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Engineering Conferences InternationalECI Digital ArchivesBioEnergy IV: Innovations in Biomass Conversionfor Heat, Power, Fuels and Chemicals Proceedings
Spring 6-11-2013
Clean hydrogen rich gas from catalytic steamgasification of biomassSergio RapagnaFaculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo
Annalisa D'OrazioFaculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo
Katia GalluciDepartment of Industrial Engineering, Information and Economy, University of L’Aquila
Manuela Di MarcelloFaculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo
Manfred NackenPall Filtersystems GmbH Werk Schumacher
See next page for additional authors
Follow this and additional works at: http://dc.engconfintl.org/bioenergy_iv
Part of the Chemical Engineering Commons
This Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion inBioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives. Formore information, please contact [email protected].
Recommended CitationSergio Rapagna, Annalisa D'Orazio, Katia Galluci, Manuela Di Marcello, Manfred Nacken, Steffen Heidenreich, and Pier Foscolo,"Clean hydrogen rich gas from catalytic steam gasification of biomass" in "BioEnergy IV: Innovations in Biomass Conversion for Heat,Power, Fuels and Chemicals", Manuel Garcia-Perez,Washington State University, USA Dietrich Meier, Thünen Institute of WoodResearch, Germany Raffaella Ocone, Heriot-Watt University, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, TheNetherlands Eds, ECI Symposium Series, (2013). http://dc.engconfintl.org/bioenergy_iv/20
AuthorsSergio Rapagna, Annalisa D'Orazio, Katia Galluci, Manuela Di Marcello, Manfred Nacken, SteffenHeidenreich, and Pier Foscolo
This conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/bioenergy_iv/20
CLEAN HYDROGEN RICH GAS FROM CATALYTIC STEAM GASIFICATION OF BIOMASS
Sergio Rapagnà, Annalisa D’Orazio, 1Katia Gallucci, Manuela Di Marcello, 2Manfred Nacken, 2Steffen Heidenreich and 1Pier Ugo Foscolo
Faculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo,
Via Carlo R. Lerici 1, 64023 Mosciano Sant’Angelo, Teramo, Italy
1Department of Industrial Engineering, Information and Economy, University of L’Aquila,
Via Campo di Pile, Zona industriale di Pile 67100 L’Aquila, Italy
2Pall Filtersystems GmbH Werk Schumacher
Zur Flügelau 70, 74564 Crailsheim, Germany
IntroductionBiomass gasification is a thermo-chemical conversion process which produces a
fuel gas rich in hydrogen and carbon monoxide, with a significant content of
methane and carbon dioxide. Steam is also present in the producer gas,
in addition to organic (tar) and inorganic (H2S, HCl, NH3, alkali metals)
impurities, and particulate.
Gas cleaning is normally done by filtration and scrubbing of the producer gas, to
drastically reduce particulate and tar content.
Biomass particles
+ heat
Gas + hydrocarbons
+ steam
H2, CO, CO2, CH4, CnHm
To increase the efficiency of the utilization of thermal and
chemical energy of the producer gas, hot gas cleaning and
conditioning systems (abatement of particulate content and tar
conversion at a temperature close to the gasification temperature)
should be developed and implemented through a compact design
and reliable and simple-to-operate equipment.
Process simplification and intensification could play a very
important role to a real breakthrough in the utilization of biomass
in general, and specifically of gasification plants.
Catalytic filter candles have been proposed as an alternative, very
promising technology to be coupled to biomass gasification
processes (UNIQUE and UNIfHY Projects).
T2 T3
T1
T4
T5
DP1 DP1 DP1
Pump
Ciller
Gas
Gasmete
r
Gas Analysers
Ciller
Pump
Heater
Water
Air
N2
H2 CO, CO2
CH4
H2S NH3
The organic component (tar) in the
condensate samples was determined by
Total Organic Carbon (TOC) analysis
Tar fraction sampled in 2-
propanol, according to the
Technical Specification
CEN/TS 15439
The composition of the tar
fraction was determined by
GCMS or HPLC/UV
Experimental apparatus
Candle
• Outer diameter= 60 mm
• Inner diameter= 40 mm
• Total length 450 mm
• Filtering length 400 mm
Process conditions
• Biomass feed rate = (8 ÷ 10) g/min
• Steam flow rate = (7.7 ÷ 9.5) g/min
• Steam/biomass dry = (0.9 ÷ 1.11)
• Bed temperature = (800 ÷ 815) °C
• Reactor outlet temperature = (760 ÷ 800) °C
• Olivine dm= 350micron
• Biomass dm= 1100micron
Biomass properties
• Dry matter = 92.3%
• Ash= 1.1%
• Volatile matter= 71.9
• Fixed carbon= 19.5
N260912,1 : Al2O3 based hot filter candle of new improved candle
support type (UHT) and with an Al2O3 outer membrane.
