b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1

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A promising new on-line method of tar

quantification by mass spectrometry during steam
gasification of biomass

F. Defoort*, S. Thiery, S. Ravel

CEA, DRT/LITEN/DTBH/LTB, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France

article info abstract

Article history: This paper presents an on-line method of measuring at mm3 m
3 level some organic
Received 23 July 2013 compounds such as BTX (Benzene, Toluene, Xylene) and PAH (Polycyclic Aromatic Hy-
Received in revised form drocarbon) which are called tar for biomass gasification applications. This method is
25 March 2014 based on the ion molecule reaction (IMR) mass spectrometer (MS) principle. Due to the low
Accepted 2 April 2014 energy of ionization of Hg, Xe or Kr almost no overlapping spectra can damage the inter-
Available online 19 April 2014 pretation of the detected results. IMR-MS results of concentrated (above cm3 m
3) and trace
(below cm3 m
3) tars are presented after a bubbling fluidized bed and a tar cracker
Keywords: respectively. Results are compared with other measurement methods such as microgas
BTX chromatography for benzene and toluene or Tar Protocol or Solid Phase Adsorption tech-
PAH nique both methods for BTX and PAH giving good confidence to the results.
On-line 2014 Elsevier Ltd. All rights reserved.
Mass spectrometry
Gasification
Biomass

On-line measurements of BTX are currently made by

1. Introduction
Contaminants present in the gas obtained from the biomass
gasification may induce saturation of the gas cleaning sys-
tems or degradation of the catalysts used for fuel synthesis.
They are important to be measured on-line in order to detect
rapidly their variations for process control. Furthermore, after
gas cleaning systems, they are at a trace level, i.e. at mm3 m
3
level. These contaminants are gaseous organic compounds
such as BTX (Benzene, Toluene, Xylene) and PAH (Polycyclic
Aromatic Hydrocarbon) which are called tar for biomass
gasification applications. Some gaseous inorganic compo-
nents as sulfured species (H2S, COS, thiophene.) are also
contaminants.
micro-gas chromatography with a thermal conductimetry
detector (mGC-TCD). The detection limit is above several
cm3 m
3 [1]. Naphthalene can also be measured on-line
directly in the gas phase by FTIR (Fourier Transform Infra-
Red) [2]. Naphthalene, fluoranthene and pyrene by LIF (Laser
Induced Fluorescence) [3e5]. The detection limit is above
several cm3 m
3 level for FTIR. LIF presents strong in-
terferences with other species present in the gas. Molecular
beam mass spectrometry (MBMS) is another on-line method
capable of measuring all tars from BTX to PAHs and others [6]
using a specific gas sampling to collect condensable species
thanks to a molecular beam inlet system. This method suffers
from the conventional high ionization energy (70 eV) when the

* Corresponding author. Tel.: 33 (0)4 38 78 46 53; fax: 33 (0)4 38 78 52 51.

E-mail address: francoise.defoort@cea.fr (F. Defoort).
http://dx.doi.org/10.1016/j.biombioe.2014.04.001
0961-9534/ 2014 Elsevier Ltd. All rights reserved.
 b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1 65

Fig. 1 e IMR-MS principle (partly reported from Ref. [17]).

