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Fuel 116 (2014) 94102

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Fuel
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HPTLC and UV spectroscopy as innovative methods for biomass gasication tars analysis
Manuela Di Marcello a, Katia Gallucci b, Sergio Rapagn c, Ren Gruber a, Muriel Matt a,
a

Laboratoire de Chimie et Physique Approche Multichelle des Milieux Complexes, University of Lorraine, 1 Bd Arago, 57078 Metz Cedex 3, France University of LAquila, Dept. of Industrial Engineering, Via G. Gronchi 18, 67100 LAquila, Italy c University of Teramo, Dept. of Food Science, Via Carlo R. Lerici 1, 64023 Mosciano S. Angelo, TE, Italy
b

h i g h l i g h t s
 Two original methods based on HPTLC and UV spectroscopy are proposed for tar analysis.  HPTLC allows qualitative and quantitative tar analysis.  Aromatic hydrocarbons are separated into families on HPTLC RP-plate.  The standard addition method is used to quantify tar concentration in HPTLC.  UV spectroscopy allows quick tar quantication by use of UVSD technique.

a r t i c l e

i n f o

a b s t r a c t
The present work investigates the potential of two analytical tools to ensure rapid and affordable analysis of tar, produced during biomass gasication. On one hand, high performance thin layer chromatography (HPTLC) provides quantitative and qualitative information on tar composition and on the other, UV spectroscopy allows rapid quantitative total polycyclic aromatic hydrocarbon (PAHs) determination. An original separation method, based on HPTLC coupled with UV and uorescence detection, enables the resolution of non-volatile hydrocarbons into families from two to ve aromatic rings, with a difference between condensed and non-condensed structures. The method uses a two-stage migration with ethyl acetate/n-hexane and n-hexane on RP-plates, at 23 C. HPTLC is also used for tar quantication, by means of standard addition method after merging all the aromatic compounds in one peak. Thereafter, two approaches are proposed for UV quantication: the rst, UV direct quantication, consists in determining the absorbance and concentration of a reference sample, which permits to calculate unknown tar concentration. The second, based on UV spectra deconvolution (UVSD), calculates tar concentration by UV deconvolution of selected standard spectra without the need of reference samples. Both approaches were applied on thirty-seven samples formed in three gasiers, a Bubbling Fluidized Bed (BFB), an Internal Circulating Bubbling Fluidized Bed (ICBFB) and a Circulating Fluidized Bed (CFB). All the methods applied show a good agreement between the results obtained and the concentration of tar determined by HPLC/UV, the reference method. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 18 March 2013 Received in revised form 26 July 2013 Accepted 28 July 2013 Available online 13 August 2013 Keywords: Tar analysis HPTLC UV spectroscopy Biomass gasication

1. Introduction Tar is a complex mixture of condensable organic compounds present in the gasication product gas, excluding gaseous hydrocarbons from C1 through C6 [1]. It is undesirable because of various problems associated with its condensation, formation of tar
Corresponding author. Tel.: +33 (0)87547435.
E-mail addresses: manuela.di-marcello@univ-lorraine.fr (M. Di Marcello), katia.gallucci@univaq.it (K. Gallucci), srapagna@unite.it (S. Rapagn), rene.gruber@ univ-lorraine.fr (R. Gruber), muriel.matt@univ-lorraine.fr (M. Matt). 0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.fuel.2013.07.117

aerosols and polymerization of complex organic structures, which may induce severe problems in the process equipment as well as the engines and turbines used in the application of the product gas. The necessity of reducing tar content in the product gas pushes on the development of innovative and cost-effective gas cleaning treatment. Tar problem is not only associated with its quantity, but also with its properties and composition [2]. In fact, tar condensation behavior is strictly related with its composition. Higher molecular weight hydrocarbons (>three aromatic rings) have a great inuence on the tar dewpoint: heavy tars condense out as the gas

