Vous êtes sur la page 1sur 20

Biomass to Liquid Fuels via Gas to Liquids Technology

Biomass Energy Opportunities in Indian Country

September 15, 2004 John Scahill

Fuels via Gas to Liquids Technology Biomass Energy Opportunities in Indian Country September 15, 2004 John

BiomassBiomass FeedstocksFeedstocks

Biomass Biomass Feedstocks Feedstocks Forest Wood Residues Thin Thin n n in in g g Re

Forest Wood Residues

ThinThinnniningg ReRessiidueduess WoodWood cchhipsips UrbaUrbann WoodWood wwaassttee

pallepalletsts cratecrate ddiiscardsscards

wood wood yard yard trimmings trimmings

Agricultural Residues

CornCorn stostovveerr RiRicece hhuullllss

SuSuggaarcanrcanee bbaaggasseasse

AnAniimmaall biosolids biosolids

Energy Crops

HyHybridbrid poppoplalarr SSwwitchitchggrrassass WillWillooww

biosolids biosolids Energy Crops Hy Hy brid brid pop pop la la r r S S

Biomass Constituents

H 3 CO H 3 CO HO OCH 3 O O O OH OCH 3
H
3 CO
H
3 CO
HO
OCH 3
O
O
O
OH
OCH 3 OCH 3
O
O
HO
OHO
OCH 3
OCH 3
OH
O
O
HO
OH
HO
OH
O
O
O
HO
HO
O
OHO
OH
OH
OH
OH
OH
O
OCH 3
H
3 CO
HO
OCH 3
O
O
OH
HO
HO
OHO
OHO
O
OCH 3 OCH 3
OH
O
O
OH
O
HO
HO
OCH 3
OH
OH
O
O
HO
O
HO
O
O
OH
O
OHO
OHO
O
OH
OH
OH
OH
OH
OH
O
OH
O
HO
HO
HO
OH
O
O
O
OH
HO
OH
HO
H
3 CO
HO
OHO
OHO
O
O
OCH 3
OH
OH
O
OH
O
OH
O
HO
HO
OH
O
O
HO
O
HO
O
OH
O
OH
OHO
OHO
OH
OH
OH
OH
OH
O
OH
O
HO
HO
O
O
O
HO
OH
HO
OH
HO
OHO
OHO
O
O
OH
OH
O
OH
O
OH
O
HO
HO
O
O
O
HO
O
HO
O
OH
O
OH
OHO
OHO
OH
OH
OH
O
OH
O
HO
HO
Solid
O
HO
O
OH
OH
HO
OHO
O
O
OH
OH
OH
O
OH
O
HO
O
HO
OH
O
OH
OHO
OH
OH
O
HO
O
OH
HO
O
OH
OH
O
OH

Lignin: 15-25%

OH OH O HO O OH HO O OH OH O OH Lignin: 15-25% Complex aromatic

Complex aromatic structureOH OH O HO O OH HO O OH OH O OH Lignin: 15-25% Very high

Very high energy contentO OH OH O OH Lignin: 15-25% Complex aromatic structure Hemicellulose: 23-32% Polymer of 5 &

Hemicellulose: 23-32%

structure Very high energy content Hemicellulose: 23-32% Polymer of 5 & 6 carbon sugar Cellulose: 38-50%

Polymer of 5 & 6 carbon sugar

Cellulose: 38-50%

Polymer of glucose, very good biochemical feedstock biochemical feedstock

Gas or Sugars

Polymer of 5 & 6 carbon sugar Cellulose: 38-50% Polymer of glucose, very good biochemical feedstock
Polymer of 5 & 6 carbon sugar Cellulose: 38-50% Polymer of glucose, very good biochemical feedstock

Biomass Conversion Pathways

Thermal Excess air Partial air No Air Combustion Gasification Pyrolysis Heat (CO + H Liquids
Thermal
Excess air
Partial air
No Air
Combustion
Gasification
Pyrolysis
Heat
(CO + H
Liquids
2 )
Synthesis gas
Synthesis
gas

H 2

Liquid fuels

Biological Physical Pretreatment A/D Hydrolysis Fermentation (Heat & Pressure) CH Ethanol 4 Liquids
Biological
Physical
Pretreatment
A/D
Hydrolysis
Fermentation
(Heat & Pressure)
CH
Ethanol
4 Liquids
fuels Biological Physical Pretreatment A/D Hydrolysis Fermentation (Heat & Pressure) CH Ethanol 4 Liquids

