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
 Fuels, Chemicals, Materials, Heat and Power from Biomass
USES
Fuels:
Ethanol
Renewable Diesel

Electricity

Heat

Chemicals
– Plastics
– Solvents
– Pharmaceuticals
Biomass Conversion – Chemical Intermediates
– Phenolics
Feedstock Processes – Adhesives
– Furfural
– Trees – Fatty acids
– Forest Residues - Gasification – Acetic Acid
– Grasses - Combustion and Cofiring – Carbon black
– Agricultural Crops - Pyrolysis – Paints
– Agricultural Residues – Dyes, Pigments, and Ink
- Enzymatic Fermentation
– Animal Wastes – Detergents
- Gas/liquid Fermentation – Etc.
– Municipal Solid Waste - Acid Hydrolysis/Fermentation
- Other Food and Feed
 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.
 Basic Definitions
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

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
• 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
 Thermal
Conversion

Excess air Partial air No Air

Pyrolysis &
Combustion Gasification Pyrolysis
Hydrothermal

Heat Fuel Gases Liquids

(CO + H 2)
 POTENTIAL BIOMASS PRODUCTS
• Potential Biomass Products
• Biomass
• Syngas
• Hydrogen
• Pyrolysis Oil – Whole or Fractionated
• Hydrothermal Treatment Oils
• Biomass
• Solid
• CH1.4O0.6
• HHV = 16 – 17 MBTU/ton (MAF)
• Syngas
• Major components – CO, H2, CO2
• CO/H2 ratio set by steam rate in conditioning step, typical range 0.5 – 2
• HHV: 450-500 BTU/scf
• Pyrolysis Oil
• CH1.4O0.5
• 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 (40°C, 25% water) – 40 to 100 cp, vacuum distillation
residue – up to 50%
• Hydrothermal Treatment Oils
• Water plus alkali at T = 300-350°C, P high enough to keep water liquid. Use of CO is option
• Yield > 95%
• Distillate (-500°C): 40 – 50%
• Distillate Composition: Hardwood (300°C) – CH1.2O0.2, Manure (350°C) – CH1.4O0.1
• 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
to Thermal Conversion
 Representative Biomass & Black Liquor Compositions

Poplar Corn Stover Chicken Litter Black Liquor

Prox ima te (w t% as received)

Ash 1.16 4.75 18.65 52.01

Vola tile Ma tte r 81.99 75.96 58.21 35.26
Fixe d Ca rbon 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

Ultima te, w t% a s receive d

Ca rbon 47.05 43.98 32.00 32.12

Hydrogen 5.71 5.39 5.48 2.85
Nitroge n 0.22 0.62 6.64 0.24
Sulfur 0.05 0.10 0.96 4.79
Oxyge n (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

Eleme nta l Ash Analysis, w t% of fue l as re ce ive d

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 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 Higher Heating Value
(with 95% confidence interval)
12000

10000
Actual HHV (Btu/lb)

8000

6000

4000

2000

0
4000 5000 6000 7000 8000 9000 10000

Calculated HHV (Btu/lb)

HHV (Btu/lb) = 8 5.6 5 + 13 7.0 4 C + 21 7 .55 H + 6 2.5 6 N + 1 07 .73 S + 8.0 4 O - 12 .94 A (E q 3 -15 ) 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

Rice straw
Imperial wheat straw
California wheat straw
Alfalfa stems
Oregon wheat straw
Switchgrass, OH
Rice husks
Danish wheat straw
Wood - yard waste
Almond wood
Wood - land clearing
Miscanthus, Silberfeder
Poplar - coarse
Forest residuals
Demolition wood
Switchgrass, D Leaf, MN
Hybrid poplar
Switchgrass, MN
Alder/fir sawdust
Willow - SV1-1 yr
Furniture waste
Willow - SV1-3 yr
Urban wood waste
Sugar Cane Bagasse
Red oak sawdust
RFD - Tacoma
Fir mill waste
Mixed waste paper