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temperature drops and cause major fouling, efciency loss and unscheduled plant stops; the reduction of heavy aromatics and consequently the tar dewpoint is a benecial factor [3]. Therefore, tar characterization, along with its quantication, represents a key step in the evaluation of a gasication process. In parallel with the technological advancements, the cost of chemical analysis largely increased. Therefore, economic efciency can only be achieved by the application of adequate equipment and the well-calculated use of time and materials [4]. The present paper investigates a new approach for the analysis of biomass gasication tars, based on two traditional analytical techniques: UV spectroscopy is proposed for the determination of total tar content and High Performance Thin Layer Chromatography (HPTLC) for the characterization of aromatic families. Both techniques take the advantages of ease to use and limited impact on costs. In 2010, Sun et al. [5] developed an on-line tar analysis based on uorescence spectroscopy, exciting the tar with a 266 nm laser. The measurement was only tested on a synthetic mixture of four standards showing a large variability of uorescence response factor of each molecule. The necessity of a robust, cost-effective and rapid technique for tar quantication drove our interest on UV spectroscopy. Aromatic hydrocarbons, in fact, have intense absorption peaks in UV range, due to the presence of multiple conjugated double bonds. Off-line UV analysis was tested on tar samples from three gasication plants (Dep. of Food Science, University of Teramo, Italy; ICB CSIC Zaragoza, Spain; ENEA Research Center Trisaia, Italy). Two approaches are proposed: the rst is based on direct correlation between absorbance at chosen wavelength and tar concentration using one tar sample quantied by HPLC/UV as reference, whereas the second consists on the application of mathematical treatment of UV spectra (UVSD). The deconvolution method has been largely investigated and several works are already described in literature concerning the determination of PAHs in environmental samples [68]. Along with quantication, rapid characterization of tar samples is desirable: tar families were separated and characterized using HPTLC. The technique shows a renewed interest in the analysis of PAHs thanks to the substantial progress made with automation, the wide choice of stationary phases, the reduced time of analysis and the simultaneous analysis of a large number of standards and samples on the same plate. The possibility of scanning the complete surface of the plates in UV or uorescence avoids the loss of information related with the adsorption problems, traditionally associated with column chromatographic methods (HPLC, GC) [9]. Several publications concern the use of HPTLC in separation and group type analysis of heavy petroleum fractions rened to various degrees, including natural base oils and coal tar pitch [914]. However, until now no applications in biomass gasication tars have been reported. The protocol of analysis allowed the separation of tar molecules into families from two to ve aromatic rings, with a differentiation between condensed and non-condensed structure using reversed phase HPTLC plates and elution at low temperature. Preliminary studies were also dedicated to the application of HPTLC in tar quantication: all the compounds were merged in a single large peak and quantied by means of standard addition method. Then, HPTLC enables the possibility for both characterization and quantication of heavy tar fraction. The promising results obtained with the studied techniques, suggest planar chromatography and UV spectroscopy as innovative analytical strategies to provide qualitative (HPTLC) and quantitative (UV, HPTLC) analysis of tars in a single step, without separation, evaporation or other additional time-consuming operations.

2. Materials and method 2.1. Samples and chemicals Tar samples were collected in 2-propanol according to the CEN/ TS 15439 protocol [1] and properly stored at 4 C before the analysis. Pure aromatic hydrocarbon standards are: phenol, toluene, styrene, indene, naphthalene, biphenyl, uorene, phenanthrene, anthracene, uoranthene and pyrene. All the standards were provided from Acros Organics (Geel, Belgium). Stock standard solutions of 1 mg ml1 were prepared in dichloromethane. Phenol solution at 1 mg ml1 was prepared in 2-propanol. Each subsequent dilution was made in 2-propanol, in accordance with the solvent used during tar sampling. All the organic solvents used in this work are of HPLC gradient grade and were provided from Fisher Scientic (Loughborough, Leicestershire, UK). Thirty-seven samples were available for this study: twenty-ve of them coming from bench scale gasiers operating in the laboratory of the University of Teramo (Italy) and ENEA Research Center Trisaia (Italy), and twelve from the ICB CSIC Zaragoza (Spain). All the samples considered in the work are the results of uidized bed steam gasication of biomasses. The gasier layouts and their performances were largely investigated under different catalytic conditions and biomass fuels [1520]. Table 1 summarizes the main data regarding the origin of the samples used in this study; the bed temperature range is between 750 and 850 C. In addition, one sample from Fixed Bed Updraft (FBU) updraft gasication (ENEA Trisaia) was used for UV spectrum comparison. 2.2. Reference method: HPLC/UV HPLC quantitative analysis was carried out by external calibration using at least six levels of PAHs concentration, to cover the range measured in the various samples. Each point of the calibration curves was repeated at least three times. Standards and tar solutions were analyzed by HPLC (Hitachi Elite LaChrom L-2130). The injection volume was 20 ll. The detection was carried out at 254 nm (Hitachi UV-detector L2400). The column used to separate tar molecules is a C18, 150 4.6 mm (Alltech Apollo C18 5 lm). A gradient elution was applied using methanol/water at a ow rate of 1 ml min1 (Table 2). 2.3. High performance thin layer chromatography All HPTLC equipments were provided from CAMAG (Muttenz, Switzerland): standards and samples were spotted on the plates using a CAMAG Linomat 5 autosampler and then eluted in a CAMAG horizontal developing chamber 100 100 mm, which minimizes the amount of solvent to be used (2 ml of solvent for each migration step); after the insertion of the plate and before each developing step, the chamber was saturated with mobile phase vapor for 2 min. HPTLC plates were then analyzed using a CAMAG TLC Scanner 3 (Slit length 3 mm; slit width 0.3 mm), in UV/VIS absorption and/or uorescence spectroscopy (K300 or K400 cut-off lters). Data were registered using WinCAT software version 1.3.4, incorporating track optimization position. 2.3.1. Qualitative HPTLC tar analysis HPTLC Silica gel 60 RP-18 glass plates with concentrating zone (200 25 mm) were purchased by Merck KGaA (Darmstadt, Germany). The plates of 200 100 mm were cut at 100 100 mm

