An Introduction to Biomass Thermochemical Conversion

Richard L. Bain
Group Manager, Thermochemical Conversion
National Bioenergy Center
DOE/NASLUGC Biomass and Solar Energy Workshops
August 3-4, 2004
Presentation Outline
Objective & Definitions
Biomass Properties
Combustion
Gasification
Pyrolysis
Other
Research Areas
Conversion
Processes
Biomass
Biomass
Feedstock
Feedstock
Trees
Forest Residues
Grasses
Agricultural Crops
Agricultural Residues
Animal Wastes
Municipal Solid Waste
USES USES
Fuels:
Ethanol
Renewable Diesel
Electricity
Heat
Chemicals
Plastics
Solvents
Pharmaceuticals
Chemical Intermediates
Phenolics
Adhesives
Furfural
Fatty acids
Acetic Acid
Carbon black
Paints
Dyes, Pigments, and Ink
Detergents
Etc.
Food and Feed
- Gasification
- Combustion and Cofiring
- Pyrolysis
- Enzymatic Fermentation
- Gas/liquid Fermentation
- Acid Hydrolysis/Fermentation
- Other
Fuels, Chemicals, Materials, Heat and Power from Biomass
Basic Definitions
Basic Definitions
Biomass is plant matter such as trees, grasses, agricultural
crops or other biological material. It can be used as a solid fuel, or
converted into liquid or gaseous forms for the production of
electric power, heat, chemicals, or fuels.
Black Liquor is the lignin-rich by-product of fiber extraction
from wood in Kraft (or sulfate) pulping. The industry burns black
liquor in Tomlinson boilers that 1) feed back-pressure steam
turbines supplying process steam and electricity to mills, 2)
recover pulping chemicals (sodium and sulfur compounds) for
reuse.
Pyrolysis
Pyrolysis
Thermal conversion (destruction) of organics in the absence of oxygen
In the biomass community, this commonly refers to lower temperature thermal
processes producing liquids as the primary product
Possibility of chemical and food byproducts
Gasification
Gasification
Thermal conversion of organic materials at elevated temperature and
reducing conditions to produce primarily permanent gases, with char, water,
and condensibles as minor products
Primary categories are partial oxidation and indirect heating
Basic Definitions
Basic Definitions
Combustion
Combustion
Thermal conversion of organic matter with an oxidant (normally oxygen)
to produce primarily carbon dioxide and water
The oxidant is in stoichiometric excess, i.e., complete oxidation
Thermal
Conversion
Combustion Gasification Pyrolysis
Heat Fuel Gases
(CO + H
2
)
Liquids
No Air
Partial air Excess air
Thermal
Conversion
Combustion Gasification
Pyrolysis &
Hydrothermal
Heat Fuel Gases
(CO + H
2
)
Liquids
No Air
Partial air Excess air
POTENTIAL BIOMASS PRODUCTS
Potential Biomass Products
Biomass
Syngas
Hydrogen
Pyrolysis Oil Whole or Fractionated
Hydrothermal Treatment Oils
Biomass
Solid
CH
1.4
O
0.6
HHV = 16 17 MBTU/ton (MAF)
Syngas
Major components CO, H
2
, CO
2
CO/H
2
ratio set by steam rate in conditioning step, typical range 0.5 2
HHV: 450-500 BTU/scf
Pyrolysis Oil
CH
1.4
O
0.5
Chemical composition: water (20-30%), lignin fragments (15-30%), aldehydes (10-20%), carboxylic
acids (10-15%), carbohydrates (5-10%), phenols (2-5%), furfurals (2-5%), ketones (1-5%)
Other (ca.): pH - 2.5, sp.g. - 1.20, viscosity (40C, 25% water) 40 to 100 cp, vacuum distillation
residue up to 50%
Hydrothermal Treatment Oils
Water plus alkali at T = 300-350C, P high enough to keep water liquid. Use of CO is option
Yield > 95%
Distillate (-500C): 40 50%
Distillate Composition: Hardwood (300C) CH
1.2
O
0.2
, Manure (350C) CH
1.4
O
0.1
Qualitative: long aliphatic chains, some cyclic compounds containing carbonyl groups, and a few
hydroxy groups, ether linkages, and carboxylic acid groups
HHV = 28 34 MBTU/ton
Biomass Properties Relevant
Biomass Properties Relevant
to Thermal Conversion
to Thermal Conversion
Poplar Corn Stover Chicken Litter Black Liquor
Proximate (wt% as received)
Ash 1.16 4.75 18.65 52.01
Volatile Matter 81.99 75.96 58.21 35.26
Fixed Carbon 13.05 13.23 11.53 6.11
Moisture 4.80 6.06 11.61 9.61
HHV, Dry (Btu/lb) 8382 7782 6310 4971
Ultimate, wt% as received
Carbon 47.05 43.98 32.00 32.12
Hydrogen 5.71 5.39 5.48 2.85
Nitrogen 0.22 0.62 6.64 0.24
Sulfur 0.05 0.10 0.96 4.79
Oxygen (by diff) 41.01 39.10 34.45 0.71
Chlorine <0.01 0.25 1.14 0.07
Ash 1.16 4.75 19.33 51.91
Elemental Ash Analysis, wt% of fuel as received
Si 0.05 1.20 0.82 <0.01
Fe --- --- 0.25 0.05
Al 0.02 0.05 0.14 <0.01
Na 0.02 0.01 0.77 8.65
K 0.04 1.08 2.72 0.82
Ca 0.39 0.29 2.79 0.05
Mg 0.08 0.18 0.87 <0.01
P 0.08 0.18 1.59 <0.01
As (ppm) 14
Representative Biomass & Black Liquor Compositions
Representative Biomass and Coal Properties
Representative Biomass and Coal Properties
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT Athabasca
Classification HvBb sub B Bitumen
Proximate Analysis, wt% Dry
Moisture 25-60 16 8.16 19.84
Volatile Matter 77-87 ca. 80 40.6 39.02
Fixed Carbon 13-21 -- 45.47 49.08
Ash 0.1-2 4 13.93 9.16
Ultimate Analysis, wt % Dry
C 50-53 45 68.58 68.39 83.6
H 5.8-7.0 5.8 4.61 4.64 10.3
N 0-0.3 2.4 1.18 0.99 0.4
Cl .001-0.1 -- 0.12 0.02 --
O 38-44 42.5 6.79 16.01 0.2
S 0-0.1 0 4.76 0.79 5.5
Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47
HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass Higher Heating Value
0
2000
4000
6000
8000
10000
12000
4000 5000 6000 7000 8000 9000 10000
Calculated HHV (Btu/lb)
A
c
t
u
a
l

