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Energy 50 (2013) 333e342

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Energy
journal homepage: www.elsevier.com/locate/energy

Characterisation of tars from biomass gasication: Effect of the


operating conditions
J.J. Hernndez*, R. Ballesteros, G. Aranda
Escuela Tcnica Superior de Ingenieros Industriales, Universidad de Castilla-La Mancha, Avda. Camilo Jos Cela s/n (edif. Politcnica), 13071 Ciudad Real, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Tars formation remains the main technical hurdle in the development of biomass gasication at
Received 20 July 2012 commercial scale, due to its associated operating problems (condensation, catalyst deactivation,
Received in revised form polymerisation). This work aims to study the effect of the operating conditions (biomass/air ratio,
5 December 2012
temperature and gasifying agent) on the production and the technical and environmental hazard
Accepted 7 December 2012
(tar dew point and carcinogenic potential) of tars produced in a small-scale drop-tube gasier,
Available online 5 January 2013
dealcoholised marc of grape being used as biomass fuel. An analytical HPLC method has been used for the
detection of polycyclic aromatic hydrocarbons (PAHs), benzene, toluene, ethyl-benzene and xylenes
Keywords:
Biomass gasication
(BTEX), phenol, and pyridine. Results show that an increase in the relative biomass/air ratio, a decrease in
Tar characterisation temperature, and higher steam content lead to a higher tar production. BTEX have been found as the
Temperature main constituents of tars (60e70% wt.), whereas among PAHs, the most signicant are the lighter ones
Relative fuel/air ratio (naphthalene, acenaphtylene, acenaphtene). Phenol production is favoured at lower temperatures or/and
Steam content higher steam content (around 50% wt. of the tar mixture at 750  C and steam gasication). A progressive
aromatisation of tars has been observed when increasing the temperature, the effect of steam addition
on tar composition being not signicant at temperatures higher than w1000  C.
2012 Elsevier Ltd. All rights reserved.

1. Introduction transformed into producer gas, but remains as carbonaceous solid


residue (char and soot particles), and as a condensable product
Gasication is a complex thermochemical process in which (tars).
a carbonaceous solid fuel (coal, biomass, wastes) is transformed at Tars are the most troublesome pollutants of producer gas, being
high temperatures (700e1500  C) and in the presence of a gasifying the main technical hurdle for the commercial implementation of
agent (air or oxygen under sub-stoichiometric conditions, steam, biomass gasication [1,8,9]. Tars consist of a complex mixture of
carbon dioxide, hydrogen, and mixtures of them) into a gas with organic compounds (including aromatic and heteroaromatic
a useful heating value, called producer gas or synthesis gas. The key species as well as polycyclic aromatic compounds, PAHs) with high
advantage of gasication is the possibility of converting a solid fuel boiling points, which is produced during the devolatilisation stage
into a gas (easier to clean, transport and burn efciently) which [9,10,11]. The main technical problems caused by biomass gasi-
keeps 70e80% of the chemical energy of the original fuel [1]. cation tars include tar condensation (which causes plugging and
Moreover, gas from gasication can be used in a wide range of fouling problems, thus giving place to unwanted plant shutdowns),
applications: production of heat and power, and as feedstock for tar polymerisation at high temperatures (which produces poly-
the synthesis of fuels and chemicals (the latter in the cases of cyclic compounds and even soot in extreme cases), the need for
oxygen and/or steam gasication) [2e7]. In the case of biomass managing hazardous residual efuents derived from wet cleaning
gasication, the advantages associated with the use of biomass (an systems, and catalyst deactivation due to tar deposition [8,12].
abundant, widespread renewable energy source) are added into The gravimetric amount of tars produced is claimed not to be
those of the gasication technology. However, during the gasica- enough to assess the performance of the gasication process.
tion process, part of the fuel (around 20%, although the amount Rather, the criterion of the quality of the product gas and the
depends on the operating conditions and the type of gasier) is not efciency of the gas cleaning system that is increasingly receiving
attention is the tar dew point, dened as the temperature at which
* Corresponding author. Tel.: 34 926 295 300x3880. condensation is produced when cooling the gas. Tar dew point
E-mail address: JuanJose.Hernandez@uclm.es (J.J. Hernndez). mainly depends on tar composition, in particular on the amount of

0360-5442/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2012.12.005
334 J.J. Hernndez et al. / Energy 50 (2013) 333e342

Table 1 Tar properties have been evaluated through several parameters:


Thermochemical characterisation of dealcoholised marc of grape. individual production of the tar components, TPi (expressed in
Fuel Dealcoholised marc of grape mg/Nm3 of product gas), total tar production, TP (in mg/Nm3), tar
Ultimate analysis (% wt., dry basis) dew point (in  C) and tar carcinogenic potential, KE (in mg/Nm3).
C (%) 52.06 These parameters have been dened in Section 2.3 and, as
H (%) 5.75 mentioned before, they affect the selection of the gas cleaning
N (%) 2.05
system, the nal use of the gasication gas and the management of
S (%) 0.14
O (%) 32.06 the efuents from tar removal techniques. Therefore, one of the
Proximate analysis (% wt., dry basis) most interesting features of this work is the extensive and
Volatile matter 64.02 combined analysis of the tar properties (including a detailed
Fixed carbon 28.04 speciation) and the gasication performance when changing the
Ash 7.94
LHV (MJ/kg, dry basis) 20.41
operating conditions of a drop-tube gasier.
Stoichiometric fuel/air ratio, 0.14
Fstoic (dry, ash-free basis) 2. Experimental

heaviest compounds [13,14], while tar composition and amount 2.1. Biomass feedstock and experimental schedule
depend on several factors, namely the nature of the initial feedstock
(coal, biomass) [9,10,15], fuel properties (in particular, moisture The biomass fuel used in this work has been dealcoholised marc
content [11,16e19]), the operating conditions (temperature, pres- of grape, an agro-industrial residue obtained in the winery and
sure, residence time) [8,9,12,14,20e25], the type of gasier [17], the distillery industries from the water washing of marc of grape,
gasifying agent used [12,15,22,26,27], the use of catalysts, and the material consisting of skins, stalks and seeds of grape. This feed-
method of tar sampling and analysis [8,9,10,20]. stock has been selected because of its high energy potential in the
In this work, the effect of the main operating conditions of the central and southern regions of Spain. Table 1 contains the ther-
gasication process (relative fuel/air ratio, operating temperature mochemical characterisation of dealcoholised marc of grape.
and composition of air and steam in the gasifying agent) on the
production and properties of the resulting tars has been analysed. 2.2. Gasication facility and test procedure
Air and steam are inexpensive, extensively used gasifying agents in
small- and medium-scale gasiers for energy production. With this All the tests performed have been carried out in a small-scale
purpose, an analytical method based in liquid chromatography drop-tube gasication pilot plant located at the laboratories of
(HPLC) for the detection of the main species present in gasication the Fuels and Engines Group of the University of Castilla-La Mancha
tars has been used. HPLC is acknowledged as a feasible technique (GCM-UCLM), described elsewhere [37e39] and shown in Fig. 1.
for the identication of both polar and non-polar compounds ob- The reactor consists of an alumina tube (60 mm internal diameter,
tained from biomass pyrolysis/gasication [28e30]. However, the 1.2 m long). Given the small dimensions of the gasier, it is
use of HPLC for the detection of tars produced in biomass gasi- necessary to externally heat it in order to compensate for heat
cation is less extended, since the most important off-line methods losses. Therefore, the tube is surrounded by an electrical furnace
for tar sampling (the guideline method, and the solid phase with three independent temperature zones, which allows the
adsorption method, SPA) use gas chromatography coupled to mass separate analysis of the operating conditions (unlike usual
spectrometry (GCeMS) [14,31e36]. The HPLC method developed is commercial auto-thermal facilities, where fuel/air ratio and
able to detect 16 PAHs compounds, BTEX, phenol, and pyridine, temperature are variables closely related). A steam production
these compounds being considered as the most abundant at high- system, composed of a water pump provided with a frequency
temperature gasication [35]. Moreover, the PAHs detected (listed controller and a 3 kW steam generator allows one to select and
in Table 4) have also been speciated for being the group pointed by keep a constant steam ow up to 6.7 L/h. In addition, a cold trap
the US Environmental Protection Agency (EPA) as priority pollut- (consisting of a sealed stainless steel container surrounded by
ants due to their higher carcinogenic potential. Phenol and pyridine a water jacket at room temperature) installed at the gas outlet
can be considered as representative of oxygen-containing and enables to collect the condensates (water, tars and entrained
nitrogen-containing heteroatomic compounds, respectively. particles) contained in the product gas. Lastly, a gas metre makes

Table 2
Experimental tests carried out for tar sampling and analysis.

Fuel T ( C) _ f (kg/h)
m _f
m daf (kg/h) _ a (kg/h)
m _ s (kg/h)
m YH2 O (% wt.) Frg
Dealcoholised 1200 0.61 0.51 2.4 0 0 1.53
marc of grape 1.33 1.14 3.38
2.04 1.74 5.17
750 1.4 1.19 2.4 0 0 3.54
750 1.11 0.94 1.08 0.9 45.4 6.23
1050 1.11 0.94 6.24
1200 1.105 0.94 6.22
750 0.99 0.84 0 1.6 100 e
1050 0.90 0.76 e
1200 0.925 0.79 e

m_ f : fuel mass ow rate in kg/h.


m_ f daf : dry, ash-free fuel mass ow rate in kg/h.
m_ s : steam mass ow rate in kg/h.
m_ a : air mass ow rate in kg/h.
YH2 O : steam content in the gasifying agent in % wt.
Frg : relative fuel/air ratio (with respect to the stoichiometric one).
J.J. Hernndez et al. / Energy 50 (2013) 333e342 335

Table 3
List of detected compounds in the HPLC analytical methods developed.

