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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, F. LABALETTE#, M. CAMPARGUE*


CEA, DRT, LITEN/DTBH/LTB, 17 rue des Martyrs; 38054 Grenoble Cedex 9; France
#
GIE-Arvalis ONIDOL Paris France * RAGT Energie SAS Albi France

Corresponding author: francoise.defoort@cea.fr – phone: 33-(0)4 38 78 46 53 – fax: 33-(0)4 38 78 52 51

ABSTRACT: This paper presents a method of measuring on line ppbv level of BTX and PAH tar for biomass
gasification applications. This method is based on the Ion Molecule Reaction (IMR) mass spectrometer principle.
Due to the low energy of ionisation of Hg, Xe or Kr almost no overlapping spectra can damage the interpretation of
the detected results. IMR-MS results of concentrated and trace tars are presented after a bubbling fluidized bed and a
tar cracker respectively. Results are compared with others tar measurement methods such as micro gas
chromatography for benzene and toluene or Tar Protocol or Solid Phase Adsorption technique for BTX and
Polycyclic Aromatic Hydrocarbon (PAH) giving good confidence to the results.
Keywords: tar, measurement, gasification, biomass, syngas

1 INTRODUCTION components (CO, CO2 etc) as well as some inorganic


(SO2, NO) or organic (benzene, acetaldehyde) pollutants
Contaminants such as tar present in the gas obtained at the exhaust of incineration processes [11], [12].
from the biomass gasification are important to be However this method has never measured the
measured online for detecting rapidly their variations composition of a syngas from a biomass gasification
which may induce saturation of the gas cleaning systems process.
or degradation of the catalysts used for fuel synthesis.
Furthermore it is necessary to find an online method able
to measure tar at ppbv level after gas cleaning systems. 2 EXPERIMENTAL
On line measurements of BTX (Benzene, Toluene,
Xylene) are currently made by micro-gas 2.1 IMR-MS
chromatography with a thermal conductimetry detector Principle of the method: The IMR method is well-
(µGC-TCD) above several ppmv (50 mg/Nm3) [1]. known in ion physics. It is an important path of primary
Heavier tars PAH (Polycyclic Aromatic Hydrocarbon) as ion loss in a plasma and can be represented as:
naphthalene by FTIR (Fourier Transform Infra-Red) [2]
or naphthalene, fluoranthene and pyrene by LIF (Laser A+ + G = G+ + A [eq.1] Ion molecule reaction
Induced Fluorescence) [3], [4], [5] can also be measured
on line directly in the gas phase but again above several The monograph by Harrison is especially
ppmv level for FTIR or present strong interferences with recommended for further reading [13]. A simplified
other species present in the gas for LIF. Molecular beam description is given in our paper.
mass spectrometry (MBMS) is an on line method to IMR-MS method is similar to CI-MS (Chemical
measure all tars from BTX to PAHs and even more [6] Ionization Mass Spectrometry) but one of the differences
using a specific gas sampling to collect condensable is that the primary ion source is run with an inert gas such
species thanks to a molecular beam inlet system. But this as Hg, Xe, Kr instead of a chemical gas such as NH3,
method suffers from the conventional high ionization CH4 or N2/H2O mixture. The main pathway in IMR-MS
energy (70 eV) due to the electronic impact method. to ionize a sampling gas G with a primary inert gas ion
Therefore the major draw-back with this instrument is the A+ (A= Hg, Xe or Kr) is a charge transfer as in [eq.1].
fragmentation of molecules leading to complex mass For CI-MS more complex ionization pathways are
spectra and multiple overlapping intensities in complex occurring as protons transfer [Eq.2]
gas mixtures. To overcome this limitation several soft
ionizations have been used with photoionization G + [NH4]+ → [GH]+ + NH3 [eq.2]
techniques such as Resonance-enhanced multiphoton
ionization (REMPI) or single-photon ionization (SPI) The principle of the IMR-MS method is shown in
with Time-of-flight mass spectrometry (TOFMS) [7], Figure 1.
however, only identification and no quantification are Chamber of
primary ion
Reaction
chamber
performed. Other methods measuring online total tar generation
Quadrupole ion
Ion detector
contents exist, such as the ECN Tar Dew Point [8], the Octopole ion guide separation