electronic impact (EI) method is employed. Indeed the major
drawback with this ionization energy is the fragmentation of
molecules leading to complex mass spectra and multiple
overlapping intensities in complex gas mixtures. To overcome
this limitation several soft ionizations have been used with
photoionization techniques such as Resonance-Enhanced
Multiphoton Ionization (REMPI) or Single-Photon Ionization
(SPI) with Time-Of-Flight Mass Spectrometry (TOFMS) [7e9].
However, mainly identification and few quantifications are
performed. Other methods measuring on-line total tar con-
tents exist, such as the ECN Tar Dew Point [10], the FID (Flame
Ionization Detector) tar analyzer (TA 120-3) currently used by
IFK University of Stuttgart [11] or the PID (Photo-Ionization
Detection) tar analyzer recently developed by Ahmadi [12] but
the nature of the species is not known for these methods.
This paper presents a soft ionization mass spectrometry
method based on the ion molecule reaction (IMR) mass spec-
trometry (MS) principle. Such an IMR-MS method has already
been used to measure on-line major components (CO, CO2
etc.) as well as some inorganic (SO2, NO) or organic (benzene,
acetaldehyde) pollutants at the exhaust of incineration pro-
cesses [13,14]. However, to our knowledge, this method has
never measured the composition of a syngas from a biomass
gasification process.
2. Principle of IMR-MS
The IMR method is well known in ion physics. It is an
important path of primary ion loss in plasma. The monograph
by Harrison is especially recommended for further reading
[15]. A simplified description is given in our paper. IMR-MS
method is similar to CI-MS (Chemical Ionization Mass Spec-
trometry) but one of the differences is that the primary ion
source is run with an inert gas such as Hg, Xe, Kr instead of a
reactant gas such as NH3, CH4 or N2eH2O mixture. The main
pathway in IMR-MS to ionize a sampling gas G with a primary
inert gas ion A (A Hg, Xe or Kr) is a charge transfer as given
in [eq. (1)].
G NH4  /GH NH3 (2)
The principle of the IMR-MS method is explained in Ref.
[16] and schematized in Fig. 1.
An inert gas (Hg, Xe or Kr) is ionized by electron impact (EI)
in the chamber of primary ion ionization as:
A e/A 2e (3)
primary ionization.
Primary ions A are conducted to the reaction chamber
through a high frequency octopole ion guide. Here the primary
ions react with the sampled gas G with the ion molecule re-
action [eq. (1)]. Contrary to CI-MS, the chamber of primary ion
generation and the reaction chamber are separated in IMR-
MS. In addition, the ion molecule reaction happens with a
vacuum of w10 mPa (CI-MS about 100 Pa). The G ions
generated are conducted to a classical quadrupole and a
downstream counter to be separated (mass separation),
detected and quantified.
The ion molecule reaction [eq. (1)] can only occur if the
ionization potential of the primary ion A is higher than the one
of the gas sample G. Fig. 2 shows the ionization potential of
several molecules of interest and to the inert gas Hg, Xe and Kr.
For example the ionization potential of mercury
(IP(Hg) 10.43 eV) is higher than the one of BTX, PAHs and
thiophene (C4H4S). If the excess energy IP(Hg) e IP(G) is small
(w<1 eV) no fragmentation will occur otherwise it might be
used to break the weakest bond of the ionized molecule
leaving a lower molecular weight fragment ion. Mercury is
able to ionize these species almost without fragmentation as

G A /G A (1)

ion molecule reaction.

For CI-MS more complex ionization pathways are occur-
ring as proton transfer [Eq. (2)] Fig. 2 e Ionization potential of several molecules.
66 b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1