Air (0.3) O 2 (0.3) Steam

Air (0.3) O 2 (0.3) Steam Heat Gasification Producer Gas (mol%) CO H 2 CH 4

Heat

Air (0.3) O 2 (0.3) Steam Heat Gasification Producer Gas (mol%) CO H 2 CH 4

Gasification

Producer Gas (mol%)

CO

H 2

CH 4

CO 2

N 2

24

13

3

8

52

Fuel Gases
Fuel Gases

(tars & particulate)

Synthesis Gas (mol%)

CO

H 2

CH 4

C 2 H 2 CO 2

N 2

39

20

17

6

18

0

(tars & particulate)

particulate) Synthesis Gas (mol%) CO H 2 CH 4 C 2 H 2 CO 2 N

Different Gasifier Designs

C

C

C

C

+ CO2 = 2CO

+ CO2 = 2CO

+ H2O = CO + H2

+ H2O = CO + H2

C

C

+ O2 = CO2

+ O2 = CO2

4H + O2 = 2H2O

4H + O2 = 2H2O

Biomass Biomass Gas, Tar, Water Gas, Tar, Water Pyrolysis Pyrolysis C C + O2 =
Biomass
Biomass
Gas, Tar, Water
Gas, Tar, Water
Pyrolysis
Pyrolysis
C C
+ O2 = CO2
+ O2 = CO2
Reduction
Reduction
4H + O2 = 2H2O
4H + O2 = 2H2O
C C
+ CO2 = 2CO
+ CO2 = 2CO
Combustion
Combustion
C C
+ H2O = CO + H2
+ H2O = CO + H2
Ash
Ash
Air
Air
Updraft Gasifier
Updraft Gasifier
Secondary
Secondary
Primary
Primary
Primary
Cyclone
Cyclone
Cyclone
Gasifier
Gasifier
Gasifier
Cyclone
Cyclone
Cyclone
Fly Ash
Fly Ash
Fly Ash
Biomass
Biomass
Biomass
Air/Steam
Air/Steam
Air/Steam
Bottom Ash
Bottom Ash
Bottom Ash

Circulating Fluid-Bed Gasifier

Circulating Fluid-Bed Gasifier

Biomass Biomass Gas, Tar, Water Gas, Tar, Water Pyrolysis Pyrolysis Combustion Combustion Reduction Reduction
Biomass
Biomass
Gas, Tar, Water
Gas, Tar, Water
Pyrolysis
Pyrolysis
Combustion
Combustion
Reduction
Reduction
Air
Air
Ash
Ash

Downdraft Gasifier

Downdraft Gasifier

Flue Gas

Flue Gas

Cyclone Cyclone Freeboard Freeboard Ash Ash Fluid Bed Fluid Bed Biomass Biomass Plenum Plenum Air/Steam
Cyclone
Cyclone
Freeboard
Freeboard
Ash
Ash
Fluid Bed
Fluid Bed
Biomass
Biomass
Plenum
Plenum
Air/Steam
Air/Steam
Fluid-Bed Gasifier
Fluid-Bed Gasifier
Char Char Biomass Biomass Furnace Furnace Recycle Gas Recycle Gas N2 or Steam N2 or
Char
Char
Biomass
Biomass
Furnace
Furnace
Recycle Gas
Recycle Gas
N2 or Steam
N2 or Steam

Air

Air

Entrained Flow Gasifier

Entrained Flow Gasifier

Furnace Recycle Gas Recycle Gas N2 or Steam N2 or Steam Air Air Entrained Flow Gasifier

Entrained Flow Gasification

(Steam Reforming)

Flue Gas

Entrained Flow Gasification (Steam Reforming) Flue Gas 850 C Burner Char Biomass Gas Slip stream Steam

850 C

850 C Burner

Burner

850 C Burner
Flow Gasification (Steam Reforming) Flue Gas 850 C Burner Char Biomass Gas Slip stream Steam Air
Flow Gasification (Steam Reforming) Flue Gas 850 C Burner Char Biomass Gas Slip stream Steam Air
Flow Gasification (Steam Reforming) Flue Gas 850 C Burner Char Biomass Gas Slip stream Steam Air

Char

Biomass

Flow Gasification (Steam Reforming) Flue Gas 850 C Burner Char Biomass Gas Slip stream Steam Air