Group Compound name Abbreviation Standard TEF [37]


concentration
(mg/ml)
PAHs Acenaphtene Ac 1000 0.001
Acenaphtylene Acy 1000 0.001
Anthracene Anth 100 0.001
Benz(a)anthracene BaA 100 0.1
Benz(b)uoranthene BbF 200 0.1
Benz(k)uoranthene BkF 100 0.1
Benz(g,h,i)perylene BghiPe 200 0.01
Benz(a)pyrene BaPy 100 1
Chrysene Chy 100 0.01
Dibenz(a,h)anthracene DahA 200 1
Fluoranthene FluA 200 0.001
Fluorene Fluo 200 0.001
Inden (1,2,3-cd)pyrene InPy 100 0.1
Naphtalenea Naph 1000 0.001
Phenanthrene Phe 100 0.01
Pyrene Pyr 100 0.001
BTEX Benzene Ben 2000 e
Toluene Tol 2000 e
Ethylbenzeneb Et-Ben 2000 e
Xylene (o-, m-, p-) Xyl 2000 (each one) e
Heteroatomic compounds Phenol Phen e
Pyridine Pyrd 1 mL, pure e
a
Coeluted with ethylbenzene.
b
Coeluted with naphthalene.

possible to obtain the ow rate of the non-condensable fraction of the gas composition and the gas outlet temperature were period-
the product gas ow. The dry-basis gas composition is determined ically registered. Once the operation was stabilised, several values
on-line every 2 min by a gas micro-chromatograph VARIAN CP- of the gas metre were registered in order to calculate the average
4900 PRO located at the end of a sampling line. producer gas ow rate. After 20e30 min, when the gas composition
The experimental procedure in the gasication tests was as detected by the micro-GC (in dry basis) was steady, the test was
following: the biomass, previously ground and homogenized below nished and the duration of the test was registered. All ows
0.5 mm, was weighed and loaded into the feeding hopper. After (biomass, air and steam) were stopped. Both the ash-char hopper
reaching the set temperature point in the electrical furnace, and and the cold trap were taken out, their contents being weighed (in
having adjusted the air and steam ows according to the experi- order to perform mass balances) and sampled (the method for
mental schedule shown in Table 2, the screw feeder was turned on. sampling and analysis of tars is detailed in Section 2.3).
In all tests the steam inlet temperature was set at 400  C, and the For the overall study of the gasication process, it is necessary to
maximum steam ow rate has been 1.6 kg/h. During the test, both carry out an analysis of both the process performance and the tar

Table 4
Effect of the operating temperature and the gasifying agent on the speciation of tars.

Group Compound TPi (mg/Nm3)

Air 54.6 Air/45.4 steam (% wt.) Steam

T 750  C T 1200  C T 750  C T 1050  C T 1200  C T 750  C T 1050  C T 1200  C


PAHs Naph Et-Ben 297.2  0.6 211.3  0.6 302.2  1.5 1039.2  1.1 763.8  4.8 7418.2  6.0 4374.3  0.9 2784.9  1.6
Acy 248.6  6.8 220.2  0.2 249.6  1.0 684.3  5.8 531.0  8.3 10782.5  4.1 2209.1  0.3 1875.3  1.5
Ac 96.0  1.2 42.2  1.2 381.1  1.7 201.9  7.5 159.2  20.7 5525.5  9.6 701.3  3.9 1773.2  9.0
Fluo 88.2  0.2 15.7  0.3 67.9  1.2 185.2  0.9 57.3  72.7 593.1  29.9 920.4  0.5 238.8  0.3
Phe 77.4  0.3 44.9  0.1 47.3  2.4 229.9  0.1 119.6  3.2 2078.0  0.5 792.4  0.7 525.7  0.5
Anth 25.5  0.6 11.0  0.8 16.2  1.9 62.7  0.5 33.3  5.1 515.0  0.5 234.5  0.7 137.3  0.5
FluA 75.1  31.6 39.3  0.8 61.2  12.9 152.8  0.2 77.4  5.2 1524.9  1.7 501.8  0.2 467.1  0.6
Pyr 43.9  0.4 30.0  0.3 60.0  2.2 94.9  2.6 52.0  8.3 1125.5  2.1 305.3  1.1 253.8  0.9
BaA 14.8  1.2 6.4  1.0 15.7  84.9 33.9  21.2 11.8  8.9 343.4  33.0 139.1  1.8 81.5  18.8
Chy 10.8  0.3 2.7  1.4 6.2  43.0 19.6  2.5 9.7  9.6 230.5  35.5 67.6  2.9 52.8  4.5
BeBF 11.75  1.34 0.61  0.76 19.9  21.8 19.0  9.40 11.5  21.7 300.4  9.6 70.9  6.6 52.2  1.0
BeKF 4.37  1.25 1.66  0.17 4.8  36.8 8.3  19.7 8.1  36.0 155.3  42.8 39.5  13.3 29.8  8.2
BaPy 0.81  0.48 0.68  0.53 19.9  61.6 19.0  19.0 11.5  27.0 300.4  71.2 70.9  10.5 52.2  13.6
DahA 7.08  0.73 2.71  0.40 4.8  76.3 8.3  20.8 8.1  48.5 155.3  5.0 39.5  28.9 29.8  35.7
BghiPe 5.94  0.3 3.09  0.9 2.1  48.7 2.2  14.8 1.4  85.3 21.2  15.3 6.9  33.5 3.2  11.8
InPy 4.7  0.7 1.6  1.9 6.1  73.5 17.9  2.5 24.4  86.2 578.5  5.6 69.2  15.7 160.4  2.2
BTEX Ben 5.9  2.7 3.1  2.8 3739.5  6.6 1633.4  14.0 1000.8  20.5 566.3  21.9 52.5  3.4 86.6  4.2
Tol 4.7  2.7 1.6  0.5 1377.0  4.8 297.7  22.7 738.2  60.1 331.3  22.1 35.4  6.3 52.1  10.7
Xyl (o- m p-) 2598.6  0.6 1847.6  0.6 2642.8  1.5 9087.6  1.4 6679.3  4.8 64872.2  6.0 38253.7  0.9 24354.2  1.6
Heteroatomic Phen 1584.74  0.6 162.4  1.1 5883.5  0.6 1574.3  0.5 962.3  0.3 189914.9  0.6 7343.7  0.5 3239.7  0.3
compounds Pyrd N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D.

