1
16.10.2006Clausthal-Zellerfeld,
CUCU TECTEC
Biomass forBiomass for FutureFuture BtLBtL -- ProcessesProcesses::RequirementsRequirements andand CharacterisationCharacterisation
Dr.-Ing. Stefan Vodegel
2nd International BtL-Congress, Berlin, 12.+13. October 2006
Ken
nung
Juni
02
2
CUCUTECTEC
Check List for Biomass Requirements
Technical Check List forRequirements to Biomass from
Operator View
Ash cementing/ -melting flow
Corrosion
Coatingcreation
Quality ofSynthesis Gas
Properties ofResidues Biomass
entry
Heatingvalue
Alkali = Maxima ?Erdalkali = Minima ?
HCl = Maximum ?H2S = Minimum / Maximum ?
other acid Gas Parts = ?
Dust = ?
H/C – Relation,Properties of Material = ?
Particle-Morphology = ?
Heavy Metals= ?
Water, AshContent = ?
2
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Juni
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CUCUTECTEC
Routes for BtL-Production
Hei
ßer
Wär
met
räg
er
Abgas
Str
oh-
Sch
nip
sel
Rohgas
Pyrolyse-Restgas
Pyrolyseölunterkühlt
AbgekühlterWärmeträger
PyrolyseölProdukt
PyrolyseölKondensat
Koks +Wärmeträger
KoksSlurry
Stroh
Kühler
Grobzerkleinerung
Feinzerkleinerung
Trocknung
Nachverbrennung Pyrolysegas+ Aufheizung des Wärmeträgers
Doppelschnecken-Reaktor
M
Hei
ßer
Wär
met
räg
er
Abgas
Str
oh-
Sch
nip
sel
Rohgas
Pyrolyse-Restgas
Pyrolyseölunterkühlt
AbgekühlterWärmeträger
PyrolyseölProdukt
PyrolyseölKondensat
Koks +Wärmeträger
KoksSlurry
Stroh
Kühler
Grobzerkleinerung
Feinzerkleinerung
Trocknung
Nachverbrennung Pyrolysegas+ Aufheizung des Wärmeträgers
Doppelschnecken-Reaktor
M
LuftDampf
Biomasse
Schornstein
G
Luft
Luft
Produkt-gaskühler
Produkt-gasfilter
Katalysator
WasserheizkesselÖlbrenner
Abgaskühler
BettascheFlugstaub
Produkt-gaswäscher
AbgasfilterAbgaskühler
Ver
gasu
ngsz
one
Ver
bre
nnu
ng
szo
ne
Gasmotor
Um
lau
f-k
ühle
r
LuftDampf
Biomasse
Schornstein
G
Luft
Luft
Produkt-gaskühler
Produkt-gasfilter
Katalysator
WasserheizkesselÖlbrenner
Abgaskühler
BettascheFlugstaub
Produkt-gaswäscher
AbgasfilterAbgaskühler
Ver
gasu
ngsz
one
Ver
bre
nnu
ng
szo
ne
Gasmotor
Um
lau
f-k
ühle
r
FTS
HTV-ReaktorEintragssystem
NTV-Reaktor400-500°C
Koks
Trennstufe
ReststoffeMahlung
Brennkammer1300-1500°C
Sauerstoff
Dampf
Schlacke
H2O
Rohgas≈800°C
Rekuperator Gasentstaubung
Upgrading
Gas-Wäsche Abwasser
Vergasungs-mittel
Zerkleinerte undgetrocknete Biomasse
Staub
Dampf
CO-Conversion
SELEXOL-ProzessCO2
Adsorption
Bel. Adsorbens
Adsorbens
Lösungsmittel
Sonstige
Fe(OH)2
SunDiesel
Wachse
Sonstiges
ChemischeQuenche
Schwelgas
FTSFTS
HTV-ReaktorEintragssystemEintragssystem
NTV-Reaktor400-500°C
Koks
Trennstufe
ReststoffeMahlung
Brennkammer1300-1500°C
Sauerstoff
Dampf
Schlacke
H2O
Rohgas≈800°C
Rekuperator GasentstaubungGasentstaubung
UpgradingUpgrading
Gas-WäscheGas-Wäsche Abwasser
Vergasungs-mittel
Zerkleinerte undgetrocknete Biomasse
Staub
Dampf
CO-ConversionCO-Conversion
SELEXOL-ProzessSELEXOL-ProzessCO2
AdsorptionAdsorption
Bel. Adsorbens
Adsorbens
Lösungsmittel
Sonstige
Fe(OH)2
SunDiesel
Wachse
Sonstiges
ChemischeQuenche
Schwelgas
1. FZK / FE – Concept2. Güssing / TU Wien
3. CHOREN
4. ArtFuel
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Juni
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CUCUTECTEC
Ash Melting Points: Alkali
Non-Equilibrium-Phase
Tem
per
atu
re[
°C]
Eutectica
Tem
per
atu
re[
°C]
Eutecticum
3
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Juni
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CUCUTECTEC
Ash Melting Points: Phosphor
Tem
per
atu
re[
°C]
Eutectic Area
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Juni
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CUCUTECTEC
Ash Melting Points: Erdalkali
CaOSiO2
Tem
per
atu
re[
°C]
Eutectica
SiO2MgO
Eutecticum
4
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Juni
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CUCUTECTEC
Ash Melting Points: Tri-Systems
Conclusion: K and Na decrease the melting point strongly. This effect can be wishedin Entrained Flow Gasification; in Fluidised Bed Reactors CaO and MgOare necessary. A maximum level should be in the biomass.