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Table 1 Operating conditions of tar analyzed and selected samples represented in gures.

BFB: bubbling uidized bed gasier; ICBFB: internal uidized bed gasier; CFB: circulating uidized bed gasier.

Table 2 Gradient for tar analysis by HPLC/UV. Time, min 0 5 21 28 32 40 42 48 Methanol, % 45 45 75 75 85 85 100 100 Water, % 55 55 25 25 15 15 0 0

Tests were performed at room temperature and at 23 C, by placing the horizontal migration chamber in a cold box. In this case, the temperature of materials, plate and solvents was equilibrated for 30 min in the cold box, before starting the rst migration step. 2.3.2. Quantitative HPTLC tar analysis The quantication was performed by merging tar compounds in a single large peak and using the standard addition method. The composition of the standard used is detailed in Table 3 (synthetic sample). Four dilutions of the sample TAR 1 were prepared at 1/8 v/v, 1/10 v/v, 1/15 v/v, 1/20 v/v. In accordance with the classical procedure, one diluted sample was split into several even aliquots and an increasing volume of standard was added to the sample (with the exception of the rst vial); each vial was then completed with the same nal volume of 2-propanol. The procedure was repeated for the four dilutions. The spiked samples were then spotted on a HPTLC RP-18W and eluted with ethyl acetate/n-hexane 50/50 (v/ v) over 40 mm and n-hexane until the solvent front reaches 90 mm. The detection was performed scanning the plate in UV at 254 nm. The standard addition curve was obtained by plotting the amount of added standard (lg applied on the HPTLC plate) vs.

with the SmartCUT plate cutter from CAMAG (Muttenz, Switzerland). Before the analysis, each plate was pre-washed by migrating acetonitrile over the whole plate. The migration was performed with a rst elution step of ethyl acetate/n-hexane 50/50 (v/v) over 40 mm, followed by a second step of pure n-hexane until the solvent front reaches the distance of 90 mm from the beginning of the plate. The peak identication was performed by spotting on the same plate selected standards of PAHs and sample (0.5 lg in the proper volume) and comparing their distance of migration, rate of ow (Rf) and UV or uorescence spectra.

M. Di Marcello et al. / Fuel 116 (2014) 94102 Table 3 Concentration of PAHs in a gasication tar sample and in the corresponding synthetic tar mixture. # Tar compound Molecular structure Tar sample quantied by HPLC, mg l1 212.3 40.5 Synthetic sample, mg l1 212.5 40.0

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271, 280, and 285 nm). The chosen reference sample was obtained from the bench-scale bubbling uidized bed (BFB) gasier in Teramo. Once measured the absorbance a tar sample (As), its concentration (Cs) is then determined as the results of the proportion:

1 2

Toluene Styrene

Cs

C r As Ar

Indene

29.1

29.0

4 5 6

Naphthalene Biphenyl Fluorene

282.5 20.8 6.1

281.6 21.0 6.0

Phenanthrene

44.3

44.0

2.4.2. Quantitative tar analysis by UVSD UV spectra deconvolution is based on the assumption that an unknown UV spectrum can be reconstituted by a linear combination of a small number of well-dened and representative reference spectra. In the present work, the spectrum of each standard described in Section 2.1 was used as reference. The resulting spectra were imported as data les in Excel 2003 version 11.0. The coefcient contribution of each reference spectrum was calculated using Excel solver function [21]. This numerical optimization add-in leads to calculate the best t between measured and restituted spectra with a least-squared method and the associated quadratic error for a procedure check [7]. 3. Results and discussion