H
H
V

(
B
t
u
/
l
b
)
(with 95% confidence interval)
85.65 + 137.04 C + 217.55 H + 62.56 N + 107.73 S + 8.04 O - 12.94 A (Eq 3-15) 85.65 + 137.04 C + 217.55 H + 62.56 N + 107.73 S + 8.04 O - 12.94 A (Eq 3-15)
HHV (Btu/lb) = N = 175
Bain, R. L.; Amos, W. P.; Downing, M.; Perlack, R. L. (2003). Biopower Technical Assessment: State of the
Industry and the Technology. 277 pp.; NREL Report No. TP-510-33123
Potassium Content of Biomass
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Mixed waste paper
Fir mill waste
RFD - Tacoma
Red oak sawdust
Sugar Cane Bagasse
Urban wood waste
Willow - SV1-3 yr
Furniture waste
Willow - SV1-1 yr
Alder/fir sawdust
Switchgrass, MN
Hybrid poplar
Switchgrass, D Leaf, MN
Demolition wood
Forest residuals
Poplar - coarse
Miscanthus, Silberfeder
Wood - land clearing
Almond wood
Wood - yard waste
Danish wheat straw
Rice husks
Switchgrass, OH
Oregon wheat straw
Alfalfa stems
California wheat straw
Imperial wheat straw
Rice straw
Potassium Content (lb/MBtu)
Bain, R. L.; Amos, W. P.; Downing, M.; Perlack, R. L. (2003). Biopower Technical Assessment: State
of the Industry and the Technology. 277 pp.; NREL Report No. TP-510-33123
Nitrogen Content of Biomass
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Red oak sawdust
Fir mill waste
Mixed waste paper
Sugar Cane Bagasse
Urban wood waste
Furniture waste
Miscanthus, Silberfeder
Willow - SV1-3 yr
Wood - land clearing
Danish wheat straw
Alder/fir sawdust
Oregon wheat straw
California wheat straw
Demolition wood
Poplar - coarse
Imperial wheat straw
Hybrid poplar
Willow - SV1-1 yr
Rice husks
Switchgrass, MN
Almond wood
Switchgrass, D Leaf, MN
Switchgrass, OH
Bana Grass, HI
Forest residuals
RFD - Tacoma
Wood - yard waste
Rice straw
Alfalfa stems
Nitrogen (lb/MBtu)
Bain, R. L.; Amos, W. P.; Downing, M.; Perlack, R. L. (2003). Biopower Technical Assessment:
State of the Industry and the Technology. 277 pp.; NREL Report No. TP-510-33123
Combustion
Combustion
Stages of Combustion of Solids
Stages of Combustion of Solids
Drying
Devolatilization
Pyrolysis
Gasification
Flaming Combustion
Residual Char Combustion
) ( ) ( ) (
2 2
g CO g O s C +
) ( ) (
2
1
) (
2 2 2
l O H g O g H +
) ( 2 ) ( 2 ) (
2 2 2 4
l O H g CO O g CH + +
HHV = water as liquid
LHV = water as gas
Combustion Reactions
Combustion Reactions
Combustor Types
Combustor Types
Stoker Grate
Fluid Bed
Circulating Fluid Bed
Entrained Flow
Wood
Pile
Truck Tipper
F
e
e
d
s
t
o
c
k
Dump Conveyor #1
Radial
Stacker
Radial Screw Active
Reclaim Feeder
Rotary Airlock
Feeder
S
e
p
a
r
a
t
o
r
Bin
Vent
Wood Silo
Valve
Valve
Air Intake
Mechanical
Exhauster
M
e
t
a
l
D
e
t
e
c
t
o
r
M
a
g
n
e
t
ic
S
e
p
a
r
a
t
o
r
S
c
a
le
Scale
Scale
Conveyor #2
Disc Feeder
Primary
Hogger
Secondary
Hogger
Collecting
Conveyors
Pressure Blowers
Biomass Co-Firing System
Retrofit for 100 MW Pulverized
Coal Boiler
Existing
Boiler System
Biomass
Feedstock
Handling
Equipment
Existing
Boiler
System Boundary for
Biomass Feedstock
Handling System
SO
X
NO
X
CO PM-10
1
Comments
Stoker Boiler,
Wood Residues (1,4)
0.08 2.1
(biomass type
not specif ied)
12.2
(biomass type
not specif ied)
0.50
(total particulates)
(biomass type
not specif ied)
Based on 23 Calif ornia grate
boilers, except f or SO
2
(uncontrolled)
Fluidized Bed,
Biomass (4)
0.08
(biomass type
not specif ied)
0.9
(biomass type
not specif ied)
0.17
(biomass type
not specif ied)
0.3
(total particulates)
(biomass type
not specif ied)
Based on 11 Calif ornia f luid
bed boilers.
Energy Crops
(Poplar)
Gasification
(a,b)
0.05
(suggested value
based on SOx numbers
f or Stoker and FBC,
adjusted by a f actor of
9,180/13,800 to account
f or heat rate
improvement)
1.10 to 2.2
(0.66 to 1.32 w /SNCR;
0.22 to 0.44 w ith SCR)
0.23 0.01
(total
particulates)
Combustor f lue gas goes
through cyclone and
baghouse. Syngas goes
through scrubber and
baghouse bef ore gas turbine.
No controls on gas turbine.
Bituminous Coal,
Stoker Boiler (f)
20.2
1 wt% S coal
5.8 2.7 0.62
PM Control only
(baghouse)
Pulverized Coal
Boiler (d)
14.3 6.89 0.35 0.32
(total particulates)
Average US PC boiler
(typically:baghouse,
limestone FGC)
Cofiring 15% Biomass
(d2)
12.2 6.17 0.35 0.32 (total
particulates)
?
Fluidized Bed,
Coal (f)
3.7 (1 w t% S coal
Ca/S = 2.5)
2.7 9.6 0.30
Baghouse f or PM Control, Ca
sorbents used f or SO
x
4-Stroke NG
Reciprocating
Engine (g)
0.006 7.96-38.3
(depends on load
and air:f uel ratio)
2.98-35.0
(depends on load
and air:f uel ratio)
0.09-0.18
(depends on load
and air:f uel ratio)
No control except
PCC at high-end of
PM-10 range
Natural Gas
Turbine (e)
0.009
(0.0007 w t% S)
1.72 0.4 .09
(total particulates)
Water-steam
injection only
Natural Gas
Combined Cycle (c,e)
0.004 0.91
(0.21 w / SCR)
0.06 0.14
(total particulates)
Water-steam
injection only
Direct Air Emissions from Wood Residue Facilities by Boiler Type
Biomass Technology
Coal Technology
Natural Gas Technology
(lb/MWh)
NOx Emissions - Life Cycle Total and Plant Operating Emissions
0
1
2
3
4
5
6
7
8
BIGCC direct coal - avg co-firing coal - NSPS NGCC
N
O
x

