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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
(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.
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
Fluidized bed Toluene (92, Hg) Fluidized bed Thiophene (84, Hg)
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-
thiophene to have higher confidence in the measurement. (2011)
A major interest of the method is its capability to [11]K.R. Campbell, D.J. Hallett, R.J. Resch, J. Villinger
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