N.D.: not detected.


336 J.J. Hernndez et al. / Energy 50 (2013) 333e342

Fig. 1. Biomass entrained-ow gasication pilot plant.

production. The former issue is determined through several gasi- at 4  C. The lters containing the solid particles are Soxhlet
cation parameters presented in previous works [38]: producer gas extracted with 250 mL of 2-propanol for 6e8 h, until the solvent
net heating value (LHVpg, in MJ/kg), gas yield (GY, in Nm3/kgdaf, drops are clear. The volume of the liquid fraction obtained after
dened as the dry, N2-including gas ow rate produced for every the Soxhlet extraction is measured, and added into the rest of
kilogramme of dry, ash-free fuel introduced), and cold gas ef- sample, whereas the particles extracted are oven-dried at 105  C
ciency (CGE, in %, dened as the chemical energy content of the for 3e4 h, and then weighed. The volume and temperature of the
product gas compared to that of the original solid fuel). total tar sample are measured after being homogenised. 100 mL of
Table 2 sums up the gasication tests performed in this work, the total tar sample are introduced in an atmospheric distillation
where m _ f is the fuel mass ow rate in kg/h; m _ f daf is the dry, ash- facility in order to determine the gravimetric tar production.
free fuel mass ow rate in kg/h; m _ a represent the steam
_ s and m Simultaneously, 1 mL of the tar sample is microltered before
and air mass ow rates in kg/h, respectively; YH2 O is the steam being introduced into vials and HPLC analysed. Analysis vials
content in the gasifying agent in %wt., and Frg is the relative fuel/air made of dark glass are kept in the freezer in order to prevent tar
ratio (dened with respect to the stoichiometric one). Although polymerisation until they are completely HPLC analysed. An HPLC
some operating conditions (in particular, high steam content and Shimadzu system with ultravioletevisible detector was used for
low temperature) lead to an excessive tar production and thus are the determination of the tar composition. Two different analytical
not realistic conditions of commercial gasication plants, it is worth methods (each one with a different chromatographic column) were
remarking that the objective of this work is not tar removal, but an developed. The rst one was used for the analysis of PAHs and BTEX,
extensive comparison of tar properties (composition, technical and whereas the second method detects phenol and pyridine. After the
environmental hazard) when modifying the gasier operating analytical method for PAH and BTEX detection is started up and all
conditions, for which extreme values have also been evaluated. In tar samples obtained from gasication tests are properly sampled
addition, the low residence times of reactants within this small- and HPLC analysed, the HPLC column is replaced and the analytical
scale reactor leads to lower fuel conversion and higher tar method for phenol and pyridine detection is developed and cali-
production than those typical of commercial drop-tube gasiers. brated. After the method is ready to use, all the analysis samples
(which, in the meanwhile, had been stored in dark vials at very low
2.3. Tar sampling and analysis temperature) are injected again according to the analytical condi-
tions of each column. PAHs and BTEX analytical method uses
The procedure used to sample and analyse the tars produced in a SUPELCO Analytical 5 mm 250  4.6 mm column, a mobile phase of
the gasication process is as follows: the content of the cold trap is water/acetonitrile at a ow rate of 1.5 mL/min, the analysis
weighed and extracted after each gasication test. This fraction temperature and the analysis time being 25  C and 50 min respec-
contains water, some tars and particles dissolved. Next, the trap is tively. On the other hand, phenol and pyridine analysis is carried out
rinsed three times with 500 mL of 2-propanol (solvent recom- with a Supelcosil LC8 3 mm 150  4.6 mm, at 30  C and with a mobile
mended by the guideline method) [35]. This second fraction phase of water/methanol/acetic acid (1 mL/min), the analysis time
contains non-polar tars and some remaining particles dissolved in being 25 min. The detector wavelength has been 254 nm in both
2-propanol. After both fractions are separately ltered and their methods. As recommended in [35], the elapsed time between
volume measured, they are homogenised and stored in dark bottles sampling and HPLC analysis did not exceed a month in any case.
J.J. Hernndez et al. / Energy 50 (2013) 333e342 337