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CUCUTECTEC
Chlorine = Corrosion ?
Corrosion rate[μm]
„Flinger´schesKorrosionsdiagramm“,
common for incineration
Corrosion
Corrosionpossible
No Corrosion
Expansionof Warnecke
Flue gas temperature [ °C ]
Tu
be
wal
ltem
per
atu
re[
°C]
0
0,05
0,10
0,15
0,20
0,25
0,30
300 325 350 375 400 425 450
Tube wall temperature [°C]
„Prof. Born, Berlin2006“
Example
Alternative 1: Steam generation in uncritical temperature area to avoid corrosion.
Remark: Numbers are valid in incineration atmosphere. Under gasificationconditions long therm experiences have to be collected. Safety distance should bekept in the first commercial plants.
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CUCUTECTEC
Chlorine = Corrosion ?
<0.005<0.005<0.005
0.270.470.02
n.m.6.10n.m
7.4461.00.27
0622-1-Wheat straw0622-2-Rapse0622-7-Wood
HClH2SHCNNH3
Trace component [g/m3is,dry]
Exp. No.:
Alternative 2: Using of additives in a temperature field of ≈ 800 to 900 °C.
Remark: Experimental results in a Circulating Fluidized Bed, made in the EU-Project RENEW.
No HCl could be detected inthe raw gas after using CaO
Conclusion: Cl in biomass is in principle a corrosion danger. But under the specialconditions of BtL-plants (need of low-pressure steam, some heatingsources and sags, using CaO in CFBs) there is a great potential tominimize corrosion.
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Juni
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10
CUCUTECTEC
Removal of Sulphur + CO2-Reduction: Rectisolscrubbing
Clean Gas
Cooling
Steam
Cooling
CO2-Scrubbing
H2S-Scrubbing
Benzin-Scrubbing
Raw Gas
Water andHeavy Benzin
Steam
6
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Juni
02
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CUCUTECTEC
Removal of Sulphur + CO2-Reduction: Selexolscrubbing
Raw GasSteam Air
Exit
to Methanator
H2S-Scrubber
to ClausPlant
CO2-Scrubber
CO2-RemovalH2S-Removal
Conclusion: For H2S-Removal and CO2-Reduction in BtL Plants the alternativesRectisol and variations of Selexol are favoured. With Rectisol to meetlimits is shure; with variations of Selexol it has to be checked. The pricefor the biomass which can be payed will differ in the two routes.
H2S-Absorber
CO2-Absorber
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Juni
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CUCUTECTEC
Influence of kind of Biomass on Synthesis Gas Quality
39.234.4 35.8 33.6 31.4
17.320.3
20.319.4 21.2
32.332.8 32.8 32.8
37.4
7.08.0 7.1
8.86.2
1.110.711.700.82
2.52
1.67 3.69 2.33 4.71 2.62
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Wheat Straw Rape Sugar BeetResidue
Sunflower Husks
CO2 N2 CO H2 CH4 C2C3
loose Pellets
32.1
24.9
33.1
7.6
0.00
2.24
Wood
Gas
Co
nce
ntr
atio
nd
ry[m
ol-
%]
H2:CO-Relation*: 1,9 1,6 1,6 1,7 1,8 1,3
Hu [MJ / kgdry ]*: 8,1 9,8 9,2 11,2 10,3 10,2
* : Experimental results in a Circulating Fluidized Bed under the same process parameters.
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CUCUTECTEC
Requirements to the biomass at the entry of thermal system from thepoint of quality
*: as long as minimal ash-melting point in the mixture isnot met → CaO- and MgO-content to maximize.
- is concepted for difficultbiomass.
- Hu, Fuel Entrained FlowGasification ≥ 11 MJ/kg.
**: at the entry of the Entrai-ned Flow Gasifier
Remarks
Carbon-containing suspensionsand liquids.
Carbon-containing dusts,suspensions and liquids.
Other possibilities
maybe Si-content. Still open.no bodes in biomass.Other restructions
any*anyContent of Phosphor
any*anyContent of Earth- + Alkali
anyanyContent of Cl, S, N
≥ 950*anyAsh melting point [°C]
any1 ≤ X 40**Ash content [mass-%]
10 to 60 15Water content [mass-%]
2 to 150in the area of millimetersParticle dimensions [mm]
Güssing / TU WienFZK / FE
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Juni
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CUCUTECTEC
Requirements to the biomass at the entry of thermal system from thepoint of quality
*: As long as minimal ash-melting point in the mixture isnot met → CaO- and MgO-content to maximize.