FID (Flame Ionization Detector) tar analyzer (TA 120-3) A A+ G+


currently used by IFK U. of Stuttgart [9] or the PID
(Photo-ionization detection) tar analyzer recently
Inert gas Mass
developed by [10] but the nature of the species is not A = Kr, Xe or Hg spectra
sampled Gas G
known for these methods.
A + e- A+ + 2 e- A+ + G G+ + A
This paper presents a soft ionization mass
spectrometry method based on the Ion Molecule Reaction Ion Molecule Reaction

(IMR) mass spectrometer (MS) principle. Such IMR-MS Figure 1: IMR-MS principle (partly reported from
method has already been used to measure online major [14])
technical characteristics are summarized in Table 1. The
An inert gas (Hg, Xe or Kr) is ionized by electron apparatus is equipped with a combined primary ion
impact in the chamber of primary ion ionization as: source for Kr, Xe and Hg.

A + e = A+ + 2e [eq.3] primary ionisation

Primary ions 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 reaction [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 high vacuum of ~10-4
mbar for IMR-MS (CI-MS about 1 mbar). The ions G+
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 Figure 3: photo of the Airsense apparatus
ionisation potential of the primary ion A is higher than
the one of the gas sample G. Figure 2 shows the Table 1: Technical details of the Airsense apparatus
ionisation potential of several molecules of interest and to
the inert gas Hg, Xe and Kr. Mass range 0 – 512 amu
Resolution < 1 amu
Analysis time > 1 msec
Measuring range 104
Response time T90 < 50 msec
< 1 ppb (Benzene in air)
Lower detection
< 10 ppb (Benzene in exhaust
limit
gas)
< ± 5% over 12 h (1ppm
Drift concentration
Benzene)
Reproducibility < ± 3% (1ppm Benzene)
Accuracy < ± 2% (1ppm Benzene)

Figure 2: ionization potential of several molecules To avoid condensation of water and condensable
species (tars, NH4Cl) a heated (180°C) low pressure
For example the ionisation potential of mercury capillary samples the gas of the process (Figure 4). A
(IP(Hg)= 10.43 eV) is higher than the one of BTX, PAHs small filter is positioned just before the capillary to avoid
and thiophene (C4H4S). If the excess energy IP(Hg) – clogging by dust or deposits. A dilution with a neutral gas
IP(G) is small (~< 1 eV) no fragmentation will occur is possible just entering the vacuum chamber.
otherwise it might be used to break the weakest bond of
the ionised molecule leaving a lower molecular weight
fragment ion. Mercury is able to ionize these species
almost without fragmentation as the Hg excess energy is
small. Figure 2 shows also that NH3, H2S and C2H4 can
be ionized by mercury. Xenon (IP(Xe)= 12.12 eV) is able
to ionize COS, CH4, C2H2, C2H6 and H2O. Kripton
(IP(Kr)= 13.99 eV) is able to ionize CO, CO2, HCl and
HCN. Finally all syngas molecules can be measured by
these three inert ionized gases. Mercury primary ionized
gas is the best case as it is not sensitive to species having
higher ionization potential than Hg. The Hg mass
spectrum is simpler than the Xe one that is itself simpler
than the Kr one. A careful study must be done with Xe
and Kr to check if there is a mass overlapping due to Figure 4: photo of the heated capillary sampling line
isotopes and fragmentation.
The software is able to pilot the apparatus with two
Apparatus tested: The IMR mass spectrometer modes:
apparatus tested in this work is called “Airsense” and it 1- The “scan” mode where all masses from 1 to 500 amu
has been developed by an Austrian company (V&F are scanned for each ion source. This mode allows
analyze: www.vandf.com). It was rented for one month at isotopes and overlapping to be checked and the choice of
CEA grenoble. It is currently used by V&F customers the correct amu to record during the process.
mainly for automotive, food, beverages & tobacco 2- The “monitoring” mode, in which more than 20 mass
applications but also for medical use [14], [15]. It has amu for each of the three ion sources are recorded versus
never been used to analyse syngas. A picture of the time. This allows the tracking of the process versus time
apparatus is shown in Figure 3. It is very compact for the selected amu.
(59x65x73cm) and easy to carry (100kg - wheels). Its
methods allow measurements of BTX and PAHs. TP
2.2 Gasification tests and tar measurement methods allows measurement above ppmv and SPA above roughly
Gasification tests were performed to measure tars in 10 ppbv [1].
concentrated as well as in trace amounts. Concentrated
tar measurements were performed at the exhaust of the
fluidized bed facility (LFHT) developed at CEA- 3 RESULTS
Grenoble and traces at the exhaust of the tar cracker (gas
reforming) reactor (PEGASE). Both facilities are linked 3.1 Mass spectra
by an insulated line, heated to 800°C in order to avoid An example of syngas mass spectra acquired on wet
condensation of inorganic species. Full description of gas (dilution 4:1) at the exhaust of the fluidized bed with
both facilities is emphasized in [16]. Steam gasification the mercury ions source is presented in Figure 6a and 6b
of straw at 850°C 2 bar (S/B = 2g/g) 1kg/h has been for mass 10 to 100 and 100 to 200 respectively.
performed in the fluidized bed. The temperature of the tar
cracker has been set at 1400°C. Figure 5 is a schematic
view of the facilities where tars sampling are presented. Fluidized bed