e
m
i
s
s
i
o
n
s

(
l
b
/
M
W
h
)
total NOx
operating plant NOx
Life Cycle CO2 and Energy Balance
Life Cycle CO2 and Energy Balance
for a Direct
for a Direct
-
-
Fired Biomass System
Fired Biomass System
Current biomass power industry
Direct-Fired Biomass Residue System
134% carbon closure
Net greenhouse gas emissions
-410 g CO
2
equivalent/kWh
Landfill and
Mulching
Transportation Construction
Power Plant
Operation
10 3
1,204
1,627
Avoided Carbon
Emissions
1.0
Fossil
Energy
In
Fossil
Energy
In
Electricity
Out
28.4
Figure 5.11: Biomass CHP - Effect of Plant Size on Cost of Electricity and Steam
0
2
4
6
8
10
12
14
0 25 50 75 100 125 150 175
Equivalent Plant Size (MW)
E
l
e
c
t
r
i
c
i
t
y

(
c
e
n
t
s
/
k
W
h
)

a
n
d

S
t
e
a
m

(
$
/
1
0
0
0

l
b
)

C
o
s
t
s
Combustion - Electricity
Combustion - CHP
Gasification - Electricity
Gasification - CHP
Purchased Electricity
Purchased Steam
15% Cofiring CHP
Incremental Cost
Feed Cost = $2/MBtu
Bain, R. L.; Amos, W. P.; Downing, M.; Perlack, R. L. (2003). Biopower Technical Assessment:
State of the Industry and the Technology. 277 pp.; NREL Report No. TP-510-33123
Biomass CHP - Sensitivity to Feed Cost
-2
0
2
4
6
8
10
12
-2 -1 0 1 2 3 4 5
Feed Cost ($/MBtu)
E
l
e
c
t
r
i
c
i
t
y

(
c
e
n
t
s
/
k
W
h
)

a
n
d

S
t
e
a
m

(
$
/
1
0
0
0

l
b
)