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

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

Alfalfa stems
Rice straw
Wood - yard waste
RFD - Tacoma
Forest residuals
Bana Grass, HI
Switchgrass, OH
Switchgrass, D Leaf, MN
Almond wood
Switchgrass, MN
Rice husks
Willow - SV1-1 yr
Hybrid poplar
Imperial wheat straw
Poplar - coarse
Demolition wood
California wheat straw
Oregon wheat straw
Alder/fir sawdust
Danish wheat straw
Wood - land clearing
Willow - SV1-3 yr
Miscanthus, Silberfeder
Furniture waste
Urban wood waste
Sugar Cane Bagasse
Mixed waste paper
Fir mill waste
Red oak sawdust

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

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
Stages of Combustion of Solids

•Drying
•Devolatilization
9Pyrolysis
9Gasification
•Flaming Combustion
•Residual Char Combustion
Combustion Reactions

C ( s) + O2 ( g ) → CO2 ( g )
1
H 2 ( g ) + O2 ( g ) → H 2 O (l )
2
CH 4 ( g ) + 2O2 → CO2 ( g ) + 2 H 2 O(l )

HHV = water as liquid

LHV = water as gas
 Combustor Types

•Stoker Grate
•Fluid Bed
•Circulating Fluid Bed
•Entrained Flow
 ck
ed s to
M Fe
De etal Dump Conveyor #1
tec
tor Ma
Primary S e g n e t ic
p ar
Hogger ato Wood
r
Pile Radial
Stacker Truck Tipper

Secondary
Hogger Radial Screw Active
Sc Reclaim Feeder
ale
System Boundary for
Biomass Feedstock
Disc Feeder
Biomass Existing
Handling System
Feedstock Boiler System
Conveyor #2
Rotary Airlock Handling
Feeder Equipment

Air Intake
Existing
Valve Boiler
Separator

Valve
Bin Mechanical
Vent Exhauster

Wood Silo

Biomass Co-Firing System

Collecting Retrofit for 100 MW Pulverized
Conveyors
Coal Boiler
Scale

Scale

Pressure Blowers
 Direct Air Emissions from Wood Residue Facilities by Boiler Type
(lb/MWh)
SO X NO X CO PM-101 Comments
Biomass Technology
Stoker Boiler, 0.08 2.1 12.2 0.50 Based on 23 Calif ornia grate
W ood Residues (1,4) (biomass type (biomass type (total particulates) boilers, except f or SO2
not specif ied) not specif ied) (biomass type (uncontrolled)
not specif ied)
Fluidized Bed, 0.08 0.9 0.17 0.3 Based on 11 Calif ornia f luid
Biomass (4) (biomass type (biomass type (biomass type (total particulates) bed boilers.
not specif ied) not specif ied) not specif ied) (biomass type
not specif ied)
Energy Crops 0.05 1.10 to 2.2 0.23 0.01 Combustor f lue gas goes
(Poplar) (s ugge s te d value (0.66 to 1.32 w /SNCR; (total through cyclone and
based on SOx numbers 0.22 to 0.44 w ith SCR) particulates) baghouse. Syngas goes
Gasification
f or Stoker and FBC, through scrubber and
(a,b) baghouse bef ore gas turbine.
adjusted by a f actor of
9,180/13,800 to account No controls on gas turbine.
f or heat rate
improvement)

Coal Technology
Bituminous Coal, 20.2 5.8 2.7 0.62 PM Control only
Stoker Boiler (f) 1 wt% S coal (baghouse)

Pulverized Coal 14.3 6.89 0.35 0.32 A verage US PC boiler

Boiler (d) (total particulates) (typically:baghouse,
limestone FGC)
Cofiring 15% Biomass 12.2 6.17 0.35 0.32 (total ?
(d2) particulates)

