Applied Energy 113 (2014) 932945 Contents lists available at ScienceDirect Applied Energy journal homepage: www.elsevier.com/locate/apenergy Method for online measurement of the CHON composition of raw gas from biomass gasier Daniel Neves a,b,, Henrik Thunman b, Luớs Tarelho a, Anton Larsson b, Martin Seemann b, Arlindo Matos a a b Department of Environment and Planning, Centre of Environmental and Marine Studies, University of Aveiro, Campus Universitỏrio de Santiago, PT 3810-193 Aveiro, Portugal Department of Energy and Environment, Chalmers University of Technology, SE-412 96 Gửteborg, Sweden h i g h l i g h t s  Measuring the CHON composition of a raw gas by current methods is challenging  An alternative method is to burn the raw gas before measuring the CHON composition  The CHON contents of the raw gas can be accurately measured by the alternative method  Measuring the CHON contents of the raw gas is now performed in a one-step analysis  The new method is used to evaluate the operation of a dual uidised bed gasier a r t i c l e i n f o Article history: Received 13 February 2013 Received in revised form 29 July 2013 Accepted 13 August 2013 Available online 11 September 2013 Keywords: Method Gas Tar Biomass Gasication Fluidised bed a b s t r a c t For unattended biomass gasication processes, rapid methods for monitoring the elemental composition (CHON) of the raw gas leaving the gasier are needed Conventional methods rely on time-consuming and costly laboratory procedures for analysing the condensable part of the raw gas An alternative method, presented in this work, assesses the CHON composition of raw gas in a one step analysis without the need to previously characterise its chemical species composition Our method is based on the quantitative conversion of a raw gas of complex chemical composition into CO2, H2O, and N2 in a small combustor The levels of these simple species can be measured with high accuracy and good time resolution, and the CHON composition of the raw gas can be determined from the mass balance across the combustor To evaluate this method, an online combustion facility was built and used to analyse the raw gas from the Chalmers 2-MWth dual uidised bed steam gasier Test runs of the developed facility demonstrated complete combustion of the raw gas and the measurements were both fast and reliable The new method used in combination with zero-dimensional reactor modelling provides valuable data for the operational monitoring of gasication processes, such as the degree of fuel conversion, composition of the char exiting the gasier, oxygen transport by catalytic bed material, and amount of condensables in raw gas ể 2013 Elsevier Ltd All rights reserved Introduction To accelerate the industrialisation of biomass gasication, various demonstration plants are or have been in operation around the world [1] Allothermal gasication in a dual uidised bed (DFB) is one of these processes [24] that has enabled essential progress towards the ideal gasication process [5] The most well-known DFB gasication project is the 8MWth CHP plant in Gỹssing, Austria [4,6,7] In this technology, the bed material is continuously circulated between two interconnected uidised bed (FB) reactors Fresh chopped biomass is fed into the rst reactor, the steam gas Corresponding author at: Department of Environment and Planning, Centre of Environmental and Marine Studies, University of Aveiro, Campus Universitỏrio de Santiago, PT 3810-193 Aveiro, Portugal Tel.: +351 234370349; fax: +351 234370309 E-mail address: dneves@ua.pt (D Neves) 0306-2619/$ - see front matter ể 2013 Elsevier Ltd All rights reserved http://dx.doi.org/10.1016/j.apenergy.2013.08.032 ier, where it is heated and partially converted into gaseous fuel The remainder of the biomass (i.e., the char) leaves the gasier in the direction of the second reactor, the air combustor, where it is burned This enables reheating of the bedmaterial in the combustor, which is subsequently circulated back into the rst reactor for endothermic gasication The gas streams that leave each reactor are streamed off separately which permits to produce a raw gas with low N2 content (300 C) during about per sample The syringe tube