N051112,1 : Al2O3 based hot filter candle of new improved candle
support type (UHT) and with an Al2O3 outer membrane.
C280912,1 : catalytically activated Al2O3 filter candle of new improved
candle support type (UHT) with an Al2O3 outer membrane. MgO-
NiO catalytic layer system was applied.
C181212,1 : catalytically activated Al2O3 filter candle of new improved
candle support type (UHT) with an Al2O3 outer membrane and
with integrated catalytic ceramic foam. MgO-NiO catalytic layer
system was appliedon the catalytic filter candle support; a MgO-
Al2O3-NiO based catalytic layer system was applied on the
integrated catalytic ceramic foam.
Filter Candles
C1/NC C1/NC C3/C C4/CF
Candle N260912,1 N051112,1 C280912,1 C181212,1
Type No catalytic No catalytic Catalytic Layer
Catalytic +
catalytic foam
Legend
Test code 0101 0102 0103 0104 0105 0106 0107 0108 0109 0110 0111 0112 0113
Candle C1/NC C1/NC C3/C C3/C C3/C C3/C C3/C C4/CF C4/CF C4/CF C4/CF C4/CF C4/CF
Test number I I I II III IV V I II III IV V VI
Biomass feed
rate, [g/min] 8,1 8,1 8,1 8,1 8,1 10 10 10 10 10 10 10 10
Steam/biomass
dry 1,11 1,15 1,13 1,19 1,18 1,03 1 0,94 0,94 0,95 1,08 1,12 1,10
Total
gasification
time [min] 247 313 210 420 420 183 180 190 240 111 180 300 239
Tests
0
10
20
30
40
50
60
H2 CO2 CO CH4
USED
FRESH
N260912,1 / N051112,1 : Al2O3 based hot filter candle of new improved candle support type
(UHT) and with an Al2O3 outer membrane
No-catalytic Candle
Test 0101 0102
Candle C1/NC C1/NC
Bed state USED FRESH
Bed using-time >10:00:00 0
Biomass feed rate, g/min 8.1 8.1
Steam/biomass dry 1.11 1.15
Condensate [g/min] 6.09 6.49
Water conversion % 29 25.2
Gas yield, Nm3/kgdaf 1.76 1.41
Tar content, g/Nm3, by TOC 0.049 0.651
Tar content, g/Nm3 by GCMS 5.958 ------
H2
(vol% dry N2 free) 55 51.5
CO2
(vol% dry N2 free) 22,5 25
CO
(vol% dry N2 free) 20 18
CH4
(vol% dry N2 free) 2,5 5,5
N260912,1 / N051112,1 : Al2O3 based hot filter candle of new improved candle support type
(UHT) and with an Al2O3 outer membrane
X-Ray Fluorescence Measured - w%
K 4,03
Si 1,64
Ni 0,11 (expected < 0,03)
Biomass composition mg / Kg_dry
K 5237,9
Ni 16,7
Olivine composition w%
SiO2 42
NiO 0,3
No catalytic Candle 1st Test - Ni %
Test 0106 0107
Candle C3/C C3/C
Bed state USED FRESH
Bed using-time 23:30:00 0
Biomass feed rate, g/min 10 10
Steam/biomass dry 1.03 1
Condensate [g/min] 6 6.36
Water conversion % 36.8 31
Gas yield, Nm3/kgdaf 1.63 1.48
Tar content, g/Nm3 by TOC 0.022 0.120
Tar content, g/Nm3 by GCMS 1.071 2.545
H2
(vol% dry N2 free) 54 52
CO2
(vol% dry N2 free) 22 24
CO
(vol% dry N2 free) 19 18
CH4
(vol% dry N2 free) 5 6
C280912,1 : catalytically activated Al2O3 filter candle of new improved candle
support type (UHT) with an Al2O3 outer membrane. MgO-NiO catalytic
layer system was applied.