the Hg excess energy is small. Fig. 2 shows also that NH3, H2S
Table 1 e Technical details of the airsense apparatus.
and C2H4 can be ionized by mercury. Xenon (IP(Xe) 12.12 eV)
is able to ionize COS, CH4, C2H2, C2H6 and H2O. Krypton Mass range 0e512 amu
Resolution <1 amu
(IP(Kr) 13.99 eV) is able to ionize CO, CO2, HCl and HCN.
Analysis time >1 ms
Finally, these three inert ionized gases can measure all syngas
Measuring range Four decades possible
molecules (except H2). Mercury primary ionized gas is the best Response time T90 < 50 ms
case as it is not sensitive to species having higher ionization Lower detection limit <1 ppbv (benzene in air)
potential than Hg. The Hg mass spectrum is simpler than the <10 ppbv (benzene in exhaust gas)
Xe one that is itself simpler than the Kr one. A careful study Drift concentration <5% over 12 h (1 ppmv benzene)
must be done with Xe and Kr to check if there is a mass Reproducibility <3% (1 ppmv benzene)
Accuracy <2% (1 ppmv benzene)
overlapping due to isotopes and fragmentation.
Apparatus tested: The IMR mass spectrometer apparatus
tested in this work is called Airsense. An Austrian company
has developed it (V&F Analyse- und Messtechnik GmbH: the gas of the process (Fig. 3). A small filter is positioned just
www.vandf.com). It was rented for one month by CEA Gre- before the capillary to avoid clogging by dust or deposits. A
noble. It is currently used by V&F customers mainly for dilution with a neutral gas is possible just entering the vac-
automotive, food, beverages & tobacco applications but also uum chamber (Fig. 3).
for medical use [16e18]. It has never been used to analyze
syngas to our knowledge. A picture of the apparatus is shown
in Fig. 3. It is very compact (59 cm  65 cm  73 cm) and easy to 3. Experimental
transport thanks to wheels (100 kg). Its technical character-
istics are summarized in Table 1. The apparatus is equipped 3.1. Gasification tests
with a combined primary ion source for Kr, Xe and Hg. Each
inert gas is successively introduced in the chamber. The time Gasification tests were performed to measure tars in
required for each inert gas is controlled by a program written concentrated as well as in trace amounts. Concentrated tar
in the software. This is decided before the experiment. The measurements, i.e. above cm3 m
3 level, were performed in
software is able to operate the apparatus with two modes: the raw product gas at the exhaust of the fluidized bed fa-
cility (LFHT) developed at CEA-Grenoble. Traces tar mea-
1 The scan mode where all masses from 1 to 500 amu are surements, i.e. below cm3 m
3 level, were performed at the
scanned for each ion source. This mode allows checking of exhaust of the tar cracker (gas reforming) reactor (PEGASE).
isotopes and overlapping. Then, the correct amu can be An insulated line, heated to 800  C in order to avoid
chosen to be recorded during the process. condensation of inorganic species, links both facilities. Full
2 The monitoring mode, in which more than 20 mass amu description of both facilities is emphasized in Ref. [19]. Steam
for each of the three ion sources are recorded versus time. gasification of wheat straw at a temperature of 850  C, total
This allows the tracking of the process versus time for the pressure of 0.2 MPa and biomass flow rate of 1 kg h
1 (steam
selected amu. to biomass mass ratio of 2) has been performed in the flu-
idized bed. The temperature of the tar cracker has been set at
The software and the required skills for operation are very 1400  C. Fig. 4 is a schematic view of the facilities where tars
easy to use. sampling are presented.
To avoid condensation of water and condensable species Sampling is possible before and after the cold traps for both
(tars, NH4Cl), a heated (180  C) low pressure capillary samples facilities.