C
o
s
t
s
Direct Combustion
100 MWeq
Gasification
75 MWeq
Gasification
150 MWeq
Purchased
Electricity
Purchased
Steam
15% Cofiring 105 MWeq
Incremental Cost
Bain, R. L.; Amos, W. P.; Downing, M.; Perlack, R. L. (2003). Biopower Technical Assessment:
State of the Industry and the Technology. 277 pp.; NREL Report No. TP-510-33123
Gasification Cleanup Synthesis
Conversion
or Collection
Purification
Separation Purification
Pyrolysis
Other
Conversion *
Biomass
Biomass Thermochemical Conversion
For Fuels and Chemicals
* Examples: Hydrothermal Processing, Liquefaction, Wet Gasification
PRODUCTS
Hydrogen
Alcohols
FT Gasoline
FT Diesel
Olefins
Oxochemicals
Ammonia
SNG
Hydrogen
Olefins
Oils
Specialty Chem
Hydrogen
Methane
Oils
Other
Low
(300-600C)
Medium
(700-850C)
High
(900-1200C)
Temperature
Low
Pressure
0.2 MPa
High
Pressure
ENSYN
Dynamotive
BTG
Fortum
Bio-Oil
Changing World
Technologies
Chemrec (O2)
Noell
GTI (O2)
Carbona (O2)
HTW O2)
Foster Wheeler (O2)
FERCO (Indirect)
MTCI (Indirect)
Pearson (Indirect)
TUV (Indirect)
For CHP:TPS (Air)
Carbona (Air)
Lurgi (Air)
Foster Wheeler (Air)
EPI (Air)
Prime Energy (Air)
Chemrec (Air)
Feed: Biomass Feed: Black Liquor
Feed: Biomass
MTCI-also Black
Liquor
Gas Product: PNNL Wet
Gasification (CH4/H2)
Thermochemical Conversion
Of Biomass and Black Liquor
10-25 MPa 1- 3 MPa 2 3 MPa
Syngas
Product
Dry Ash Slag
Primary Processes Secondary Processes
Tertiary Processes
Vapor
Phase
Liquid
Phase
Solid
Phase
Low P
High
P
Low P
High
P
Biomass
Charcoal
Coke
Soot
Primary
Liquids
Primary
Vapors
Light HCs,
Aromatics,
& Oxygenates
Pyrolysis Severity
Condensed Oils
(phenols, aromatics)
CO, H
2
,
CO
2
, H
2
O
PNAs, CO,
H
2
, CO
2,
H
2
O, CH
4
Olefins, Aromatics
CO, H
2
, CO
2
, H
2
O
CO, CO
2
,
H
2
O

C o n v e n t i o n a l
F l a s h
P y r o l y s i s
( 4 5 0 - 5 0 0
o
C )
H i - T e m p e r a t u r e
F l a s h
P y r o l y s i s
( 6 0 0 - 6 5 0
o
C )
C o n v e n t i o n a l
S t e a m
G a s i f i c a t i o n
( 7 0 0 - 8 0 0
o
C )
H i - T e m p e r a t u r e
S t e a m
G a s i f i c a t i o n
( 9 0 0 - 1 0 0 0
o
C )

A c i d s
A l d e h y d e s
K e t o n e s
F u r a n s
A l c o h o l s
C o m p l e x
O x y g e n a t e s
P h e n o l s
G u a i a c o l s
S y r i n g o l s
C o m p l e x
P h e n o l s

B e n z e n e s
P h e n o l s
C a t e c h o l s
N a p h t h a l e n e s
B i p h e n y l s
P h e n a n t h r e n e s
B e n z o f u r a n s
B e n z a l d e h y d e s


N a p h t h a l e n e s
A c e n a p h t h y l e n e s
F l u o r e n e s
P h e n a n t h r e n e s
B e n z a l d e h y d e s
P h e n o l s
N a p h t h o f u r a n s
B e n z a n t h r a c e n e s

N a p h t h a l e n e *
A c e n a p h t h y l e n e
P h e n a n t h r e n e
F l u o r a n t h e n e
P y r e n e
A c e p h e n a n t h r y l e n e
B e n z a n t h r a c e n e s
B e n z o p y r e n e s
2 2 6 M W P A H s
2 7 6 M W P A H s

* A t t h e h i g h e s t
s e v e r i t y , n a p h t h a l e n e s
s u c h a s m e t h y l
n a p h t h a l e n e a r e
s t r i p p e d t o s i m p l e
n a p h t h a l e n e .