Table 3 contains the compounds detected, as well as the name


abbreviations used in the gures, the concentration of every indi-
vidual compound in the standard mixtures, and the values of their
toxicity factor (TEF). The standards mixtures injected for calibration
purposes were the following:

- A PAHs standards mixture (SUPELCO EPA 610 Polynuclear


Aromatic Hydrocarbons Mix 100e2000 mg/mL methanol:
chloroform 1:1, 1 mL).
- A certied BTEX standard mixture (HC BTEX Mix 2000 mg/mL in
methanol, 1 mL). The mixture contained benzene, toluene,
ethyl-benzene and o-, m-, and p-xylene.
- Individual standards of benzene, toluene, and o-, m-, and
p-xylene (5000 mg each one) in order to identify the order or
the peaks detected in the BTEX standard mixture.
- A certied phenols standard (SUPELCO EPA Phenols Mixture
500e2500 mg/L in methanol, 1 mL).
- An individual standard of phenol (1000 mg).
- A standard of pure pyridine (1 mL).

Calibration of the HPLC system was carried out using the stan-
dards at different concentrations (350, 300, 200, and 50 mL of
standard mixture diluted in acetonitrile or methanol). Each cali-
bration sample was injected three times in order to check the
analysis repeatability.
The correlation factor obtained after the calibration procedure
was R2 0.999 for all the PAH compounds, except for anthracene
and chrysene, with lower but admissible correlation factors
(R2 0.995 and R2 0.989, respectively). In the case of BTEX
calibration, correlation factors ranged from R2 0.966 (p-xylene) to
R2 0.998 (toluene). Concentrations lower than 0.3 mg/mL were not
considered by the software (lower detection limit of the HPLC
system). It is worth mentioning that both ethyl-benzene and
naphthalene co-elute, thus, the detection peak corresponds to the
sum of both compounds.
As for the analysis of the tar obtained from gasication tests, Fig. 3. Effect of the relative fuel/air ratio (Frg) on the composition of the tars produced:
each tar sample was analysed three times in order to check the (a) PAHs, and (b) BTEX and phenol.
repeatability of the test. Calibration was controlled before each
analysis introducing a standard sample. In case any compound was
wrongly detected, the calibration process was repeated. iHPLC $Vtotal $103
Tar production was evaluated through several parameters: TPi (1)
V_ pg $ttest
- Individual production of tar compounds detected by liquid
being [i]HPLC the concentration of the individual compounds from
chromatography, TPi (expressed in mg/Nm3 product gas).
HPLC, in mg/mL, obtained from the chromatographic analyses; Vtotal
the measured volume of total tar sample in mL; V_ pg the product gas

Fig. 4. Effect of the relative fuel/air ratio (Frg) on the tar dew point and the carcino-
Fig. 2. Effect of the relative fuel/air ratio (Frg) on the total tar production. genic potential of the tars produced.
338 J.J. Hernndez et al. / Energy 50 (2013) 333e342