Fig. 3 e Photos of the airsense apparatus and of the heated capillary sampling line.
 b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1
Fig. 4 e Schematic view of the pilot scale facilities LFHT linked to PEGASE and gas analysis.
3.2. Gaseous measurement methods
The IMR-MS measurements were performed after and before
cold traps to check the accuracy of results in dry and wet gas
and to measure steam content on wet gas. Because the gas
inlet chamber is not heated, a dilution factor of 4 with nitrogen
was applied for wet sampling to make sure no condensation
has happened. This has been performed by introducing a
neutral gas flow rate just before entering the gas inlet cham-
ber of the apparatus (Fig. 3). The dilution factor was adjusted
before to connect the apparatus to the sampling point by
measuring O2 from ambient air. No dilution was applied on
dry gas because it was unnecessary. Calibration of the appa-
ratus was done for BTX, steam and some other components
(H2S, COS, NH3, HCN, HCl, CH4, C2H4) with certified gas stan-
dard bottle tanks. No calibration was done for PAH and thio-
phene. However, a semi-quantitative results could be
obtained from the experience of V&F, by applying the benzene
sensitivity (in cps (cm3 m
3)
1) to these compounds. IMR-MS
records are every 25 s.
Other tar measurement methods were performed in order
to compare the results between them and the IMR-MS one:
 BTX gaseous species C6H6, C7H8 C8H10 are measured on-
line by micro-gas chromatography (mGC) coupled with
thermal conductivity detectors (TCD). As dry gas is neces-
sary for this apparatus, gas is sampled after the cold traps.
Other species are also analyzed by mGC because the
analyzer is equipped with four columns allowing the
measurement of Ar, CO2, CO, CH4, N2, H2, C2H2, C2H4, C2H6,
C3H8 and H2S and COS. Every 3 min a spectrum is acquired.
This method allows measurement of BTX above several
cm3 m
3.
Two other measurement methods are also implemented:
the well known tar protocol method (TP) [20] and the solid
phase adsorption SPA method [21]. Both methods are off-
line and based on condensation of tar in liquid phase
(isopropanol) thanks to an impinger train for TP and in a
solid amino phase adsorbent for the SPA. Gas is sampled
before the cold trap in order to measure condensable
67
species such as PAHs in addition to BTX. SPA probes and
liquid samples of TP are analyzed later by gas chromatog-
raphy (GC) with a flame ionization detector (FID) and after a
thermal desorption for SPA. Both methods allow mea-
surements of BTX and PAHs. TP allows measurement
above cm3 m
3 level and SPA above roughly 10 mm3 m
3
[1].
For all these gas analysis methods, a great care was made
on the sampling method in order to avoid any deposit of tar
and water or any change in the tar content before the sam-
pling point (heated line or dilution by a neutral gas).
4. Results
4.1. Mass spectra
An example of syngas mass spectra acquired on wet gas
(dilution 4:1) in the raw product gas at the exhaust of the
fluidized bed with the mercury ions source is presented in
Fig. 5a and b for mass 10e100 and 100e200 respectively.
a: mass 10e100 amu
b: mass 100e200 amu
It is observed that the masses corresponding to benzene,
toluene, thiophene, phenol, indene, acenaphthylene,
biphenyl acenaphtene, fluorene,
phenanthrene anthracene are well defined. The other
masses observed are from their isotopes. Calculations of the
isotopic ratio are in line with the intensity ratio measured in
Fig. 5. Furthermore it is observed that some others masses
corresponding to some inorganic gaseous species such as H2S,
NH3 or hydrocarbon C2H4 are present (Fig. 5a).
4.2. Concentrated tars (above cm3 m
3)
Figs. 6e10 present the concentration of benzene, toluene,
thiophene, indene, acenaphthylene, biphenyl acenaphtene,
68 b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1
Fig. 5 e Mass spectra in the raw product gas at the exhaust
of LFHT (wet gas).
fluorene, phenanthrene anthracene recorded versus time in
the raw product gas at the exhaust of the fluidized bed before
the cold traps in wet gas (12:00 to 13:25) and after the cold
traps in dry gas (13:25 to 14:40).
In these figures the dilution correction and the wet to dry
correction have been done to present all results as cm3 m
3
dry with neutral gas included. Results obtained are in agree-
ment with expected BTX and PAH values currently obtained in
these conditions, i.e. in the 1000 cm3 m
3 level for benzene,
50 cm3 m
3 for naphthalene, 10 cm3 m
3 for toluene and
1 cm3 m
3 for PAHs [19,22].
A very good agreement is observed for benzene and
toluene between the four analytical methods IMR-MS, mGC-
Fig. 6 e Benzene volume concentration (fluidized bed)
measured by IMR-MS, mGC-TCD, TP and SPA in wet gas
sampling and dry gas sampling.
Fig. 7 e Toluene volume concentration (fluidized bed)
measured by IMR-MS, mGC-TCD, TP and SPA in wet gas
sampling and dry gas sampling.
TCD, TP and SPA. Results are in the 15% relative uncertainties
range.
Naphthalene measurements are shown in Fig. 8. IMR-MS
results are lower than TP and SPA (factor 2). Taking into ac-
count that naphthalene is not calibrated but is linked to the
benzene IMR-MS response, the agreement is acceptable.
PAH results, shown in Fig. 9, indicate that IMR-MS results
are in between TP and SPA results. As naphthalene, PAHs are
not calibrated but are linked to benzene response.
Fig. 10 presents the IMR-MS results for thiophene that is
between 1 and 10 cm3 m
3. Thiophene is not calibrated and
there is no other method to compare. However, it is seen in the
literature that thiophene is measured in the 1e10 cm3 m
3
range in fluidized bed gasification [23].
Variations observed in the IMR-MS (and in the mGC-TCD)
records which are in the 10e20% relative uncertainties are not
significant to process events. However, the variations above
these uncertainties are significant. As an example, it is
observed that the apparatus is disconnected from the syngas
flux during the TP. A strong decrease of all components is thus
observed 25 s later. In Fig. 10 strong variations of the IMR-MS
signal between 10:55 and 11:02 that are related to process
event (over pressure in the reactor) are observed. This shows
the capability of and the interest in having an on-line method
even if the example cited is also observed with pressure sen-
sors. A study should be made with compositional change
Fig. 8 e Naphthalene volume concentration (fluidized bed)
measured by IMR-MS, TP and SPA in wet gas sampling and
dry gas sampling.
 b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1 69