Mixed
Oxygenates
Phenolic
Ethers
Alkyl
Phenolics
Heterocyclic
Ethers PAH
Larger
PAH
400
o
C 500
o
C 600
o
C 700
o
C 800
o
C 900
o
C
Chemical Components in biomass tars (Elliott, 1988)
Gasification
Gasification
Circa 1898
1792 and all that
Murdoch (1792) coal distillation
London gas lights 1802
Blau gas Fontana 1780
1900s Colonial power
MeOH 1913 BASF
Fischer Tropsch 1920s
Vehicle Gazogens WWII
SASOL 1955 - Present
GTL 1995 Present
Hydrogen Future?
Acid Gas
Removal
Feed Preparation
& Handling
Synthesis
Product CO2
Catalytic
Conditioning
& Reforming
Compression
LP Indirect
Gasification
Biomass
Shift
Conversion
Compression
Low Pressure
Gasification
LP Indirect
Gasification
Compression
& Reforming
Cold Gas
Cleanup
Representative Gasification Pathways
Representative Gasification Pathways
Hot Gas
Cleanup
High Pressure
Gasification
Oxygen
Compression Reforming
Freeboard
Fluid Bed
Plenum
Air/Steam
Biomass
Ash
Cyclone
Fluid-Bed Gasifier
Freeboard
Fluid Bed
Plenum
Air/Steam
Biomass
Ash
Cyclone
Fluid-Bed Gasifier
Secondary
Circulating Fluid-Bed Gasifier
Fly Ash
Bottom Ash
Biomass
Air/Steam
Gasifier
Primary
Cyclone
Cyclone
Secondary
Circulating Fluid-Bed Gasifier
Fly Ash
Bottom Ash
Biomass
Air/Steam
Gasifier
Primary
Cyclone
Cyclone
Fly Ash
Bottom Ash
Biomass
Air/Steam
Gasifier
Primary
Cyclone
Cyclone
Biomass
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
Ash
Air
C + CO2 = 2CO
C + H2O = CO + H2
C + O2 = CO2
4H + O2 = 2H2O
Downdraft Gasifier
Biomass
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
Ash
Air
C + CO2 = 2CO
C + H2O = CO + H2
C + O2 = CO2
4H + O2 = 2H2O
Downdraft Gasifier
Biomass
N2 or Steam
Furnace
Char
Recycle Gas
Product
Gas
Flue Gas
Entrained Flow Gasifier
Air
Biomass
N2 or Steam
Furnace
Char
Recycle Gas
Product
Gas
Flue Gas
Entrained Flow Gasifier
Air
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
Ash
Biomass
Air
C + CO2 = 2CO
C + H2O = CO + H2
C + O2 = CO2
4H + O2 = 2H2O
Updraft Gasifier
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
Ash
Biomass
Air
C + CO2 = 2CO
C + H2O = CO + H2
C + O2 = CO2
4H + O2 = 2H2O
Updraft Gasifier
Gasifier Types
Gasifier Types
-
-
Advantages and Disadvantages
Advantages and Disadvantages

Gasifier Advantages Disadvantages
Updraft Mature for heat
Small scale applications
Can handle high moisture
No carbon in ash
Feed size limits
High tar yields
Scale limitations
Producer gas
Slagging potential

Downdraft Small scale applications
Low particulates
Low tar

Feed size limits
Scale limitations
Producer gas
Moisture sensitive

Fluid Bed Large scale applications
Feed characteristics
Direct/indirect heating
Can produce syngas

Medium tar yield
Higher particle loading

Circulating Fluid Bed Large scale applications
Feed characteristics
Can produce syngas

Medium tar yield
Higher particle loading

Entrained Flow Can be scaled
Potential for low tar
Can produce syngas


Large amount of carrier gas
Higher particle loading
Potentially high S/C
Particle size limits

Table 2: Gas composition for fluid bed and Table 2: Gas composition for fluid bed and
circulating fluid bed gasifiers circulating fluid bed gasifiers
Gasifier FERCO Carbona Princeton IGT
Model
Type Indirect CFB Air FB Indirect FB PFB
Agent steam air steam O2/steam
Bed Material olivine sand none alumina
Feed wood chips wood pellets black liquor wood chips
Gas Composition
H2 26.2 21.70 29.4 19.1
CO 38.2 23.8 39.2 11.1
CO2 15.1 9.4 13.1 28.9
N2 2 41.6 0.2 27.8
CH4 14.9 0.08 13.0 11.2
C2+ 4 0.6 4.4 2.0
GCV, MJ/Nm
3
16.3 5.4 17.2 9.2
Gasifier Inlet Gas Product Gas Product Gas
Type HHV
MJ/Nm
3
Partial Oxidation Air Producer Gas 7
Partial Oxidation Oxygen Synthesis Gas 10
Indirect Steam Synthesis Gas 15
Natural Gas 38
Methane 41
Typical Gas Heating Values
Typical Gas Heating Values
Biomass Coal
Oxygen
Sulfur
Ash
Alkali
H/C Ratio
Heating Value
Tar Reactivity
Use coal gasifier cleanup technology for
biomass
Issues
Coal cleanup designed for large, integrated
plants
Extensive sulfur removal not needed for
biomass
Biomass tars very reactive
Wet/cold cleanup systems produce
significant waste streams that require
cleanup/recovery large plant needed for
economy of scale for cleanup/recovery
Biomass particulates high in alkali
Feed biomass to coal gasifiers
Issues
Feeding biomass (not just wood) many
commercial coal gasifiers are entrained
flow requiring small particles
Gasifier refractory life/ash properties
biomass high in alkali
Character/reactivity of biomass tars may
have unknown impact on
chemistry/cleanup
Volumetric energy density a potential issue
Biomass reactivity may react in feeder
FERCO GASIFIER FERCO GASIFIER- - BURLINGTON, VT BURLINGTON, VT
350 TPD 350 TPD
Community Power Corporation Community Power Corporation s s
BioMax 15 Modular Biopower System BioMax 15 Modular Biopower System
Carbona Project: Skive, Denmark
Carbona Project: Skive, Denmark
BIOMASS BIOMASS
ASH ASH
AIR AIR
ASH ASH
POWER POWER
HEAT HEAT
FUEL FUEL
FEEDING FEEDING
GASIFIER GASIFIER
TAR CRACKER TAR CRACKER
GAS COOLER GAS COOLER GAS COOLER GAS COOLER
STACK STACK
HEAT RECOVERY HEAT RECOVERY
GAS TANK GAS TANK
GAS ENGINE(S) GAS ENGINE(S)
Contribution to Hydrogen Price for BCL Low Pressure Indirectly-Heated Gasifier
System (2,000 tonne/day plant; $30/dry ton feedstock)
-10% -5% 0% 5% 10% 15% 20% 25% 30% 35% 40% 45%
By-product steam credit
Heat exchange, pumps,
& BOP
PSA
Reforming & shift
conversion
Syngas compressor
Gasification & gas clean
up
Feed handling & drying
Biomass feedstock
Capital Feedstock Process Electricity
Operating Costs By-Product Credit
41%
8%
11%
22%
7%
10%
6%
-5%
41%
Contribution to Hydrogen Price for BCL Low Pressure Indirectly-Heated Gasifier
System (2,000 tonne/day plant; $53/dry ton feedstock)
-10% -5% 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50% 55%
By-product steam credit
Heat exchange, pumps,
& BOP
PSA
Reforming & shift
conversion
Syngas compressor
Gasification & gas clean
up
Feed handling & drying
Biomass feedstock
Capital Feedstock Process Electricity
Operating Costs By-Product Credit
55%
6%
8%
17%
6%
8%
4%
-4%
31%
Life Cycle GWP and Energy Balance for Advanced IGCC
Technology using Energy Crop Biomass
Future, wide-spread potential
Syngas
CO + H
2
Methanol
H
2
O
WGS
Purify
H
2
N
2
over Fe/FeO
(K
2
O, Al
2
O
3
, CaO)
NH
3
Cu/ZnO
Isosynthesis
ThO
2
or ZrO
2
i-C
4
A
l
k
a
l
i
-
d
o
p
e
d
Z
n
O
/
C
r
2
O
3
C
u
/
Z
n
O
;