Fluidized Bed, 3.7 (1 w t% S coal 2.7 9.6 0.30 Baghouse f or PM Control, Ca

Coal (f) Ca/S = 2.5) sorbents used f or SOx

Natural Gas Technology

4-Stroke NG 0.006 7.96-38.3 2.98-35.0 0.09-0.18 No control except
Reciprocating (depends on load (depends on load (depends on load PCC at high-end of
and air:f uel ratio) and air:f uel ratio) and air:f uel ratio) PM-10 range
Engine (g)
Natural Gas 0.009 1.72 0.4 .09 Water-steam
Turbine (e) (0.0007 w t% S) (total particulates) injection only

Natural Gas 0.004 0.91 0.06 0.14 Water-steam

Combined Cycle (c,e) (0.21 w / SCR) (total particulates) injection only
 NOx Emissions - Life Cycle Total and Plant Operating Emissions

8
total NOx
7
operating plant NOx
6
NOx emissions (lb/MWh)

0
BIGCC direct coal - avg co-firing coal - NSPS NGCC
 Life Cycle CO2 and Energy Balance
for a Direct-Fired Biomass System
Current biomass power industry

Net greenhouse gas emissions

-410 g CO2 equivalent/kWh
1,204

Avoided Carbon
Emissions Electricity
1.0
1,627 Out
10 3 28.4
Fossil
Energy Landfill and Transportation Construction Power Plant
In Mulching Operation

Direct-Fired Biomass Residue System

134% carbon closure
 Figure 5.11: Biomass CHP - Effect of Plant Size on Cost of Electricity and Steam
Feed Cost = $2/MBtu
14

12
Electricity (cents/kWh) and Steam ($/1000 lb) Costs

10
Combustion - Electricity

Combustion - CHP
Gasification - Electricity
8

Gasification - CHP

4 Purchased Electricity

Purchased Steam
15% Cofiring CHP
2 Incremental Cost

0
0 25 50 75 100 125 150 175
Equivalent Plant Size (MW)

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
12

10

Gasification
Electricity (cents/kWh) and Steam ($/1000 lb) Costs

75 MWeq
8
Direct Combustion
100 MWeq
Gasification
150 MWeq
6

Purchased
4 Electricity

Purchased
Steam
2

15% Cofiring 105 MWeq

0 Incremental Cost

-2
-2 -1 0 1 2 3 4 5
Feed Cost ($/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 Thermochemical Conversion
PRODUCTS
For Fuels and Chemicals
• Hydrogen
• Alcohols
• FT Gasoline
• FT Diesel
Gasification Cleanup Synthesis
• Olefins
• Oxochemicals
• Ammonia
• SNG

• Hydrogen
Conversion • Olefins
Biomass Pyrolysis Purification
or Collection • Oils
• Specialty Chem

• Hydrogen
Other • Methane
Separation Purification
Conversion * • Oils
• Other

* Examples: Hydrothermal Processing, Liquefaction, Wet Gasification

 Thermochemical Conversion
Of Biomass and Black Liquor
Product Bio-Oil Syngas
Dry Ash Slag
Changing World
Technologies
GTI (O2) Chemrec (O2)
Gas Product: PNNL Wet Carbona (O2) Noell
Gasification (CH4/H2) HTW O2)
High Foster Wheeler (O2)
Pressure 10-25 MPa 1- 3 MPa 2 – 3 MPa

Feed: Biomass
Feed: Biomass MTCI-also Black Feed: Black Liquor
Liquor

FERCO (Indirect)
MTCI (Indirect)
Pearson (Indirect)
Low TUV (Indirect)
ENSYN For CHP:TPS (Air)
Pressure Carbona (Air) Chemrec (Air)
Dynamotive
0.2 MPa Lurgi (Air)
BTG
Fortum Foster Wheeler (Air)
EPI (Air)
Prime Energy (Air)

Low Medium High

(300-600°C) (700-850°C) (900-1200°C)
Temperature
 Primary Processes Secondary Processes Tertiary Processes

Light HCs, PNA’s, CO,

Vapor CO, CO2, Primary Olefins, Aromatics CO, H2,
Aromatics, H2, CO2, CO2, H2O
Phase H2O Vapors CO, H2, CO2, H2O
& Oxygenates H2O, CH4

