced molecular fluorescence,” Analytica Chimica Acta, vol. 151, no. 1, pp. 19-27, 26 October 1982.