8 9

Anthracene Fluoranthene

7.5 8.3

7.0 8.2

10

Pyrene

15.1

10.0

11

Chrysene

<LOQ

2.0

12

Dibenzanthracene

<LOQ

2.0

The sampling method described in the technical standard CEN/ TS 15439: 2008 was used to obtain a representative set of all the organic compounds that compose the tar fraction [1]. According to the tar maturation scheme for pyrolysis tars [22], the conditions used in the investigated experiments (Table 1) should not induce the formation of PAHs with more than ve aromatic rings. Tar gasication samples were rstly characterized by HPLC/UV, which provided the reference data to compare with the analytical method proposed in this work: HPTLC/UV/FL and UV spectroscopy. HPLC was chosen thanks to the advantage of having no need of pretreatment step or additional measurements, such as gravimetric analysis. 3.1. Application of high performance thin layer chromatography in tar analysis 3.1.1. Qualitative HPTLC tar investigation: separation of PAHs according their aromatic structures Several combinations of HPTLC plates and solvents were tested to achieve the nest separation of the hydrocarbon, according to aromaticity. Best results were obtained on HPTLC RP-18 plates with concentrating zone, using a two step migration with ethyl acetate/n-hexane and then n-hexane. The rst mobile phase was used to elute all the compounds from the deposition spot, including the slightly polar molecules in the tar, and the second permitted the separation on the RP plate. The samples TAR 1 and TAR 2 used in this part of the work (Figs. 1 and 2) were produced in two different uidized bed reactors, during almond shell gasication with Fe/olivine as primary catalyst. The samples have signicant differences in their concentration, which was 0.68 g l1 and 2.65 g l1 respectively. The simultaneous migration with selected PAHs standards (phenanthrene, pyrene, chrysene and dibenzoanhracene) allowed the identication of the observed peaks. The effect of the temperature on the separation was evaluated eluting samples and PAHs standards at 20 C and at 23 C. The chromatograms obtained at 20 C are reported in Fig. 1: in both samples a poor separation was observed between the peaks of 3-aromatic compounds (e.g. phenanthrene and anthracene) and 4-aromatic with condensed structure (e.g. pyrene and uoranthene); their Rf are respectively 0.82 and 0.79. The separation of

Total content LOQ: limit of quantication.

681.5

678.3

the area of the peak. Each point in the curve was repeated at least four times. 2.4. UV spectroscopy The UV/VIS spectra of the samples, as well as those of the standards, were recorded in a UV/VIS double-beam spectrometer (UV8500 TECHCOMP, Kowloon, Hong Kong) in the wavelength range between 235 and 300 nm. The acquisition software UVVIS Analyst (Techcomp, Kowloon, Hong Kong) produces a data le (WAV le) that can be directly exported to any datasheet. Measurements were performed using a standard 1 cm 1 cm quartz cell and 2-propanol as blank. Samples and standards were diluted in 2-propanol in adapted concentration to obtain absorbance values within 0.2 and 1.5 AU in the 235300 nm range. 2.4.1. Quantitative tar analysis by UV Tar concentration was calculated using a reference sample of known concentration (Cr) and absorbance (Ar). The concentration of the reference sample was obtained in HPLC/UV, and its absorbance was measured at several selected wavelengths (254, 260,

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Fig. 1. HPTLC chromatograms of samples TAR 1 and TAR 2. Analysis at 20 C, on Silica gel 60 RP-18 plate with concentrating zone. Detection in UV at 254 nm.