C
u
/
Z
n
O
/
A
l
2
O
3
C
u
O
/
C
o
O
/
A
l
2
O
3
M
o
S
2
Mixed
Alcohols
O
x
o
s
y
n
t
h
e
s
i
s
H
C
o
(
C
O
)
4
H
C
o
(
C
O
)
3
P
(
B
u
3
)
R
h
(
C
O
)
(
P
P
h
3
)
3
Aldehydes
Alcohols
Fischer-Tropsch
F
e
,

C
o
,

R
u
Waxes
Diesel
Olefins
Gasoline
Ethanol
C
o
,

R
h
Formaldehyde
A
g
DME
A
l
2
O
3
zeolites
MTO
MTG
Olefins
Gasoline
MTBE
Acetic Acid
c
a
r
b
o
n
y
l
a
t
i
o
n
C
H
3
O
H

+

C
O
C
o
,

R
h
,

N
i
M100
M85
DMFC
D
i
r
e
c
t

U
s
e
h
o
m
o
l
o
g
a
t
i
o
n
C
o
i
s
o
b
u
t
y
l
e
n
e
a
c
i
d
i
c

i
o
n

e
x
c
h
a
n
g
e
C
R
U
D
E

T
O
W
E
R
VACUUM
UNIT
DELAYED
COKER
HYDROTREATING
OVERHEAD
DRUM
GAS PLANT
ISOMERIZATION
UNIT
CATALYTIC
REFORMING
HYDROTREATING
FLUID
CATALYTIC
CRACKING
SULFUR
TREATMENT
HYDROTREATING
GAS PLANT
ALKYLATION
UNIT
GASOLINE
TO REFORMER
COKE
TAR
DECANT OIL
HEAVY
GAS OIL
LIGHT
GAS OIL
C
O
K
E
R
G
A
S

O
I
L
F
U
E
L

G
A
S
RAW DIESEL
CRUDE
OIL
RAW
KEROSENE
H2
H2
ATMOS
RESID
HDT
TREATED NAPHTHA (TO REFORMER)
TREATED DIESEL
TREATED RESID
HYDRO
CRACKING
REFINERY FUEL GAS
LPG
REGULAR GASOLINE
PREMIUM GASOLINE
SOLVENTS
AVIATION FUELS
DIESELS
HEATING OILS
LUBE OILS
GREASES
ASPHALTS
INDUSTRIAL FUELS
REFINERY FUEL OIL
COKE
T
R
E
A
T
I
N
G