Qualification only proved forwood in published form untilnow.
Remarks
Carbon-containing suspensionsand liquids.
n.i.Other possibilities
maybe Si-content. Still open.no fibre structure like oldpaper or textiles, no chips.
Other restructions
any*n.i.Content of Phosphor
any*n.i.Content of Earth- + Alkali
anyn.i.Content of Cl, S, N
≥ 850*n.i.Ash melting point [°C]
anyno materials with a bigamount of ash like sewage
sludge or turf.
Ash content [mass-%]
3510 to 20, max. 25Water content [mass-%]
Ø 50, max. 200max. 120 * 50 * 30Particle dimensions [mm]
ArtFuelCHOREN
8
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CUCUTECTEC
0
10
20
30
40
50
60
70
80
90
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ash Content [ mass-% ]
Rev
enu
eE
ner
gy
Veg
etab
les
[€
/tW
S]
0
2
4
6
8
10
12
14
1612,7213,2213,7214,2214,72
Lower Heating Value [ MJ / kg ]
Inte
rnal
Rat
eo
fIn
tere
staf
ter
aR
un
nin
gT
ime
of
20Y
ears
[%
]
Internal Rate of Interest = 10 %
Revenue Energy Vegetables = 55 € / tWS
Reference Point
Investmentbarrier
Economy in dependence of ash content and heating value
Combustion Heat Performance = 500 MW therm
Material = (Wheat-)StrawHeating Value Hu = 14,1 MJ/kgWS
Invest = 383,5 Mio €Calculated Running Time = 8.000 h/aCalculation Period = 20 aTransport over Ø 50 km = 11,4 €/tWS
Price for Electricity Revenue/Costs = 11 cent/kWhNaphta = 500 €/tStraight Run Diesel = 1.508,- €/tWax = 1.158,- €/t
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Juni
02
16
CUCUTECTEC
Sensitive analyse: Influence of availability
100 % Fall
8.000 h/a
0
10
20
30
40
50
60
65 70 75 80 85 90 95 100 105 110
Running Time on Nominal Load [ % ]
Rev
enu
eE
ner
gy
Veg
etab
les
[€
/tW
S]
0
2
4
6
8
10
12
14
16
Inte
rnal
Rat
eo
fIn
tere
staf
ter
aR
un
nin
gT
ime
of
20Y
ears
[%
]Internal Rate of Interest = 10 %
Revenue Energy Vegetables =55 € / tWS
Reference PointInvestmentbarrier
9
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Juni
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CUCUTECTEC
Sensitive analysis: Influence of gas cleaning technology
40
45
50
55
60
0
2
4
6
8
10
12
14
16R
even
ue
En
erg
yV
eget
able
s[€
/t]
Sel
ecti
veS
elex
ol-
Scr
ub
bin
g
Rec
tiso
l-S
cru
bb
ing
Inte
rnal
Rat
eo
fIn
tere
staf
ter
aR
un
nin
gTi
me
of
20Y
ears
[%
]
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Juni
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CUCUTECTEC
Sensitive analysis: Influence of preparation
0
10
20
30
40
50
60
0 200 400 600 800 1000 1200 1400 1600
Electricity Consumption for Crushing and Shape Forming [%]
Rev
enu
eE
ner
gyV
eget
able
s[€
/tW
S]
0
2
4
6
8
10
12
14
16
Inte
rnal
Rat
eo
fIn
tere
staf
ter
aR
un
nin
gT
ime
of20
Yea
rs[
%]
Internal Rate ofInterest = 10 %
Revenue Energy Vegetables = 55 € / tWS
100 % CaseCrushing with 15 kWh / t WS
Investmentbarrier
Crushing, Conveyance +Pellet Production with
max. 150 kWh / t WS
10
Ken
nung
Juni
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19
CUCUTECTEC
Conclusions
For autothermic Circulating Fluidized Bed and FZK/FE-Process is a high variability incontents of earth-/alkali proved; for Güssing-Process and Carbo-V® it is predicted.
Corrosion danger by means of chlorine is in BtL-Plants much lower than in powerplants.
Sulphur elimination and CO2-reduction is technical complex and expensive;Variations of Selexol- und Rectisol-Processes compete.
MgO- and/or CaO-contents in the biomass should be maximized if selled to BtL-plants with Circulating Fluidized Bed as gasifier.
Ash content in the biomass should be minimized from economic considerations.
Biomass must be available over the whole year.
Preparation of the energy vegetables has to be performed with minimal electricalconsumption.
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nung
Juni
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20
CUCUTECTEC
Acknowledgment
The presented theoretical results are part of the study Anforderungen an Biomasse
zur Kraftstoffherstellung aus der Sicht von Anlagenbetreibern. The experimentel
results are descended from the EU-Project RENEW. CUTEC thanks Fachagentur
Nachwachsende Rohstoffe and Volkswagen AG for financing the study and the
European Union for participating in and financing of the network project.