Fig. 3. HPTLC chromatograms of sample TAR 1 (solid line) and a representative standard mix (dotted line). Analysis at 23 C, on Silica gel 60 RP-18 plate with concentrating zone. Detection in UV at 254 nm.

with condensed structure (pyrene and uoranthene). In accordance with the standards the peak of four-aromatic with linear structure was clearly separated and had a Rf of 0.66. The identication was then conrmed by measuring the UV and uorescence spectra. The achieved good resolution was additionally conrmed comparing the chromatograms of sample TAR 1 and a synthetic sample (Fig. 3), which was prepared according to the HPLC/UV analysis of TAR 1 (Table 3). The use of a synthetic sample is helpful to optimize resolution on the HPTLC plate, because it allows following the behavior of the complex tar mixture during the developing step and gives clear information in the peak identication. In addition to the identied tar compounds, the 4-aromatic chrysene and the 5-aromatic dibenzanthracene were added in the synthetic sample. The results in Fig. 3 show the analogous chromatogram proles acquired for the synthetic and the tar samples. In addition to the identied PAHs, two non-identied peaks were evidenced.
Fig. 2. HPTLC chromatograms of samples TAR 1 and TAR 2. Analysis at 23 C, on Silica gel 60 RP-18 plate with concentrating zone. Detection in UV at 254 nm.

the peak corresponding to 4-aromatics with linear structures, such as chrysene, appears more evident (Rf = 0.74). Additional attention should be paid to the fact that the two chromatograms in Fig. 1 do not show signicant difference concerning their composition, as both samples are the results of analogous gasication processes. Nevertheless, the difference occurring in their concentration is well evidenced, even considering that the more concentrated sample was deposited in a lower amount. In order to increase the separation of the different type of PAHs, the experiment described above was repeated at 23 C. The effect of low temperature on TLC analysis has been investigated since decades [4,23,24], as the modication of the partition equilibrium between stationary and mobile phases may inuence the separation positively. The chromatograms obtained at 23 C are provided in Fig. 2: as observed, the elution at low temperature determined a signicant increased separation. At 23 C, the Rf of phenanthrene, pyrene, chrysene and dibenzoanthracene were 0.79, 0.73, 0.65, 0.59, respectively. The main peak in Fig. 1 was divided in three partially separated peaks: the rst at 76 mm (Rf = 0.85) representing the low-volatile bi-aromatic compounds, the highest at 69 mm (Rf = 0.77) representing the three-aromatic compounds (linear and condensed structures, such as anthracene and phenanthrene) and the last at 65 mm (Rf = 0.72) for the four-aromatic compounds

3.1.2. Investigation of unknown chromatographic peaks As shown in Fig. 4, two unidentied peaks were observed in the chromatogram of sample TAR 1 at the migration distances of 49 mm (Rf = 0.54) and 56 mm (Rf = 0.62). In an effort of understanding their nature, further structural information were achieved, scanning the plate at different wavelengths in UV and uorescence emission mode. Light aromatics absorb at lower wavelength (close to 254 nm) and have reduced uorescence emissions, while heavy aromatics show their maximums at greater wavelengths and have highly intense uorescence emission peaks. Recording the UV spectrum of the B peak, a maximum was observed at 260 nm. Moreover the unknown peak B was not absorbing at 283 nm (Fig. 4A) and it had no uorescence emission when exited at 254 nm or 283 nm (Fig. 4B), suggesting that this molecule(s) could be a light aromatic polar compound. The spectral properties of the unknown peak A suggest that it should be heavy aromatic molecule(s) presents in low concentration, which does not affect the total tar quantication. This compound(s) has a chemical structure similar to that of dibenzanthracene, and when excited at 254 nm or 283 nm strongly emits (Fig. 4B). 3.1.3. Quantitative HPTLC tar investigation: Standard Addition Method (SAM) Tar concentration was quantied by SAM. It is commonly used to determine the concentration of an analyte that is in a complex

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Fig. 4. HPTLC chromatograms of sample TAR 1: (A) detection in UV; (B) detection in uorescence emission kem > 400 nm .

matrix. It can be convenient when a small number of samples should be analyzed. The idea is to add a known concentration of analyte to the sample and monitor the change in instrument response. As this procedure is generally proposed for the analysis of few samples, the method was validated on one representative tar sample, but prepared at four different dilutions. In other word, the SAM was tested four times on one tar sample. The sample TAR 1 was selected in this part of the work and its tar composition is detailed in Table 3. The synthetic tar sample was used as spiking standard. After the deposition and the migration steps, a chromatogram was recorded for all of the diluted solutions and the linear regression was established with the form of R mc0 b, where R is the response signal, m and b are the slope and the intercept respectively and c0 is the increase in PAHs in the original sample. Fig. 5 shows the standard addition obtained curves. The area of the peak was proportional to the spiking, yielding satisfactory determination coefcients. Therefore, the initial amount of the analyte was graphically extrapolated from the x-axis intercept b (c00 ), at R = 0 and b mc00 , which can be also written as c00 m , where c00 corresponds to the initial tar amount. The four amounts determined were then corrected for the dilution factor, and the initial concentration was recalculated. A mean value of 0.99 g l1 was obtained, with a low coefcient of variation (9.3%). The four results observed by means of HPTLC/UV were also compared with the reference method (HPLC/UV) and a linear correlation could be established (R2 = 0.991). However, the slope of the linear function (m = 1.19) showed that HPTLC seems to overestimate tar concentration in the samples. Even considering the necessity of further investigation, these results should be attributed to the fact that HPTLC detects the complete range of non-volatile tars, where HPLC allows to quantify the eluted and identied detectable peaks.