is then extracted with solvents to recover the tar, and the bulk liquid solution is analysed by the aforementioned GC-FID technique to quantify the light tars (typically, species up to coronene [25]) Others have modied this procedure by using a thermal desorption technique to recover the tar from the solid phase [26] A recent review of online tar measurement methods [27] reveals that the most used ones are based on FID [28], photo-ionisation [29], mass spectrometry [30], and laser spectroscopy [31] For example, the IVD-tar analyser [28] uses a FID to analyse the raw gas and the respective dry raw gas The organic carbon separated by cold trapping is then determined by difference and the result is expressed, e.g., as CH4 Given the various tar measurement methods, it would not be amiss to assume that they produce different results A comparison of four online and ofine methods revealed differences of up to 50% in the tar content of a raw gas [28] An additional problem associated with determining the CHON composition of a raw gas is that the nature of the lumped tar is largely unknown (i.e., Yj,tar in Eq (1)) Literature data [32] suggests that the CHON composition of tar is close to that of the parent fuel (i.e., it is highly oxygenated), although the data show considerable scatter The most satisfactory way to approximate the CHON composition of lumped tar is by standard method or alternatively, by measuring a large number of tar species using GC analysis Online tar measurement methods provide little help in this regard, since the nature of the lumped tar is not resolved In summary, conventional methods to evaluate the CHON composition of raw gas using Eq (1) are impractical, costly, not provide rapid feedback, and can easily generate inaccurate results 2.2 A new measurement method In combustion calculations, the aim is often to determine the oxygen requirements and the composition of ue gases formed during complete conversion of a given fuel It is equally possible to determine the CHON composition of the fuel being burned from the ow rates and chemical compositions of both the oxidiser and combustion ue gases, which is the rationale behind the measurement method proposed in the present work 2.2.1 Measurement principle The combustible elements of raw gas, carbon and hydrogen, are assumed to react with oxygen to yield CO2 and H2O, while the nitrogen appears as N2 In this work the oxidiser is dry atmospheric air and, hence, the combustion reaction of raw gas can be represented by: mG;A raw gasị ỵ air ! mCO2 ;A CO2 ỵ mN2 ;A N2 ỵ mH2 O;A H2 O ỵ mO2 ;A O2 ỵmAr;A Arị 2ị where mG,A and mk,A (k = CO2, N2, H2O, O2) are the stoichiometric coefcients The stoichiometry is written on a dry air basis (subscript A), since the respective ow rate (n_ A ) can be measured accurately The problem is to determine the amounts of CO2, N2, H2O, and O2 produced per unit mass of dry air feed (mk,A, kg k/kg A) These are related to the chemical composition (yk,E, mole fraction) and molar ow rate (n_ E ) of the combustion ue gases according to Eq (3), in which n_ E can be derived from the nitrogen balance across the combustor (e.g., Eq (4) [33]) The inclusion of the N/H mass ratio of the raw gas in Eq (4) is needed to be able to account for the nitrogen entering the combustor with the raw gas When the raw gas is nitrogen-free or contains a negligible amount of nitrogen, Eq (4) simplies to n_ E ẳ yN2 ;A n_ A =yN2 ;E ; otherwise, the N/H ratio has to be known to resolve the generalised form A simple way to measure the N/H ratio of the raw gas being burned is given later on in this paper (Section 4.1) n_ M k nA M A mk;A ẳ yk;E _ E n_ E ẳ k ẳ CO2 ; N2 ; O2 ; H2 O yN2 ;A : nA yN2 ;E Y N;G =Y H;G ị yH2 O;E 2MH =M N2 ị 3ị 4ị Now the steady-state elemental mass balances to the combustion process can be solved according to Eqs (5)(8), where the left sides represent the mass of the jth element supplied with the raw gas per unit mass of dry air; the ratio of raw gas to dry air (mG;A in Eq (2)) is then the summation value for CHON, i.e P mG;A ẳ j Y j;G mG;A ị This makes it possible to compute the CHON mass fractions of the raw gas being burned (Yj,G) using Eq (9) It shall be stressed that, when