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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

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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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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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Ash Melting Points: Alkali

Non-Equilibrium-Phase

Tem

per

atu

re[

°C]

Eutectica

Tem

per

atu

re[

°C]

Eutecticum

3

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Ash Melting Points: Phosphor

Tem

per

atu

re[

°C]

Eutectic Area

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Ash Melting Points: Erdalkali

CaOSiO2

Tem

per

atu

re[

°C]

Eutectica

SiO2MgO

Eutecticum

4

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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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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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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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Removal of Sulphur + CO2-Reduction: Rectisolscrubbing

Clean Gas

Cooling

Steam

Cooling

CO2-Scrubbing

H2S-Scrubbing

Benzin-Scrubbing

Raw Gas

Water andHeavy Benzin

Steam

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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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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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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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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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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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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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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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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

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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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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.