Low P

Liquid Primary Condensed Oils

Liquids (phenols, aromatics)
Phase High
P

Low P
Solid
Phase Biomass Charcoal Coke Soot
High
P

Pyrolysis Severity
Mixed Phenolic Alkyl Heterocyclic Larger
Oxygenates Ethers Phenolics Ethers PAH PAH
o o o o o o
400 C 500 C 600 C 700 C 800 C 900 C
C o n v e n t io n a l H i- T e m p e r a t u r e C o n v e n t io n a l H i- T e m p e r a t u r e
F la s h F la s h S te a m S te a m
P y r o l y s is P y r o ly s is G a s if i c a t io n G a s if ic a t io n
o o o o
(4 5 0 - 5 0 0 C ) (6 0 0 - 6 5 0 C ) (7 0 0 - 8 0 0 C ) (9 0 0 - 1 0 0 0 C )

A c id s B enzenes N a p h th a le n e s N a p h t h a le n e *
A ld e h y d e s P h e n o ls A c e n a p h t h y le n e s A c e n a p h t h y le n e
K e to n e s C a te c h o ls F lu o r e n e s P h e n a n th re n e
F u ra n s N a p h t h a le n e s P h e n a n th re n e s F lu o r a n t h e n e
A lc o h o ls B ip h e n y ls B e n z a ld e h y d e s P yre n e
C o m p le x P h e n a n th re n e s P h e n o ls A c e p h e n a n t h r y le n e
O x y g e n a te s B e n z o fu ra n s N a p h th o fu ra n s B e n z a n th ra c e n e s
P h e n o ls B e n z a ld e h y d e s B e n z a n th ra c e n e s B e n zo p yre n e s
G u a i a c o ls 226 M W PAH s
S y r in g o ls 276 M W PAH s
C o m p le x
P h e n o ls

* A t t h e h ig h e s t
s e v e r it y , n a p h t h a l e n e s
s u c h a s m e th y l
n a p h t h a le n e a r e
s t r ip p e d t o s i m p le
n a p h t h a le n e .

Chemical Components in biomass tars (Elliott, 1988)

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?
 Representative Gasification Pathways

Low Pressure Shift

Biomass Compression
Gasification Conversion

Feed Preparation
Oxygen
& Handling
CO2 Product

High Pressure Hot Gas Acid Gas

Reforming Compression Synthesis
Gasification Cleanup Removal

LP Indirect Cold Gas Compression

Gasification Cleanup & Reforming

Catalytic
LP Indirect
Conditioning Compression
Gasification
& Reforming
 Biomass
Biomass
Cyclone

Freeboard

Gas, Tar, Water

Gas, Tar, Water
Pyrolysis Ash
C + CO2 = 2CO Pyrolysis
C + H2O = CO + H2 Reduction C + O2 = CO2 Fluid Bed
4H + O2 = 2H2O
Combustion
Biomass
C + O2 = CO2 Combustion
C + CO2 = 2CO
4H + O2 = 2H2O C + H2O = CO + H2 Reduction Air Plenum
Ash Air/Steam
Air Ash

Updraft Gasifier Downdraft Gasifier Fluid-Bed Gasifier

Flue Gas

Secondary
Primary Cyclone
Gasifier Cyclone

Fly Ash Product

Gas

Biomass Biomass Char

Furnace
Air/Steam Recycle Gas
N2 or Steam
Bottom Ash
Air
Circulating Fluid-Bed Gasifier
Entrained Flow Gasifier
Gasifier Types-Advantages and Disadvantages

Gasifier Advantages Disadvantages

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

Downdraft Small scale applications Feed size limits

Low particulates Scale limitations
Low tar Producer gas
Moisture sensitive

Fluid Bed Large scale applications Medium tar yield

Feed characteristics Higher particle loading
Direct/indirect heating
Can produce syngas