ow rate in Nm3/h, measured from the gas metre; and ttest the by Narvez et al. [41]. The non-linear increase occurs for all the
measured duration of the gasication test in h. families considered in the tar: PAHs, BTEX, and phenol (it is worth
remarking that pyridine was not detected in any test). Moreover, it
- Total tar production, TP (in mg/Nm3, calculated as the sum of can be checked that when increasing the relative fuel/air ratio from
the individual productions). 1.5 to 3.4, the contribution of BTEX in the total tar amount suffers an
increase, whereas both PAHs and phenol slightly decrease.
X
TP TPi (2) However, beyond Frg 4, an increase in the relative fuel/air ratio
i does not inuence tar distribution. Moreover, it is worth remarking
that the BTEX group is the most abundant in the tar mixture,
- Tar dew point (in  C), calculated from the complete model accounting for 60e70% of the total tar production, whereas phenol
developed and validated by the ECN [13]. contributes in all cases with less than 10% of the total amount. PAHs
- Tar carcinogenic potential, KE (in mg/Nm3), calculated from the keeps around 20e30% in the range of Frg tested.
tar production of the individual PAH compounds and their Fig. 3 details the effect of the relative fuel/air ratio on the tar
respective factors of toxicity, TEF, as proposed by Zorn et al. [40] composition (PAHs, BTEX, and phenol). Although it had been
(see Table 3): already observed in Fig. 2 that BTEX is the most signicant group in
tars, among them xylenes are by far the most abundant
X
KE TPi $TEFi (3) compounds, reaching values around 10000 mg/Nm3, whereas
i benzene and phenol production are of the same magnitude. The
most abundant PAHs produced are by far lighter ones such as
being in this case the subscript i each one of the PAH compounds naphthalene and acenapthylene, whose production is similar to
detected. benzene and phenol, around 1000 mg/Nm3 at Frg 5.2. Similar
naphthalene production was obtained by Rapagn et al. [30],
3. Results and discussion although in their work, xylenes were not analysed by HPLC and
toluene was the most abundant tar compound. PAHs higher than
3.1. Effect of the relative fuel/air ratio chrysene have a very low concentration in the mixture. Lastly, in
Fig. 3 it can be appreciated that there is a non-linear increase of all
The relative fuel/air ratio, Frg (or inversely, the equivalent ratio the tar components with Frg. These results are consistent with the
ER), which is dened as the fuel/air mass ratio respect to the stoi- literature, since a higher availability of oxygen in the process
chiometric one, is considered one of the main operating parameters (higher when reducing the Frg values) was found to favour the
of the air- and air-steam gasication processes [18,39,41e44], since destruction via oxidation of the volatile matter released in the
it inuences fuel conversion, the heating value of the product gas pyrolysis stage [9,12,14,26].
and tar production. Fig. 4 details the effect of the relative fuel/air ratio on the tar dew
For this section, the experimental gasication tests were carried point and the carcinogenic potential. Both parameters are closely
out using air as gasifying agent. The operating temperature related to the tar composition, particularly to the production of
(measured as the external reactor temperature) was kept constant polycyclic aromatic hydrocarbons. It can be observed that the
at 1200  C, typical value of entrained-ow gasiers. The relative increase in Frg leads to a slight rise in the dew point from 174  C to
fuel/air ratio Frg was modied by adjusting the fuel ow rate in 210  C, and to an exponential boost in the carcinogenic potential for
order to keep as constant as possible the space residence time Frg values higher than 3.4, the latter being caused by the non-linear
(which has a signicant effect on the fuel conversion). Frg values increase of heavier PAHs (Fig. 3).
tested range from Frg 1.5 (value close to a combustion process) to However, in order to determine the optimal operating condi-
Frg 5.2 (high value near pyrolysis conditions), including an tions, it is necessary to take also into account the overall effect of the
intermediate value typical of gasication processes (Frg 3.4). The relative fuel/air ratio on the gasication process performance. With
results obtained in tar characterisation are displayed in Figs. 2e4. that purpose, Fig. 5 plots the effect of Frg on the heating value of the
In Fig. 2 it can be observed that tar production increases non- producer gas (LHVpg), the gas yield (GY) and the cold gas efciency
linearly with the relative fuel/air ratio, rising from 1 g/Nm3 gas (CGE). When increasing Frg, the relative amount of air available in
(at Frg 1.5) to 15.3 g/Nm3 (Frg 5.2). Similar values were obtained the process decreases, and thus char gasication reactions occur at

Fig. 5. Effect of the relative fuel/air ratio (Frg) on the gasication performance: product gas heating value (LHVpg), gas yield (GY), and cold gas efciency (CGE).
J.J. Hernndez et al. / Energy 50 (2013) 333e342 339

a higher extent compared to oxidation reactions. Consequently, the


heating value of the product gas increases. Nevertheless, as Frg rises,
the process is increasingly approaching a pyrolysis; a higher amount
of fuel remains unreacted, thus decreasing the gas yield (GY). The
opposite trends of gas heating value and fuel conversion are
responsible of the existence of a maximum in the cold gas efciency
curve at intermediate Frg values.
As a conclusion, the operation at intermediate Frg values
(Frg w 3e4) leads to a trade-off between gasication performance
(product gas heating value, gas yield) and tar properties (relatively
low tar production and carcinogenic potential values).