A
N
D

B
L
E
N
D
I
N
G
Conceptual Petroleum Refinery Conceptual Petroleum Refinery
BIOMASS SYNGAS
ETHANOL
FEED
PREP
GASIFICATION
CLEANUP &
CONDITIONING
BIOCONVERSION
SEPARATION
Ethanol From Biomass
Ethanol From Biomass
Thermochemical Syngas Thermochemical Syngas Biochemical Ethanol Biochemical Ethanol
Syngas
Syngas
Liquid Fuels/Chemicals
$5.5. billion
Pulp
$5.5 billion
BL Gasifier
Wood Residual
Gasifier
Combined Cycle System
Process to manufacture
Liquid Fuels and Chemicals
Extract Hemicelluloses
new products
chemicals & polymers
$3.3 billion
Black Liquor
& Residuals
Steam,
Power &
Chemicals
Net Revenue Potential of Biorefinery
Net Revenue Potential of Biorefinery
on the U.S. Pulp Industry
on the U.S. Pulp Industry
Freeboard
Fluid Bed
Plenum
Air/Steam
Biomass
Ash
Product Gas
Cyclone
Fluid-Bed Gasifier
Gas
Cleanup
Compressor
Cooling
Air
Isothermal
Pre-reformer
HRSG
A C
Carbonate
Fuel Cells
Burner
Air
DC/AC
Inverter
Process
Water
Exhaust
A.C.
Output
Pyrolysis
Pyrolysis
Pyrolysis
Thermal decomposition occurring in
the absence of oxygen
Is always the first step in
combustion and gasification
processes
Known as a technology for
producing charcoal and chemicals
for thousands years
Mechanisms of Pyrolysis
Many pathways and mechanisms proposed
Broido-Shafizadeh model for cellulose shows
typical complexity of pathways and
possibilities for product maximization
Cellulose
Cellulose

Active
Active

cellulose
cellulose
Vapor
Vapor

(liquid)
(liquid)
CH
CH
4 4
H
H
2 2
CO C
CO C
2 2
H
H
2 2
Secondary tar, char
Secondary tar, char
Water, char, CO CO
Water, char, CO CO
2 2
Biomass Pyrolysis
Products
Liquid Char Gas
FAST PYROLYSIS 75% 12% 13%
moderate temperature
short residence time
CARBONIZATION 30% 35% 35%
low temperature
long residence time
GASIFICATION 5% 10% 85%
high temperature
long residence time
Fast Pyrolysis of Biomass
Fast pyrolysis is a thermal process that rapidly heats biomass
to a carefully controlled temperature (~500C), then very
quickly cools the volatile products (<2 sec) formed in the
reactor
Offers the unique advantage of producing a liquid that can be
stored and transported
Has been developed in many configurations
At present is at relatively early stage of development
Process Requirements
Drying
Comminution
Fast pyrolysis
Char separation
Liquid recovery
<10% moisture; feed and reaction
water end up in bio-oil
2mm (bubbling bed), 6 mm (CFB)
High heat rate, controlled T, short
residence time
Efficient char separation needed
By condensation and
coalescence.
Fluid beds 400 kg/h at DynaMotive
20 kg/h at RTI
Many research units
CFBs 1000 kg/h at Red Arrow (Ensyn)
20 kg/h at VTT (Ensyn)
350 kg/h (Fortum, Finland)
Rotating cone 200 kg/h at BTG (Netherlands)
Vacuum 3500 kg/h at Pyrovac
Auger 200 kg/h at ROI
Operational Pyrolysis Units
Bubbling Fluid Bed Pyrolysis
BIOMASS
BIO-OIL
CHAR
For reactor or export
Gas
recycle
GAS
For fluidization or export
Fluid
bed
reactor
Fluid Bed Heating Options
Wood feed
Vapor product
3 Hot fluidizing
gas
2 Recycled
hot sand
5 Hot tubes
1 Hot wall
4 Air addition
Char+air
Bubbling Fluid Bed
250 kg/h pilot plant at Wellman, UK
Fluid Bed Reactors
Good temperature control,
Char removal is usually by ejection and
entrainment; separation by cyclone,
Easy scaling,
Well understood technology since first
experiments at University of Waterloo in
1980s
Small particle sizes needed,
Heat transfer to bed at large scale has to be
proven.
Circulating Fluid Beds
BIO-OIL
BIOMASS
Flue gas
Gas
recycle
GAS
To reactor or export
Sand+
Char
Combustor
Pyrolyzer
Air
Hot
sand
Good temperature control in reactor,
Larger particle sizes possible,
CFBs suitable for very large throughputs,
Well understood technology,
Hydrodynamics more complex, larger gas
flows in the system,
Char is finer due to more attrition at higher
velocities; separation is by cyclone,
Closely integrated char combustion requires
careful control,
Heat transfer to bed at large scale has to be
proven.
CFB and Transported Beds
Rotating Cone (BTG)
Centrifugation
drives hot sand
and biomass up
rotating heated
cone;
Vapors are
condensed;
Char is burned
and hot sand is
recirculated.