Gas Slip stream

Steam

Air

Synthesis gas

Flow Gasification (Steam Reforming) Flue Gas 850 C Burner Char Biomass Gas Slip stream Steam Air

Staged Gasification

Pyrolysis

Staged Gasification Pyrolysis Steam Reforming 850 C Biomass + Vapors + moisture steam 700 C Pyrolysis

Steam ReformingStaged Gasification Pyrolysis 850 C Biomass + Vapors + moisture steam 700 C Pyrolysis Burner Burner

850 C Biomass + Vapors + moisture steam 700 C Pyrolysis Burner Burner
850 C
Biomass +
Vapors +
moisture
steam
700 C
Pyrolysis
Burner
Burner
Biomass + Vapors + moisture steam 700 C Pyrolysis Burner Burner Synthesis Gas Carbon Conversion Technologies

Synthesis

Gas

Biomass + Vapors + moisture steam 700 C Pyrolysis Burner Burner Synthesis Gas Carbon Conversion Technologies

Carbon Conversion Technologies 2004

Biomass + Vapors + moisture steam 700 C Pyrolysis Burner Burner Synthesis Gas Carbon Conversion Technologies

General Process Description Syngas-to-Liquids

coal,

natural

gas,

biomass

Oxygen

or Steam

Syngas-to-Liquids coal, natural gas, biomass Oxygen or Steam Gasifier Gasifier Gas Gas Cleanup Cleanup and and
Gasifier Gasifier
Gasifier Gasifier
Gasifier Gasifier

Gasifier Gasifier

Gasifier Gasifier
Gasifier Gasifier
Gasifier Gasifier
Gasifier Gasifier

Gas Gas Cleanup Cleanup and and

Gas Gas Cleanup Cleanup and and Conditioning Conditioning
Gas Gas Cleanup Cleanup and and Conditioning Conditioning

Conditioning Conditioning

Gas Gas Cleanup Cleanup and and Conditioning Conditioning
Gas Gas Cleanup Cleanup and and Conditioning Conditioning
Gas Gas Cleanup Cleanup and and Conditioning Conditioning
Gas Gas Cleanup Cleanup and and Conditioning Conditioning

Catalytic tar conversion

• Sulfur scrubbing

• Shift H2/CO ratio

Particulate removal

• Wet scrubbing

• Shift H2/CO ratio • Particulate removal • Wet scrubbing Catalytic Catalytic reactor reactor Liquid Fuels
• Shift H2/CO ratio • Particulate removal • Wet scrubbing Catalytic Catalytic reactor reactor Liquid Fuels

Catalytic Catalytic reactor reactor

Catalytic Catalytic reactor reactor
Catalytic Catalytic reactor reactor
• Shift H2/CO ratio • Particulate removal • Wet scrubbing Catalytic Catalytic reactor reactor Liquid Fuels
• Shift H2/CO ratio • Particulate removal • Wet scrubbing Catalytic Catalytic reactor reactor Liquid Fuels

Liquid Fuels

• Shift H2/CO ratio • Particulate removal • Wet scrubbing Catalytic Catalytic reactor reactor Liquid Fuels

Syngas Conditioning

Syngas Conditioning C + CO 2 2 CO 800° - 850° C ( Boudouard) C +

C + CO 2

2 COSyngas Conditioning C + CO 2 800° - 850° C ( Boudouard) C + H 2

800° - 850° C

(Boudouard)

C + H 2 O

CO + H 2 2

(Water gas shift)

Control of temperature and steam content adjusts H2 / CO ratio in Syngas

C + H 2 O CO + H 2 (Water gas shift) Control of temperature and

Gas Cleanup Requirements

For Fischer-Tropsch gas-to-liquids

Impurity

Removal level

H 2 S, NH 3 , HCN

< 1 ppmv

HCl

< 10 ppbv

Soot, dust, ash

Essentially completely

Tars

Below dew point < 1 ppmv

Source: H. Boerrigter et al, October 2002

dust, ash Essentially completely Tars Below dew point < 1 ppmv Source: H. Boerrigter et al,

Syngas Cleanup

Tar Reformer / Cracker

Tar Reformer / Cracker
Tar Reformer / Cracker
Tar Reformer / Cracker

Bag House

Filtration

Bag House Filtration
Bag House Filtration
Liquid Scrubbers - Water - H 2 S O 4 - Amine - NaOH