a: mass 10 to 100 amu


Figure 5: Schematic view of the pilot scale facilities
LFHT linked to PEGASE and gas analysis
Fluidized bed
Sampling is possible before and after the cold traps
for both facilities.
The IMR-MS measurements were performed in both
places to check the accuracy of results in dry and wet gas
and to measure steam content on wet gas. A dilution
factor of 4 with nitrogen was applied for wet sampling
before cold traps. No dilution was applied on dry gas
after cold trap. Calibration of the apparatus was done for
BTX, steam and some other components (H2S, COS,
NH3, HCN, HCl, CH4, C2H4). No calibration was done
for naphthalene, PAH and thiophene. It is known by V&F b: mass 100 to 200 amu
that the sensitivity of these components is very close to Figure 6: Mass spectra at the exhaust of LFHT (wet gas)
benzene. Then the same cps/ppmv was given to these
components. IMR-MS records are every 25 seconds. It is observed that the masses corresponding to
Other tar measurement methods were performed in benzene, toluene, thiophene, phenol and some PAHs
order to compare the results between them and the IMR- (indene, acenaphthylene, biphenyl + acenaphtene,
MS one. fluorene, phenanthrene+ antharcene) are well defined.
BTX tars C6H6, C7H8 C8H10 are measured on line by The other masses observed are from their isotopes.
micro-Gas Chromatography (µGC) coupled with Calculations of the isotopic ratio are in line with the
Thermal Conductivity Detectors (TCD). As dry gas is intensity ratio measured in Figure 6. Furthermore it is
necessary for this apparatus, gas is sampled after the cold observed that some others masses corresponding to some
traps. Other species are also analyzed by µGC as the inorganics such as H2S NH3 or hydrocarbon C2H4 are
analyzer is equipped with four columns allowing the present (Figure 6a).
measurement of Ar, CO2, CO, CH4, N2, H2, C2H2, C2H4,
C2H6, C3H8 and H2S and COS. Every three minutes a 3.2 Concentrated tars
spectrum is acquired. This method allows measurement Figures 7 to 11 present the concentration of benzene,
of BTX above several ppmv. toluene, thiophene some PAHs (indene, acenaphthylene,
Two other tar measurements methods are also biphenyl + acenaphtene, fluorene, phenanthrene+
implemented: the well known tar protocol method (TP) antharcene) recorded versus time at the exhaust of the
[17] and the solid phase adsorption SPA method [18]. fluidized bed before the cold traps in wet gas (12:00 to
Both methods are off line and based on condensation of 13:25) and after the cold traps in dry gas (13:25 to
tar in liquid phase (isopropanol) thanks to an impinger 14:40).
train for TP and in a solid amino phase adsorbent for the In these figures the dilution correction and the
SPA. Gas is sampled before the cold trap in order to wet/dry correction have been done to present all results as
measure condensable heavy tar such as PAHs. Liquid ppmv dry with neutral gas included. Results obtained are
samples of TP and SPA probe are analyzed later by gas in agreement with expected BTX and PAH values
chromatography (GC) with a flame ionization detector currently obtained in these conditions, i.e. in the 1000
(FID) and after a thermal desorption for SPA. Both ppmv level for benzene, 50 ppmv for naphthalene, 10
ppmv for toluene and 1 ppmv for PAHs [16], [19].
Fluidized bed PAH
A very good agreement is observed for Benzene and
toluene between the four analytical methods IMR-
MS/µGC-TCD/TP/SPA. Results are in the 15% relative
uncertainties range.