Circulating Fluid Bed Large scale applications Medium tar yield

Feed characteristics Higher particle loading
Can produce syngas

Entrained Flow Can be scaled Large amount of carrier gas

Potential for low tar Higher particle loading
Can produce syngas Potentially high S/C
Particle size limits
 Table 2: Gas composition for fluid bed and
circulating fluid bed gasifiers

Gas ifie r FERCO Car bona Pr ince ton IGT

M ode l

Type Indir e ct CFB Air FB Indir e ct FB PFB

Age nt s te am air s te am O2/s te am
Be d M ate r ial olivine s and none alum ina
Fe e d w ood chips w ood pe lle ts black liquor w ood chips

Gas Com pos ition

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 , M J/Nm 3 16.3 5.4 17.2 9.2
 Typical Gas Heating Values

Gasifier Inlet Gas Product Gas Product Gas

Type HHV
3
MJ/Nm

Partial Oxidation Air Producer Gas 7

Partial Oxidation Oxygen Synthesis Gas 10
Indirect Steam Synthesis Gas 15
Natural Gas 38
Methane 41
 • Use coal gasifier cleanup technology for
biomass
Biomass Coal
– Issues
Oxygen • Coal cleanup designed for large, integrated
plants
Sulfur • Extensive sulfur removal not needed for
biomass
• Biomass tars very reactive
Ash • Wet/cold cleanup systems produce
significant waste streams that require
cleanup/recovery – large plant needed for
Alkali economy of scale for cleanup/recovery
• Biomass particulates high in alkali

H/C Ratio • Feed biomass to coal gasifiers

– Issues
• Feeding biomass (not just wood) – many
Heating Value commercial coal gasifiers are entrained
flow requiring small particles
Tar Reactivity • 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- BURLINGTON, VT

350 TPD
 Community Power Corporation’s
BioMax 15 Modular Biopower System
 Carbona Project: Skive, Denmark

TAR CRACKER
GASIFIER
STACK
GAS COOLER GAS COOLER
BIOMASS

ASH GAS TANK

FUEL
FEEDING

HEAT RECOVERY

POWER

AIR HEAT
GAS ENGINE(S)
ASH
 Contribution to Hydrogen Price for BCL Low Pressure Indirectly-Heated Gasifier
System (2,000 tonne/day plant; $30/dry ton feedstock)

Capital Feedstock Process Electricity

Operating Costs By-Product Credit

Biomass feedstock 41%

Feed handling & drying 8%

Gasification & gas clean 41%

11%
up

Syngas compressor 22%

Reforming & shift

7%
conversion

PSA 10%

Heat exchange, pumps, 6%

& BOP

By-product steam credit -5%

-10% -5% 0% 5% 10% 15% 20% 25% 30% 35% 40% 45%
 Contribution to Hydrogen Price for BCL Low Pressure Indirectly-Heated Gasifier
System (2,000 tonne/day plant; $53/dry ton feedstock)

Capital Feedstock Process Electricity

Operating Costs By-Product Credit
55%
Biomass feedstock

Feed handling & drying 6%

Gasification & gas clean 31%

8%
up

Syngas compressor 17%

Reforming & shift

6%
conversion

PSA 8%

Heat exchange, pumps, 4%

& BOP

By-product steam credit -4%

-10% -5% 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50% 55%
Life Cycle GWP and Energy Balance for Advanced IGCC
Technology using Energy Crop Biomass
Future, wide-spread potential
 Waxes Olefins
Diesel Gasoline
MTBE
Mixed Acetic Acid

acidic ion exchange

Alcohols Fischer-Tropsch

+ Ction
O
yla
Al

Formaldehyde

Fe, Co, Ru
ka

isobutylene

CH rbon
Zn u/Z /Co

li-

Ni
C O

do
O nO O/

3O
Ag
Cu oS 2

/C ; A

ca
pe

h,
M

r 2O Cu l 2O

,R
3

Co
/Z 3
nO
/A

zeolites
l 2O

Syngas Cu/ZnO Olefins

3

Isosynthesis
i-C4 Methanol Gasoline
ThO2 or ZrO2
CO + H2 MTO

Dir
MTG
Co

Al2O3
tion

ect
,
Ox

H2O
Rh

Co ologa
os

U
HC o( )(P

WGS
HC h(CO

se
yn
o( CO Ph
R

Purify
CO ) 3P 3) 3

hom
th

DME
e
) 4 (Bu

sis

M100
N2 over Fe/FeO Ethanol M85
H2
3
)