a measurement of the H/C ratio of raw gas is enough, it can be approximated directly from the concentrations of H2O and CO2 in the combustion ue gases without the need to solve Eqs (3)(9) Y C;G mG;A ẳ mCO2 ;A M CO2 MC yCO2 ;A MCO2 MA 5ị Y H;G mG;A ẳ mH2 O;A M H2 M H2 O 6ị Y O;G mG;A ẳ mO2 ;A ỵ mCO2 ;A M O2 M O2 M O2 ỵ mH2 O;A yO2 ;A MCO2 M H2 O MA 7ị 935 D Neves et al / Applied Energy 113 (2014) 932945 Y N;G mG;A ẳ mN2 ;A yN2 ;A Y j;G mG;A Y j;G ẳ X Y j;G mG;A ị M N2 MA 8ị j ẳ C; H; O; N 9ị j Zero-dimensional model of dual FB gasier To show how the CHON composition of the raw gas can be used for monitoring the operation of a DFB gasier, a zero-dimensional reactor model is presented below For the sake of clarity, the streams across the gasier are illustrated in Fig Note that the total entering char comprises both unburnt char from the boiler (subscript ch1) and pyrolytic char (subscript ch) formed inside the gasier during pyrolysis of fresh biomass Therefore, the unconverted char leaving the gasier together with the circulating bed material (subscript ch2) is also a mixture of unburnt char and pyrolytic char The purge gas (subscript P) refers to some unknown quantity of gas leakage as, for example, ue gases from the boiler or ambient air MexOy and MexOy1 represent different oxidation states of a suitable in-bed catalyst, which can lead to selective oxygen transport from the boiler (oxidation zone) to the gasier (reduction zone) 3.1 Degrees of fuel and char conversion In the simplied model presented here, the same degree of gasication (v) is assumed for the two types of char, as shown in Eq (10) The simplest way to evaluate v is to monitor the H/C mass ratio of the raw gas (YH,G/YC,G) Indeed, the gas-phase reactions that occur in the gasier not alter the CHON contents of the raw gas, and the respective H/C ratio depends only on the streams entering the reactor and the amount of char converted, as in Eq (11), where Yi,F is the mass ratio of the ith stream to the daf fuel feed (subscript F) and Yj,i is the mass fraction of the jth element in the ith stream vẳ Y ch;F Y ch2;F Y ch1;F ị Y ch;F ỵ Y ch1;F 10ị Y H;G Y H;F ỵ Y M;F ỵ Y S;F ị Y H;H2 O ỵ Y ch;F Y H;ch v 1ị ỵ Y ch1;F Y H;ch1 v ẳ Y C;G Y C;F ỵ Y P;F Y C;P ỵ Y ch;F Y C;ch v 1ị ỵ Y ch1;F Y C;ch1 v 11ị Ych,F is essentially independent of the steam-fuel ratio (YM,F + YS,F) and can be estimated by separate pyrolysis experiments conducted at a temperature close to that used in the gasier In turns, the inows of unburnt char (Ych1,F) and purge gas (YP,F) are difcult to measure but, they are generally minor streams that can either be neglected or combined with the major streams to simplify the treatment (see [33]) In the rst limiting case, in which only devolatilisation occurs, the H/C ratio is determined by setting v = in Eq (11); in the other limiting case, the fuel is completely gasied and v = In practice, the degree of char conversion in the gasier is obtained by searching the value of v that ts the measured H/C ratio of the raw gas Note that v can also be obtained from the O/C ratio of the raw gas if the gasier is operated without in-bed metal oxide When a measurement of the ow rate of the raw gas (YG,F) is available, an alternative method to determine the amount of char that is converted is through the CHON balances across the gasier, as shown for carbon, hydrogen, oxygen, and nitrogen in Eq (12), where Yi,F is a positive or negative value depending on whether the ith stream is entering or leaving the gasier (see Fig 2) The difference between the amounts of char moving out and into the gasier is obtained by summing the left side of Eq (12) for CHON (Eq (13)), and the obtained difference Ych2,FYch1,F is related to v by Eq (10) (see also Table 1) Y ch2;F Y j;ch2 Y ch1;F Y j;ch1 ẳ Y j;F ỵ X Y i;F Y j;i i j ẳ C; H; O; N i ẳ P; G; M; S Y ch2;F Y ch1;F ẳ X 12ị Y ch2;F Y j;ch2 Y ch1;F Y j;ch1 ị j j ẳ C; H; O; N 13ị 3.2 Composition of the char leaving the gasier The elemental composition of the escaping char (ch2) can be estimated from the CHON balances across the gasier Here, it is Ash-free raw gas (G) Ash (As) Daf fuel (F) (=volatiles + pyrolytic char, ch) Moisture (M) Ash (As) Purge gas (P) From FB