Particle trajectory
Heated
rotating
cone
Particle
Developed at Universit Laval, Canada,
scaled up by Pyrovac
Pilot plant operating at 50 kg/h
Demonstration unit at 3.5 t/h
Analogous to fast pyrolysis as vapor
residence time is similar.
Lower bio-oil yield 35-50%
Complicated mechanically (stirring
wood bed to improve heat transfer)
Vacuum Moving Bed
Developed for biomass pyrolysis by Sea
Sweep, Inc (oil adsorbent) then ROI (bio-oil);
5 t/d (200 kg/h) mobile plant designed for
pyrolysis of chicken litter;
Compact, does not require carrier gas;
Lower process temperature (400C);
Lower bio-oil yields
Moving parts in the hot zone
Heat transfer at larger scale may be a
problem
Auger Reactor
Char acts as a vapor cracking catalyst so
rapid and effective removal is essential.
Cyclones are usual method of char removal.
Fines pass through and collect in liquid
product.
Hot vapor filtration gives high quality char
free product. Char accumulation cracks
vapors and reduces liquid yield (~20%).
Limited experience is available.
Liquid filtration is very difficult due to nature
of char and pyrolytic lignin.
Char Removal
Primary pyrolysis products are vapors and
aerosols from decomposition of cellulose,
hemicellulose and lignin.
Liquid collection requires cooling and
agglomeration or coalescence of aerosols.
Simple heat exchange can cause
preferential deposition of heavier fractions
leading to blockage.
Quenching in product liquid or immiscible
hydrocarbon followed by electrostatic
precipitation is preferred method.
Liquid Collection
Bio-oil is water miscible and is
comprised of many oxygenated organic
chemicals.
Dark brown mobile liquid,
Combustible,
Not miscible with
hydrocarbons,
Heating value ~ 17 MJ/kg,
Density ~ 1.2 kg/l,
Acid, pH ~ 2.5,
Pungent odour,
Ages - viscosity increases
with time
Fast Pyrolysis Bio-oil
The complexity and nature of the liquid
results in some unusual properties.
Due to physical-chemical processes such as:
Polymerization/condensation
Esterification and etherification
Agglomeration of oligomeric molecules
Properties of bio-oil change with time:
Viscosity increases
Volatility decreases
Phase separation, deposits, gums
Bio-oil Properties
Physical Methods
Filtration for char removal,
Emulsification with hydrocarbons,
Solvent addition,
Chemical Methods
Reaction with alcohols,
Catalytic deoxygenation:
Hydrotreating,
Catalytic (zeolite) vapor cracking.
Upgrading of Bio-oils
Applications of Bio-oils

Electricity Transport fuel
Heat

Bio-oil

Extract

Upgrade

Boiler
Chemicals
Bio-oil Cost
Different claims of the cost of production:
Ensyn $4-5/GJ ($68-75/ton)
BTG $6/GJ ($100/ton)
Cost = Wood cost/10 + 8.87 * (Wood throughput)
-0.347
$/GJ $/dry ton dry t/h
A.V. Bridgwater, A Guide to Fast Pyrolysis of Biomass for Fuels and
Chemicals, PyNe Guide 1, www.pyne.co.uk
Why Is Bio-oil Not Used More?
Cost : 10% 100% more than fossil fuel,
Availability: limited supplies for testing
Standards; lack of standards and inconsistent
quality inhibits wider usage,
Incompatibility with conventional fuels,
Unfamiliarity of users
Dedicated fuel handling needed,
Poor image.
Research Opportunities
Research Opportunities
Technical Barrier Areas
Technical Barrier Areas
Feed Processing and Handling
Gasification / Conversion
Gas Cleanup and Catalytic Conditioning
Syngas Utilization
Process Integration
Process Control, Sensors, and Optimization
Feed
Processing
& Handling
Gasification
&
Pyrolysis
Gas
Conditioning
& Separation
Syngas
Utilization
Heat
& Power
Generation
Hydrogen
& Bioproducts
Fuels
& Chemicals
Export
Electricity
Biomass Residues
Dedicated Crops
Biorefinery
Residues
Biomass Thermochemical Conversion
Primary Technical Barriers
Gasification Pyrolysis Black Liquor Gasification
Feed Pretreatment
- Feeder reliability
- Feed modification
Gasification
- Tar & Heteroatom chemistry
- Gasifier Design
- Catalysis
Gas Cleanup & Conditioning
- Catalytic Conversion
- Condensing Cleanup
- Non-condensing Cleanup
Syngas Utilization
- Cleanliness requirements
- Gas composition
Process Integration
Sensors and Controls
Catalytic Pyrolysis
Oil Handling
- Toxicity
- Stability
- Storage
- Transportation
Oil Properties
- Ash
- Acidity
Oil Commercial Properties
- Commercial Specifications
- Use in Petroleum Refineries
Containment
- Metals
- Refractories
- Vessel design
- Bed behavior/agglomeration
Mill Integration
- Steam
- Power
- Causticizing
Fuels Chemistry
- Carbon management
- Tars
- Sulfur management
- Alkali management
- Halogen management
Sensors and Controls
Possible Reading
Possible Reading
1. Bain, R. L.; Amos, W. P.; Downing, M.; Perlack, R. L. (2003). Biopower
Technical Assessment: State of the Industry and the Technology. 277 pp.;
NREL Report No. TP-510-33123.
2. Bridgewater, A.V. (2003). A Guide to Fast Pyrolysis of Biomass for Fuels and
Chemicals, PyNe Guide 1, www.pyne.co.uk
3. Brown, R. C. (2003). Biorenewable Resources: Engineering New Products
From Agriculture, Iowa State Press, ISBN:0-8138-2263-7.
4. Higman, C. and M. van der Burgt (2003). Gasification, Elsevier Science (USA),
ISBN 0-7506-7707-4.
5. Probstein, R. F. and R. E. Hicks (1982). Synthetic Fuels, McGraw-Hill, Inc.,
ISBN 0-07-050908-5.
6. Van Loo, S. and J. Koppejan (eds.) (2002). Handbook of Biomass Combustion
and Co-firing, Twente University Press, ISBN 9036517737.