Fig. 5. Tar quantication in HPTLC/UV using the standard addition method on four dilutions of sample TAR 1. Dilutions: (A) 1/8 v/v; (B) 1/10 v/v; (C) 1/15 v/v; (D) 1/20 v/v.

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3.2. Application of UV spectroscopy in tar analysis 3.2.1. Requirements to use UV spectroscopy for tar quantication UV spectroscopy is an interesting analytical technique that allows rapid off-line, or eventually on-line, semi-quantitative tar analysis, the evaluation of the gasication process and the effectiveness of tar removal devices. The complexity of the prole of tar UV spectrum and its richness in absorbing molecules, allows to obtain poor qualitative information. Whatever the data treatment proposed, UV spectroscopy permits to estimate the total value of tar content, without the possibility to quantify each single molecule in the mix. In this context, it is necessary to x three essential criteria to apply the technique for tar quantication. The rst criterion concerns the origin of the samples: in fact UV method could be successfully applied only if the tar samples come from biomass uidized bed gasication. Fig. 6 compares the UV spectra of tars produced in three different uidized bed gasiers using different biomass and catalysts (samples TAR 2, TAR 3 and TAR 4). In addition, an UV spectrum of a tar produced in xed bed gasication is represented. This sample is obtained using higher temperature and a different technology. No remarkable differences were found in the spectra of all the tar samples tested if they were carried out from uidized bed gasier. On the contrary, the UV spectrum of the sample produced in the xed bed gasier appears considerably dissimilar, reecting a very different PAHs composition. The second requirement to respect, when approaching tar quantication by UV spectroscopy, is to assure a proper dilution of the samples. On one hand, the limitation of the linearity of the Beer Lamberts law imposes dilution, to avoid the electrostatic and pp interactions between molecules in close proximity, which will determine deviations in absorptivity coefcients of the mixture. On the other hand, an excessive dilution would result in a signicant loss of denition of the spectrum, with a consequent drop of information. To prevent the problems described, the absorbance values in the operating wavelength range should be within 1.5 AU and 0.3 AU. The last important criterion concerns the choice of the optimal wavelength range to use for tar quantication. According to the additivity of the BeerLamberts Law, the absorbance spectrum is the results of the contribution of each compound in the sample. Therefore, the operating range was established according to the PAHs composition. Fig. 7 shows the relation between the absorption bands in the sample TAR 3 and in the PAHs standards: the majority of compounds in tar samples have their specic absorption bands between 235 nm and 300 nm; in this range, the main

Fig. 7. Absorbance spectrum of the sample TAR 3 (bold solid line) and selected PAHs standards of low (A) to mediumhigh (B) molecular weight.

compound naphthalene and higher molecular weight PAHs (Pthree aromatic rings) show corresponding bands in the sample. 3.2.2. Direct quantitative tar investigation The principle of the method consists in using the absorbance and concentration of a reference tar sample to quantify the others. Therefore, to verify the impact of its choice on the quantication, all the available samples were tested as reference. No signicant differences were reported when the criterion of the proper dilution was respected. In order to verify an occurring inuence of the detection wavelength, all the samples were analyzed at 254, 260, 271, 280 and 285 nm, which correspond to some peaks and valley in the tar absorbance spectra. Fig. 8 shows the linear correlation established at 254 nm between the results of the direct UV quantication and the reference method (HPLC). The analysis was performed on a large number of samples yielding a good correlation for each tested wavelength (0.947 < R2 < 0.977). Those results conrm the suitability of the absorbance range adopted for the determination of tar content. In each case, the analysis of the linear regression gave a slope close to 1, evidencing that the method does not overestimate the total concentration of PAHs. 3.2.3. Quantitative tar investigation by UVSD On the basis of the promising results obtained using the direct approach, a quantication method based on spectrum deconvolution was also investigated. Fig. 9 shows the comparison between the spectra of the modeling and the corresponding sample TAR 3. Results show how the two spectra are overlapped in the range between 236 and 300 nm. The lack of specic absorption of aromatic molecules and the presence of unidentied compounds should explain the

Fig. 6. UV spectra of four gasication tar samples: three of them coming from uidized bed gasiers (TAR 2, TAR 3, TAR 4) and one from a Fixed Bed Updraft gasier (FB).