3.2. Effect of the operating temperature and steam content in the


gasifying agent

As mentioned in Section 1, temperature is one of the main


operating parameters affecting tar production and composition.
Actually, temperature inuences all the stages taking place during
the thermochemical process of solidegas conversion: fuel devola-
tilisation, and char gasication reactions. For this section, the effect
of temperature (measured as the external temperature of the
reactor) has been evaluated using three different gasifying agents:
air (YH2 O 0% wt.), steam (YH2 O 100% wt.), and a mixture of air
and steam (YH2 O 45.4% wt.), as shown in Table 2. This latter
composition was selected within the range of optimal conditions
determined in a previous study [45]. In all tests, the fuel/gasifying
agent (air steam) mass ratio was kept as constant as possible,
around 0.5, in order to study the role of air and steam while keeping
constant the space residence time.
Fig. 6 plots the effect of temperature on the total tar production
TP for the three gasifying agents tested. It can be checked that the in
the case of using pure air or pure steam, the amount of tars
generated in the process is reduced as the temperature increases,
which indicates a higher extent in the thermal cracking and steam
reforming reactions. Moreover, the decrease in tar production in
the case of steam gasication seems to follow a non-linear trend,
since the reduction of tar production is much more notable when
increasing the temperature from 750  C to 1050  C than an increase
in temperature from 1050  C to 1200  C. However, in the case of
gasication with a mixture of air and steam (YH2 O 45.4% wt.),
a peculiar trend has been obtained: the reduction of tar production
starts to be signicant only at temperatures higher than 1050  C,
being the amount of tars produced similar at 750  C and 1050  C.
The reasons behind this behaviour must be further studied, but
they might be related to the combined effect of air and steam [45].
On the other hand, it is worth observing that there is a non-
linear increase of tar production when adding steam into the
gasifying agent. This behaviour might be related to the roles of air
and steam when introduced together into the process. The
combustion reactions associated to air prevent the temperature
within the reactor to drop excessively, as well as to contribute to the
production of CO and CO2 (via combustion, partial combustion
and Boudouard reactions), so that the net effect of air is the
improvement of devolatilisation, tar cracking and gasication
endothermic reactions. On the other hand, steam mainly promotes
the steam reforming of char and tars and the water-gas shift Fig. 6. Comparison of the effect of the operating temperature and the gasifying agent
reaction (thus enhancing H2 production), as pointed by several on the production of tars.
authors [15e17,45e50]. When increasing the steam content (thus
decreasing the air proportion), several factors (namely, the reduc- In Fig. 6 it can also be appreciated that BTEX constitute the most
tion of the extent of the faster combustion reactions associated to abundant fraction in the tar mixture; nevertheless, as the steam
air, the strongly endothermic nature of steam reforming reactions, content and/or the operating temperature decrease, the proportion
and the presence of excess steam that does not take part in the of phenol in the tar samples is increasingly favoured (as shown in
reactions) lead to a drop in the temperature within the gasier, as Fig. 7). Thus, in the most extreme case (steam gasication at
observed by other authors [47,48,50e52], and therefore, tar 750  C), phenol is observed to account for almost half of the tars
production increases. produced. In addition, the total tar production is clearly boosted
340 J.J. Hernndez et al. / Energy 50 (2013) 333e342

Fig. 7. Effect of the operating temperature on the evolution of tar composition.

when increasing the steam content of the gasifying agent. There- previously observed in the air gasication process, not only is tar
fore, both the temperature and the gasiyng agent inuence not production higher, but also tar composition seems to be affected by
only the amount of tars, but also their composition. These results increasing temperature: whereas at 750  C the most important
are consistent with those found in the literature. As stated by other compounds are phenol and benzene, at 1200  C xylenes are by far
authors, lighter hydrocarbons and oxygenated compounds are the most abundant species. Moreover, at high temperatures,
transformed at higher temperatures into heavier, more stable PAHs, naphthalene concentration becomes of the same magnitude as
which are precursors of soot [8,9,12,14,20e25]. Therefore, the benzene, toluene and phenol. Lastly, it is worth noticing that, unlike
severity of the gasication process must be selected as a trade-off the results obtained in air- and steam gasication separately, higher
between the extent of the cracking reactions and the composition temperatures when gasifying with an air-steam mixture promote
of the remaining tars (more difcult to destroy via catalytic tech- the production of heavier PAHs such as dibenz(a,h)anthracene,
niques and precursors of soot) [9,14,20]. benz(g,h,i)perylene and inden(1,2,3-cd)pyrene (which might be
Table 4 provides detailed information on the effect of tempera- responsible for the increase in the carcinogenic potential of tars
ture on tar composition for the three gasifying agents tested (the produced from air-steam gasication at higher temperatures, as
standard deviation of each component concentration is also shown observed in Fig. 8).
in the table). It can be seen that, in the case of air gasication, the Lastly, in the speciation results obtained in the case of steam
most abundant compounds at 750  C are benzene, xylenes and gasication and shown in Table 4, it is remarkable the extremely
phenol, whereas at 1200  C the most representative compounds of high production of phenol at low temperatures, which exceeds
the tar mixtures are xylenes. PAHs are the least abundant 180 g/Nm3, and which is by far the most abundant species of the tar
compounds regardless of the operating temperature, keeping in sample obtained at 750  C. Phenol is followed from benzene and
all cases below 300 mg/Nm3. Moreover, the production of light xylenes, being PAHs the least abundant compounds present in tars.
PAHs (naphthalene, acenaphtylene) is signicantly higher than the However, an increase in temperature leads to a dramatic decrease of
concentration of the rest of polyaromatic compounds detected. As all the species detected in the tars. Moreover, in some cases (phenol,
found in Fig. 6, it can be conrmed the reduction of the production of benzene, toluene, and most of the PAHs) the decrease clearly follows
all the groups present in the tar mixture when temperature a non-linear trend. At 1200  C, the most abundant compounds are
increases. xylenes. Production of PAHs is signicantly less important, being
As for the case of a mixture of air and steam as gasifying lighter species such as naphthalene, acenaphtylene or acenaphtene
atmosphere (central columns of Table 4), it is worth remarking the the most abundant among the polyaromatic compounds. Therefore,
existence of non-linear trends: although compounds such as it is evident that temperature affects both tar production and
benzene, phenol and acenaphtene decrease at higher temperatures, composition. These results are consistent with those found in
most of the species detected present a maximum (e.g. xylenes, literature: as already discussed in Section 1, higher temperatures
naphthalene, acenaphtylene, uoranthene, phenanthrene, anthra- causes an increase in the extent of the reactions of thermal cracking,
cene) or a minimum (toluene) at intermediate temperatures. As thus destroying primary tars. However, the remaining tars are