Fig. 9 e PAHs volume concentration (fluidized bed)

measured by IMR-MS, TP and SPA in wet gas sampling.
Fig. 11 e Benzene volume concentration (tar cracker)
measured by IMR-MS and SPA in wet gas sampling and dry
gas sampling.

(biomass composition in homogeneity or saturation of a gas

cleaning unit).

4.3. Trace tars (below cm3 m
3)

Figs. 11 and 12 show the concentration of benzene and some

PAHs. The other tars were undetectable.
In these figures it is observed that results are more
consistent in dry gas rather than in wet gas because there is no
correction (dilution and dry gas i.e. factor 8) to apply to the dry
measurements as it is necessary for the wet one. Indeed,
before correction, measurements in wet gas are in the
mm3 m
3 level that is close to the detection limit of the
apparatus. Results obtained are in agreement with expected
BTX and PAHs values, i.e. hundred and tenth of mm3 m
3
respectively, which have already been obtained at 1400  C
[19,24].
Due to the low concentration measured (<1 cm3 m
3),
there are only SPA results available giving acceptable results Fig. 12 e PAH volume concentration (tar cracker) measured
with IMR-MS. by IMR-MS and SPA in wet gas sampling and dry gas
sampling.
4.4. Other results with Hg, Xe and Kr ionization

Good results were also obtained for other components present

in the syngas such as:

Fig. 10 e Thiophene volume concentration (fluidized bed) Fig. 13 e H2O volume concentration (fluidized bed)
measured by IMR-MS in wet gas sampling and dry gas measured by IMR-MS and compared with the measure of
sampling. the water collected in the cold trap.
70 b i o m a s s a n d b i o e n e r g y 6 5 ( 2 0 1 4 ) 6 4 e7 1
Fig. 14 e COS volume concentration (fluidized bed)
measured by IMR-MS and mGC-TCD in wet gas sampling
and dry gas sampling.
 C2H4 and H2S with mercury ionization
 CH4, H2O, COS with xenon ionization
 HCl for krypton ionization
Some results are presented in Fig. 13 for H2O and in Fig. 14
for COS as examples. These results are always in agreement
with another method giving confidence in this IMR-MS
method for such syngas species. However, some improve-
ments must be done for some species such as for COS, NH3,
HCN, and HCl. For example for COS (Fig. 14), it is observed that
it is correctly measured in mass 60 with the xenon primary ion
when sampled in dry gas. However, when sampled in wet gas,
a strong overlap is existing that must be identified and then
taken into account in the software.
5. Conclusions
With the IMR-MS method, it is possible to measure concen-
trated and traces tar on-line successfully in a real syngas at
the exhaust of the high temperature fluidized bed reactor
(LFHT) at the CEA Grenoble during steam gasification of wheat
straw and at the exhaust of the high temperature reactor tar
cracker (PEGASE).
The comparison with other tar measurement methods
such as mGC-TCD, the Tar Protocol and SPA allows a good
confidence in this new promising method.
Some improvements should be made, such as the cali-
bration of the IMR-MS apparatus with PAHs and thiophene to
have a better confidence in the measurement.
A major interest of the method is its capability to measure
major gas (except H2), tar and inorganic pollutants in one
apparatus. To achieve this objective, an analysis of the over-
laps due to fragmentation at higher ionization potential than
Hg should be done. To help users to interpret their mass
spectra it would be very useful to build a fragmentation
database coupled to an isotope database at such low ioniza-
tion potential.
Additionally, the quite high cost of the IMR-MS is more
attractive because there is no need to buy many other types of
equipment.
This method has a potential for process control monitoring
as well as research and development applications on tar
behavior.
Acknowledgments
The authors would like to thank gratefully GIE-Arvalis ONI-
DOL and RAGT-Energie for the supply of biomass samples.
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