Liquid Scrubbers -Water -H 2 SO 4 - Amine -NaOH

Liquid Scrubbers - Water - H 2 S O 4 - Amine - NaOH
Liquid Scrubbers - Water - H 2 S O 4 - Amine - NaOH
Guard Bed ZnO
Guard Bed
ZnO
Water - H 2 S O 4 - Amine - NaOH Guard Bed ZnO T a
Water - H 2 S O 4 - Amine - NaOH Guard Bed ZnO T a
Water - H 2 S O 4 - Amine - NaOH Guard Bed ZnO T a
Water - H 2 S O 4 - Amine - NaOH Guard Bed ZnO T a

Tars

Particulates

N (HCN + NH 3 ) S (H2S + COS)
N
(HCN + NH 3 )
S
(H2S + COS)

Sulfur

polishing

Cl (HCl)

Particulates

- NaOH Guard Bed ZnO T a r s Particulates N (HCN + NH 3 )

NREL TCPDU Product Gas Tar Composition

Source: VTT Research Center, Finland
Source: VTT Research Center, Finland

Averaged mass spectrum (TMBMS) of tars from indirect wood gasification 78 - benzene 142 -
Averaged mass spectrum (TMBMS) of tars
from indirect wood gasification
78
- benzene
142
- methylnaphthalenes
78
91,92 - toluene
152
- acenaphthalene
1e+5
94
- phenol
166
- flourene
104
- styrene
178
- anthracene/phenanthrene
108
- cresol
192
- methylanthracene?
8e+4
116
- indene
202
- pyrene/flouranthene
128
- naphthalene
216
- benzo(a)flourene
6e+4
91,92
128
4e+4
94
116
104
2e+4
142 152
108
166 178
202
192
216
0
75
100
125
150
175
200
6e+4 91,92 128 4e+4 94 116 104 2e+4 142 152 108 166 178 202 192 216
SYNGASYNGASS PrProduoducctt OptioOptionnss Cat: Ni, Fe, Cu-Zn Cat: Cu-Zn, BIBIOOMMAASSSS Cu-Co Cat: Cu-ZnO Cat:
SYNGASYNGASS PrProduoducctt OptioOptionnss
Cat: Ni, Fe,
Cu-Zn
Cat: Cu-Zn,
BIBIOOMMAASSSS
Cu-Co
Cat: Cu-ZnO
Cat: H3PO4,
Cr2O3
FEED PREP
Cat: Fe
Cat: Ni
SYNGAS
FTL
UPGRADING
GASIFICATION
Cat: Co/K
Cat: Cu-ZnO
MeOH
Cat: Zeolite
CLEANUP
Cat: Mixed Bases
Na, Ca
CaCN
Cat: Ni/Mg
Cat = Catalytic
Conversion Process
Combined
Cycle
Cofiring/Reburn

HYDROGEN

ETHANOL, MIXED ALCOHOLS

METHANOL, DME

OLEFINS

LPG

NAPHTHA

KEROSINE/DIESEL

LUBES

WAXES

GASOLINE

OXOCHEMICALS e.g., KETONES

AMMONIA

SNG

CHP

CHP

DME OLEFINS LPG NAPHTHA KEROSINE/DIESEL LUBES WAXES GASOLINE OXOCHEMICALS e.g., KETONES AMMONIA SNG CHP CHP

Syngas FT Chemistry

Chain building reactions

CO + 2H 2

Syngas FT Chemistry Chain building reactions CO + 2H 2 -(CH 2 )- + H 2

-(CH 2 )-

+ H 2 O

Syngas FT Chemistry Chain building reactions CO + 2H 2 -(CH 2 )- + H 2

C-5 thru C-20 + Hydrocarbons

Syngas FT Chemistry Chain building reactions CO + 2H 2 -(CH 2 )- + H 2

Syngas to Liquid fuel Options

Biomass
Biomass
Feed Prep
Feed Prep
Gasification

Gasification

Gasification
Gasification
Gasification
Syngas to Liquid fuel Options Biomass Feed Prep Gasification Gas Cleanup H2/CO Catalyst Temp PSI °

Gas

to Liquid fuel Options Biomass Feed Prep Gasification Gas Cleanup H2/CO Catalyst Temp PSI ° C