Fluidized bed Benzene (78, Hg)

Figure 10: PAH concentration (fluidized bed)

Figure 11 presents the IMR-MS results for thiophene


which is between 1 and 10 ppmv. Thiophene is not
Wet gas dry gas calibrated and there is no other method to compare.
However, it is seen in the literature that thiophene is
Figure 7: Benzene concentration (Fluidized bed) measured in the 1 to 10 ppmv range in fluidized bed
gasification [20].

Fluidized bed Toluene (92, Hg) Fluidized bed Thiophene (84, Hg)

Wet gas dry gas Wet gas dry gas


Figure 8: Toluene concentration (Fluidized bed)
Figure 11: Thiophene concentration (Fluidized bed)
Naphthalene IMR-MS results shown in Figure 9 are
lower than TP and SPA (factor 2). Taking into account Accidents observed in the IMR-MS (and in the µGC-
that naphthalene is not calibrated but is linked to the TCD) records which are in the 10 to 20% relative
benzene response, the agreement is acceptable. uncertainties are not significant to process events.
However, the accidents above these uncertainties are
significant. As an example, it is observed that the
Fluidized Naphthalene (128, Hg) apparatus is disconnected to the syngas flux during the
bed TP. A strong decrease of all components is thus observed
25 seconds later. In Figure 11 strong variations of the
IMR-MS signal between 10:55 and 11:02 which 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 sensors. A study should be
made with compositional change (biomass composition
Wet gas dry gas in homogeneity or saturation of a gas cleaning unit).

3.3 Trace tars


Figure 9: Naphthalene concentration (Fluidized bed)
The Figures 12 and 13 show the concentration of
benzene and some PAHs. The other tars were
PAH results, shown in Figure 10, indicate that IMR-
undetectable.
MS results are in between TP and SPA results. As
In these figures it is observed that results are more
naphthalene, PAHs are not calibrated but are linked to
consistent in dry gas rather than in wet gas because there
benzene response.
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 ppb level which is close to the sensitivity
limit of the apparatus. Results obtained are in agreement
with expected BTX and PAHs values, i.e. hundred and
tenth of ppbv respectively, which have already been
obtained in this very high temperature condition [16],
[21].
Due to the low concentration measured (< 1 ppmv),
there are only SPA results available giving acceptable
results with IMR-MS.
Tar cracker
CH4 (16, Xe)
Tar cracker Benzene (78, Hg)

Wet gas dry gas

Figure 15: CH4 concentration (Tar cracker)


Wet gas dry gas
Fluidized bed H2O (20, Xe)
Figure 12: Benzene concentration (Tar cracker)

Tar cracker PAH

Figure 16: H4O concentration (Fluidized bed)


Wet gas dry gas
Tar cracker
H2S (34, Hg)
Figure 13: PAH concentration (Tar cracker)

3.4 Other results


Good results are also obtained for other components
present in the syngas as C2H4, CH4, H2O, H2S, COS
(Figure 14 to 18). These results are always in some
agreement with another method giving confidence in this Wet gas dry gas
IMR-MS method for such syngas species. However some
improvements must be done for some species such as
COS, NH3, HCN, and HCl. For example for COS Figure 17: H2S concentration (Tar cracker)
(Figure 18), it is observed that it is correctly measured in
mass 60 with the Xenon primary ion in dry gas. But in Fluidized bed
wet gas, there is a strong overlap which must be
identified and then taken into account in the software. COS (60, Xe)

Fluidized bed C2H4 (28,Hg)

dry gas Wet gas

Figure 18: COS concentration (Fluidized bed)

Wet gas dry gas


7 CONCLUSIONS

Figure 14: C2H4 concentration (Fluidized bed) The IMR-MS method has measured concentrated and
traces tar on line successfully for the first time in a real
syngas at the exhaust of the high temperature fluidized
bed reactor (LFHT) at the CEA Grenoble during steam
gasification of straw and at the exhaust of the high
temperature reactor tar cracker (PEGASE).
Comparison with other tar measurements methods
such as µGCD-TCD, the Tar Protocol and SPA accords
having high confidence in this new promising method.
Some improvements should be made, such as the
calibration of the IMR-MS apparatus with PAHs and technique” Catalysis Today Vol.: 176 Issue: 1 P: 250-
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