Fig. 8. Effect of the operating temperature and the gasifying agent on the tar dew point and the carcinogenic potential of tars.
J.J. Hernndez et al. / Energy 50 (2013) 333e342 341

Fig. 9. Effect of the operating temperature on the gasication performance: product gas lower heating value (LHVpg) and cold gas efciency (CGE).

increasingly transformed into more refractory polyaromatic addition of steam leads to an increase of the product gas quality
aromatic compounds (the so-called tar maturation process) re- owing to a less dilution in N2 from air, as well as to the modication
ported by Milne et al. [9]. Moreover, soot formation (secondary char) of the extent of the gasication reactions (steam reforming and
via gas-phase nucleation mechanisms is favoured at high temper- WGS reactions are enhanced, thus favouring the production of CO
atures [23]. and H2, and therefore, increasing gas heating value). Higher
Fig. 7 plots the evolution of tar composition in function of the temperatures lead to an overall improvement of the gasication
operating temperature and the gasifying agent used. The results process regardless of the gasifying agent used. However, there is
observed in previous gures can be conrmed, namely, the a range of temperatures (T < 900  C), in which the cold gas ef-
progressive aromatisation of tars when increasing the temperature ciency of air-steam gasication exceeds the values obtained in pure
regardless of the gasifying agent used (an increase of the propor- steam gasication. On the contrary, at temperatures above 900  C,
tion of PAHs and BTEX, as well as a decrease in the content of the process efciency increases with the steam content of the
phenol). Nevertheless, it is interesting to observe both a higher gasifying agent.
sensitivity of tar composition with temperature as the steam
content increases, and the effect of steam to be signicant only at 4. Conclusions
temperatures lower than 1000  C, the latter being maybe due to the
higher rate of steam reforming reactions at high temperatures In this work, two HPLC analytical methods have been developed
(comparable to that of combustion reactions). for the detection of the most important compounds present in
Lastly, Fig. 8 plots the effect of temperature on the level of biomass gasication tars: PAHs, BTEX, phenol, and pyridine. This
technical and environmental hazard of tars produced, quantied by technique has been used for the determination of the tar compo-
the tar dew point and the carcinogenic potential, respectively. It can sition in an experimental study of the effect of the main operating
be seen that in the cases of air- and steam gasication, higher conditions of a biomass entrained-ow gasication process. The
temperatures cause a slight decrease in the tar dew point, being results obtained show that:
more notable in the case of steam gasication when increasing the
temperature from 750  C to 1050  C. On the contrary, combined - An increase of the relative fuel/air ratio Frg leads to a non-linear
air-steam gasication leads to inverse trends, increasing the tar rise of the tar production due to the lower amount of available
dew point with the operating temperature. This behaviour, as oxygen to oxidise the volatile matter released from the fuel.
discussed previously in Table 4, might be due to the increase in Moreover, a progressive increase in the BTEX fraction of tars
heavier PAHs, which exceeds the reduction in the overall tar has been found when increasing Frg from 1.5 to 3.4. However,
production. The same reason explains the increase in the carcino- taking into account the overall effect on the gasication
genic potential KE, which again shows opposite trends in the case process, it is recommended to operate at intermediate Frg
of air-steam gasication. It is worth remarking that the toxicity of values as a trade-off between gas quality, process efciency,
tars produced from steam gasication (KE w 200e800 mg/Nm3 in fuel conversion, and tar properties (production, and carcino-
the range of temperatures tested) is dramatically higher than in genic potential).
case of using air in the gasication process (keeping in the latter - Higher operating temperatures reduce the total amount of tars
case always below 40 mg/Nm3), although the reduction of KE with produced; nevertheless, it takes place a progressive aromati-
temperature is more notable when using steam. This behaviour sation of the remaining tars, as observed by the reduction in
might point out again at the roles of molecular oxygen O2 as the phenol proportion, and the increase in the PAH and BTEX
oxidiser of volatile matter released in the pyrolysis stage, and of fractions. Both tar carcinogenic potential and dew point are
temperature as promoter of thermal cracking reactions. Therefore, reduced (the latter in a lesser extent) when increasing
in autothermal gasiers the introduction of oxygen promotes the temperature for air- and steam gasication.
tar destruction via two simultaneous mechanisms: the increase of - The combination of high steam contents and low temperatures
the extent of the oxidation reactions of volatile matter and the favours the production of phenol in tars. Moreover, the use of
associated increase of temperature. steam increases the sensitivity of tar composition to changes in
The previously discussed results on tar production must be the operating temperature.
compared with the effect of temperature on the gasication - The introduction of steam in the gasifying agent at a constant
performance, displayed in Fig. 9. It can be rstly observed that the temperature leads to a non-linear increase of tar. However, it
342 J.J. Hernndez et al. / Energy 50 (2013) 333e342

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