Cleanup

H2/CO

Catalyst

Temp

PSI

°C

1.0-1.4

Cu-Zn

200-

750-

Cu-Co

420

3800

Others

H2/CO

Catalyst

Temp

PSI

°C

2.3

Cu-ZnO

< 250

1450

H2/CO

Catalyst

Temp

PSI

°C

2.0

Fe

340

340

2.0

Co-K

240

370

C 2.0 Fe 340 340 2.0 Co-K 240 370 Clean Syngas F-T Liquids Ethanol Mixed Alcohols
C 2.0 Fe 340 340 2.0 Co-K 240 370 Clean Syngas F-T Liquids Ethanol Mixed Alcohols
C 2.0 Fe 340 340 2.0 Co-K 240 370 Clean Syngas F-T Liquids Ethanol Mixed Alcohols
Clean Syngas
Clean
Syngas

F-T Liquids

Ethanol

Mixed2.0 Co-K 240 370 Clean Syngas F-T Liquids Ethanol Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax

Alcohols

240 370 Clean Syngas F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel
Zeolite Cat.
Zeolite
Cat.
Syngas F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel -Wax Hydrocracking

DME

Gasoline

F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel -Wax Hydrocracking Gasoline/diesel
F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel -Wax Hydrocracking Gasoline/diesel

Gasoline -Wax

Diesel -Wax

F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel -Wax Hydrocracking Gasoline/diesel
Hydrocracking

Hydrocracking

Hydrocracking
Hydrocracking
F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel -Wax Hydrocracking Gasoline/diesel

Gasoline/diesel

F-T Liquids Ethanol Mixed Alcohols Zeolite Cat. DME Gasoline Gasoline -Wax Diesel -Wax Hydrocracking Gasoline/diesel

Gas to Liquids Process Issues

Recycle Compressor

Tail gas Heat Catalyst Reactor H2/CO Ratio Pressure Temp - Press letdown Conversion 15-40% Selectivity
Tail gas
Heat
Catalyst Reactor
H2/CO
Ratio
Pressure
Temp - Press
letdown
Conversion 15-40%
Selectivity to Desired
Product
Liquid
Product
Heat
H2/CO Ratio Pressure Temp - Press letdown Conversion 15-40% Selectivity to Desired Product Liquid Product Heat
H2/CO Ratio Pressure Temp - Press letdown Conversion 15-40% Selectivity to Desired Product Liquid Product Heat

Liquid Fuel Properties

F-T Diesel (high quality)

Cetane

> 70 (conventional

45-50)

Total aromatics

< 3 (vol. %)

Polycyclic

< 0.01 (mass %)

aromatics

Sulfur

< 1 (ppm)

Source: www.sasol.com

Mixed Alcohols

Type

Wt%

Methanol

5-30

Ethanol

45-75

Propanol

15

Butanol

5

Pentanol

3

Hexanol & higher

2

Source: Taylor (2002)

Ethanol 45-75 Propanol 15 Butanol 5 Pentanol 3 Hexanol & higher 2 Source: Taylor (2002)

Commercial History of Gas-to-Liquids

• SASOL (South Africa) 1955

– Coal

of Gas-to-Liquids • SASOL (South Africa) 1955 – Coal CH4 hydrocarbon fuels/chemicals • Shell (Malaysia) 1993,

CH4

of Gas-to-Liquids • SASOL (South Africa) 1955 – Coal CH4 hydrocarbon fuels/chemicals • Shell (Malaysia) 1993,

hydrocarbon fuels/chemicals

• Shell (Malaysia) 1993, 12,000 bbl/day

– Natural gas

• Shell (Malaysia) 1993, 12,000 bbl/day – Natural gas syngas gasoline • BP / Davy Process

syngas

(Malaysia) 1993, 12,000 bbl/day – Natural gas syngas gasoline • BP / Davy Process Tech (Alaska)

gasoline

• BP / Davy Process Tech (Alaska) 2002

– Stranded CH4

– Compact, modular design – Small barge mounted plants under development

design – Small barge mounted plants under development short chain hydrocarbons • Syntroleum (Australia) under

short chain hydrocarbons

• Syntroleum (Australia) under construction/shakedown

barge mounted plants under development short chain hydrocarbons • Syntroleum (Australia) under construction/shakedown

Economic Comparisons

Biomass to F-T Liquids vs. Electricity

Yield

Value

$/ton

biomass

(1) 79.8 gal/ton

$1.14+.21=$1.35/gal (3)(4)

$108

(2) 455 kWh/ton

Purchase agreement $0.02- .04 / kWh

$9 - $18

(combustion-steam

Levelized COE $0.07 / kWh (2)

$32

turbine)

Basis:

1.

2.

3.

4.