0
10
20
30
40
50
60
H2 CO2 CO CH4
Catalytic Candle
USED
FRESH
Catalytic Candle
C181212,1 : catalytically activated Al2O3 filter candle of new improved candle support type
(UHT) with an Al2O3 outer membrane and with integrated catalytic ceramic foam.
MgO-NiO catalytic layer system was appliedon the catalytic filter candle support;
a MgO-Al2O3-NiO based catalytic layer system was applied on the integrated
catalytic ceramic foam
0
10
20
30
40
50
60
H2 CO2 CO CH4
Catalytic Candle + Catalytic Foam
USED
FRESH
Catalytic Candle + catalytic foam
Test 0108 0112
Candle C4/CF C4/Cf
Bed state USED FRESH
Bed using-time 31:16:00 0
Biomass feed rate, g/min 10 10
Steam/biomass dry 1.12 0.94
Condensate [g/min] 6.1 5.64
Water conversion % 41 33.5
Gas yield, Nm3/kgdaf 1.84 1.48
Tar content, g/Nm3 by TOC 0.010 0.062
Tar content, g/Nm3 by GCMS 1.311 0.142
H2
(vol% dry N2 free) 55.5 51
CO2
(vol% dry N2 free) 20 22
CO
(vol% dry N2 free) 21.5 22
CH4
(vol% dry N2 free) 3 5
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
FRESH
USED
BED USED FRESH
COMPOUNDSTAR
content
[g/Nm3]
TAR
content
[g/Nm3]
ACENAPTHYLENE 0.004 0.010
FLUORENE 0.002 0.006
PHENANTRENE 0.006 0.023
ANTHRACENE 0.006 0.004
PYRENE 0.000 0.003
PHENOL 0.000 0.000
NAPTHALENE 0.037 0.466
STYRENE 0.000 0.045
XYLENE 0.000 0.040
TOLUENE 0.087 0.714
TOTAL 0.142 1.311
0.00
0.01
0.01
0.02
0.02
0.03
GCMS- measurement on catalytic candle with catalytic foam
(C181212,1) :
TAR abatement (GCMS)
H2
CO2
CH4
CO
0
10
20
30
40
50
60
0 60 120 180 240 300 360 420 480 540 600
time, min
% b
y v
olu
me
nN
2fr
ee
0
20
40
60
80
100
0 60 120 180 240 300 360 420 480 540 600
time, min
Pre
ssure
dro
p t
hro
ug
h t
he
filt
er, c
m o
f H
2O
Gas composition and pressure drop for the catalytic candle with catalytic foam
with used olivine
Candle None C1/NC C1/NC C3/C C3/C C4/CF C4/CF
Bed state best - value USED * FRESH USED FRESH USED FRESH
Gas yeld [Nm3(dry
N2free)/kg daf]1 1.76* 1.41 1.63 1.48 1.84 1.48
H2 [%vol (dry gas,
N2free)] 39 55* 51.5 54 52 55.5 51
CH4 [%vol (dry gas,
N2free)] 10 2.5* 5.5 5 6 3 5
Water conversion [%] 16 29* 25.2 36.8 31 41 33.5
TAR content g/Nm3
by TOC3.7 0.049* 0.651 0.022 0.12 0.01 0.062
TAR content g/Nm3
by HPLC/UV or GCMS
7
(HPLC/UV)
5.958
(GCMS)-------
1.071
(GCMS)
2.545
(GCMS)
0.14
(GCMS)
1.31
(GCMS)
*Ni contamination
Candles performance comparison
Conclusions
The innovative concept of integrating a catalytic hot gas filter in
the freeboard of a fluidized bed gasifier has been tested. This
promising technology results in greatly increased gas and
hydrogen yields, as the same time giving rise to significant power
plant simplification and intensification
The best results, in respect to the gasification without candle,
show:
– Hydrogen content increases more than 40%
– Methane content decreases more than 70%
– Gas yield increases more than 80%
– Water conversion increases more than 2 times
– TAR content decreases more than 1 order