boiler: Bed material (B) Unburnt char (ch1) Ash (As) MexOy To small combustor FB gasifier Control volume Freeboard FB seal FB seal Bubbling bed Steam (S) To FB boiler: Bed material (B) Unconverted char (ch2) Ash (As) MexOy-1 Fig Illustration of the main streams across a bubbling DFB biomass gasier Abbreviations used are those listed in the nomenclature 936 D Neves et al / Applied Energy 113 (2014) 932945 Table Fuel conversion in the DFB gasier as a function of the operational parameter Ych2,F Ych1,F Condition Char conversion, v Y ch2;F Y ch1;F ẳ Y ch;F Y ch1;F < Y ch2;F Y ch1;F < Y ch;F Y ch2;F Y ch1;F ẳ Y ch1;F Y ch2;F Y ch1;F > Y ch;F v=0 0[...]... evidenced by the higher O/C mass ratio of the raw gas and the oxygen balance across the gasifier An estimate of the amount of condensables leaving the gasifier is possible by analysing both the raw gas and the respective dry gas The proposed method can be applied to determine the CHON composition of raw gas from any gasifier In the present work, it was applied to the Chalmers gasifier and the outcomes of these... Mass of element leaving the DFB gasifier with the raw gas or the respective dry gas per unit mass of dry ash-free fuel feed (F) (e.g., the water gas shift reaction), and can play a decisive role in relation to the large amount of steam leaving the gasifier during run #6 6 Conclusions For convenience and for economic reasons, current methods used to determine the CHON composition of raw gas from biomass gasifiers... mind, a method was developed in which the raw gas is converted into CO2, H2O, and N2 in a small combustor before the analysis of the CHON composition is undertaken Based on our evaluation of the method with standard gases combined with a sensitivity analysis, the error in the CHON mass fraction of raw gas can be reduced to ±3% through appropriate adjustment of the excess air condition The results of the. .. (13)) as a function of the steam-fuel ratio Char entering is unburnt char from the boiler (Ych1, F) and char leaving is unconverted char from the gasifier (Ych2, F) The dashed lines indicate the range for the yield of pyrolytic char supplied by the wood pellets (Ych, F) Table 6 Characteristics of the raw gas and respective dry gas from the Chalmers gasifier (run #6) a Parameter Raw gas Dry gas Tar + water... Amounts of condensable organics and steam in the raw gas (run #6) One combustion experiment was done during run #6, whereby the amounts of carbon and hydrogen leaving the gasifier with the raw gas and the respective dry raw gas were related to the unit mass of helium fed to the gasifier (see setup in Fig 5c) The results from this experiment are provided in Table 6 The initial result was that %8% of the total... method provides simple routesto evaluate the operation of biomass gasifiers The straightforward way to monitor the degrees of fuel and char gasification is to analyse the H/C ratio of the raw gas An alternative approach is to establish the elemental balances across the gasifier once the CHON composition and flow rate of the The financial support provided by the Fundação para a Ciência e a Tecnologia (FCT), Portugal,... with raw gas further underline the reliability of the method A recently developed moisture measurement system [37] coupled with IR gas analysers enables real-time monitoring of the H/C ratio of raw gas, while the respective CHON composition can be resolved by GC analysis with a measurement time of 3 min In combination with mass balance reactor model, the new method provides simple routesto evaluate the. .. ilmenite The experiments using ilmenite gave negative values for the oxygen balance across the gasifier (Fig 11), since the release of oxygen during the reduction stage of the metal oxide is not accounted for in Eq (12) For instance, the average value of the oxygen balance in the case of 12% ilmenite was À0.17 kgO/kgF, and this included both the oxygen supplied with the ilmenite and pyrolytic char Therefore,... balances across the Chalmers gasifier as a function of the steam-fuel ratio The quantities of carbon or oxygen entering the gasifier with fuel, steam, and purge gas minus the respective quantities leaving with the raw gas are indicated (see Eq (12))