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Fig. 8. Correlation between tar concentrations measured by HPLC/UV (reference analysis) and UV spectroscopy at 254 nm.

highlighted difference at lowest wavelength (200235 nm), as well as the presence of benzene, which absorbs in this wavelength range. The correlation between the results of the UVSD approach and the reference method is evaluated in Fig. 10. UVSD does not overestimate the total tar concentration in the sample and the coefcient of correlation points out the agreement between the two methods. The analysis of variance of the regression gave a signicant value of F (>200) and the hypothesis H0 of the independence of the values found by HPLC and UVSD could be rejected. Therefore, we could conclude that the mathematical treatment allows a reliable estimation of the total concentration of aromatics in a gasication sample, but prevents to obtain detailed information about its qualitative composition. The main limitation of the method lays on unfeasibility of quantication of a selected compound in the PAHs mixture, in fact a worst individual correlation was observed. The reason that could explain this limitation is linked to the fact that several spectra of isolated compounds are partially, until completely overlapped (e.g. phenanthrene and anthracene, indene and biphenyl, naphthalene and uorene) so the contribution of each molecule cannot be distinguished with a good agreement.

4. Conclusions Table 4 summarizes the comparison between the tar content obtained with the techniques studied (UV spectroscopy, HPTLC) and the reference method (HPLC) for four samples, which cover the concentration range between 0.1 g l1 and 1 g l1. The complete set of results may be found as Supplementary data available in electronic format. In UV spectroscopy, an average difference of 25% is reported, which is reasonable considering the high concentrations involved (g l1). The technique offers the possibility of quick tar determination laying on widely used equipment. Both the approaches investigated (direct quantication vs. UVSD) gave interesting results, showing sufcient correlation with those obtained by HPLC. The main difference to take into account concerned that direct UV is easier, but requires the results of a reference method, while UVSD does not need any additional analysis, except a library of the UV spectra of selected PAH standards. UV spectroscopy can be proposed to assure a punctual control of the process performances without searching for individual compound determination. It has the potential to be adapted for on-line tar detection and global quantication as the main compounds (aromatics containing less than ve rings) are detected in the near UV region with absorbance proportional to tar amount. On the other hand, planar chromatography, with his growing variety of stationary phases and material improvements, led to the development of an original separation method for tar analysis, which offers the possibility to characterize tar composition. Low temperature chromatographic conditions returned good resolution for PAHs composing tar fraction, with a difference between condensed and non-condensed structure. The method allowed the quantication of tar content using the standard addition method,

Fig. 9. Absorbance spectrum of the sample TAR 3 (solid line) and a modeling UV spectrum obtained by means of UVSD (dotted line).

Table 4 Example of quantication results obtained with the analytical methods studied on selected tar samples. Sample 1 2 3 4 Fig. 10. Correlation between tar concentrations measured by HPLC/UV (reference analysis) and by UVSD. HPLC, g l1 0.09 0.30 0.68 0.83 UV, g l1 0.12 0.21 0.52 0.97 UVSD, g l1 0.10 0.21 0.42 0.68 HPTLC, g l1 N.D. N.D. 0.99 N.D.

N.D. not determined.

102

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when all the compounds are merged under the same peak. Further investigations are needed concerning the quantication of each family of aromatics. In conclusion, data evidenced that both UV spectroscopy and HPTLC show promising potentialities along with signicant advantages, as they are inexpensive, rapid and low solvent consuming. Acknowledgments The authors acknowledge Dr. Francisco Garca Labiano from Instituto de Carboqumica ICB CSIC (Zaragoza, Spain) and Dr. Donatella Barisano from Centro Ricerche ENEA Trisaia (Rotondella, Italy) for their kind support to the present research activity. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.fuel.2013.07.117. References
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