GC based analysis of tar, ammonia and water - EVUR

GC based analysis of tar, ammonia and water
Matti Reinikainen, D. Sc. Principal Scientist , VTT
Measurement, Analysis and Monitoring of Condensable Gas Components (especially Tar)
in Product-Gases from Biomass Gasification and Pyrolysis
International Workshop, June 8 th 2011 at 19 th EU Biomass Conference and Exhibition,
ICC Berlin

6/15/2011
Advanced analysis techniques for gasification gas
The aim has been to develop better analysis methods for the
impurities in biomass gasification gas
Shorten the analysis time, improve accuracy and reduce labor
intensity
From off-line to on-line
Research subjects:
Analysis of small concentrations of sulphur in the gasification
gas
Improved analysis method for alkalimetals
Establish on-line-tar analysis for light tars
Improved NH 3- and HCN-measurement methods
Development work in a projects with Carbona, Neste, Stora-Enso,
Foster Wheeler , Metso, VAPO, UPM and Gasum
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6/15/2011
'Rapid' on-line tar analysis of reformed gasification gas
Analysis time 5-20 min (several
possible operation modes)
Calibrated compounds:
Benzene
Toluene
Naphthalene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
(if desired, 40 additional
compounds)
HP-1 (10 m x 0.53 mm x 0.26 µm)
or HP Ultra 2 –column (25 m x 0.32
mm x 0.52 µm)
Gas phase samples online
Connected to the gasifier
automation system
Has been in use at VTT for more
than three Years
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6/15/2011
Validation of the on-line tar measurement method
More than 500 on- and off-line tar measurements were carried out
Under carefully controlled conditions both the Tar Protocol and the on-line
method give consistent results
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mg/m3
3000
2800
2600
2400
2200
2000
1800
1600
1400
1200
1000
800
600
400
200
6/15/2011
Example of rapid tar measurement by on-line-GC
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26.8.2008 20:24 26.8.2008 21:36 26.8.2008 22:48 27.8.2008 0:00 27.8.2008 1:12 27.8.2008 2:24 27.8.2008 3:36 27.8.2008 4:48 27.8.2008 6:00 27.8.2008 7:12
Air-blown CFB gasification followed by tar reformer
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Naphthalene
Toluene
Benzene

6/15/2011
On-line analysis of tars, water and ammonia 1/3
Simultaneous injection to two different columns:
Column 1: HP-1 for the analysis of hydrocarbons (FID)
Column 2: Poraplot-Q for the analysis of water (TCD) and ammonia (PID). TCD and PID in series.
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6/15/2011
On-line analysis of tars, water and ammonia 2/3
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TCD
6/15/2011
On-line analysis of tars, water and ammonia 3/3
Synthesis gas
100 ppm NH 3
Light HC’s
H 2O
PID FID
Light tars
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Based on technology patented by VTT (e.g.
WO/2007/080221)
Can be applied to both atmospheric and
pressurised systems
Temperature range 280-800°C
Dilution ratio typically 0-100
Can be used for instance with a GC, ICP or
FT-IR
Results with tarry raw gas have been
promising
Results consistent with controlled offline
sampling
No problems with condensation of tars
in the sampling lines
Good repeatability
Now in regular use at one site Finland
Under continuous development
Dilution sampling
6/15/2011
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Benzene Acenaphtylene
Pyridine Acenaphthene
Toluene Dibenzofurane
Ethenylbenzene Bibenzyl
m-Xylene Fluorene
Ethynylbenzene Phenanthere
Styrene Anthracene
o-Xylene Carbazole
Benzaldehyde 1-Phenylnaphthalene
Phenol 2-Methylanthracene
6/15/2011
Dilution sampling: tar measurement of tarry gas
Benzonitrile 4H-Cyclopenta(def)Phenantherene
4-Methylstyrene Fluoranthene
Indene Benz(e)acenaphthylene
o-Cresol Pyrene
m+p-Cresol Chrysene
Naphthalene 1,2 Benzanthracene
Quinoline 2,3 Benzanthracene
Isoquinoline Benzo(b)fluoranthene
Quinatsoline Benzo(e)pyrene
1H-Indole Benzo(a)pyrene
2-Methylnaphthalene Perylene
1-Methylnaphthalene Benzo(ghi)peryle
Biphenyl Anthanthrene
2-Ethylnaphthalene Coronene
1.6 Dimethylnaphtalene
20000.0
18000.0
16000.0
14000.0
12000.0
10000.0
8000.0
6000.0
4000.0
2000.0
0.0
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Benzene; on-line-GC
Tars < Naphthalene
Naphthalene
Tars > Naphthalene

6/15/2011
Dilution sampling: tar measurement of tarry gas
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Development of a cheap and robust ICP-method for the on-line metal analysis
ICP can be used for the simultaneous analysis
of several metals (Na, K, Fe, Ni, Cu, Zn, Sb…)
Plasma is generated using power transistors by
ramping the freguency until resonance is
achieved according to a VTT’s patented method
Typical bands of various metals can be detected
not only from a dry gas but also from wet gas or
liquid solutions
Method was successfully tested with real
gasification gas
6/15/2011
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6/15/2011
Analysis of HCN using static head space-technique (HS/GC-FID)
5 ml of 1:2 H2SO4 / water is injected to a gas tight 20 ml ampoule. The ampoule
is sealed with a septum cap. 1 ml of sample (pH = 12) is injected through the
septum on the H2SO4-solution.
The sample ampoule is heated in the HS-apparatus at 80 °C for 5 min and then
injected to GC-FID-analysis
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