NH3 Aldehydes
DMFC
(K2O, Al2O3, CaO)
Alcohols
 REFINERY FUEL GAS

OVERHEAD
GAS PLANT
DRUM LPG

ISOMERIZATION REGULAR GASOLINE

UNIT

PREMIUM GASOLINE

CATALYTIC
H2 REFORMING SOLVENTS
CRUDE TOWER

AVIATION FUELS
HYDROTREATING
RAW
H2
KEROSENE

TREATING AND BLENDING

DIESELS

HYDROTREATING
RAW DIESEL HEATING OILS

ALKYLATION
CRUDE GAS PLANT
UNIT LUBE OILS
OIL

LIGHT
GAS OIL GREASES
FLUID
SULFUR
CATALYTIC
TREATMENT
CRACKING
ASPHALTS
HEAVY
GAS OIL

HYDRO
COKER

VACUUM GAS OIL

CRACKING
FUEL
GAS

UNIT INDUSTRIAL FUELS

HYDROTREATING
TAR
DELAYED REFINERY FUEL OIL
COKER
DECANT OIL

GASOLINE COKE
TO REFORMER

COKE
ATMOS TREATED NAPHTHA (TO REFORMER)
RESID
TREATED DIESEL
Conceptual Petroleum Refinery
HDT
TREATED RESID
 FEED CLEANUP &
BIOMASS PREP
GASIFICATION
CONDITIONING
SYNGAS

Ethanol From Biomass

BIOCONVERSION

Thermochemical Syngas – Biochemical Ethanol

SEPARATION

ETHANOL
 Net Revenue Potential of Biorefinery
on the U.S. Pulp Industry
Syngas
Syngas
Liquid Fuels/Chemicals
$5.5. billion

Black Liquor
& Residuals

¬Extract Hemicelluloses
¬new products Steam,
¬BL Gasifier Power &
chemicals & polymers ¬Wood Residual Chemicals
$3.3 billion Gasifier
¬Combined Cycle System
¬Process to manufacture
Liquid Fuels and Chemicals
¬Pulp
$5.5 billion
 Cyclone
Gas
Cleanup
Freeboard Product Gas

Exhaust

Ash Isothermal
Pre-reformer
Compressor
Fluid Bed

Biomass
Cooling
Plenum Air
Air/Steam HRSG

Fluid-Bed Gasifier

Carbonate
A C
Fuel Cells Process
Water

DC/AC A.C.
Inverter Output

Air
Burner
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

Water, char, CO CO2

Cellulose “Active” cellulose

Secondary tar, char
Vapor
·(liquid) CH4 H2 CO C2H2
 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 (~500°C), 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
<10% moisture; feed and reaction
Drying water end up in bio-oil

Comminution 2mm (bubbling bed), 6 mm (CFB)

Fast pyrolysis High heat rate, controlled T, short

residence time

Char separation Efficient char separation needed

Liquid recovery By condensation and

coalescence.
 Operational Pyrolysis Units
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

 Bubbling Fluid Bed Pyrolysis

GAS
For fluidization or export

BIOMASS

Fluid
bed Gas
reactor recycle

BIO-OIL
CHAR
For reactor or export
 Fluid Bed Heating Options

Vapor product

1 Hot wall
Char+air
Wood feed 5 Hot tubes

2 Recycled 4 Air addition

hot sand

3 Hot fluidizing
gas
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
GAS
Pyrolyzer To reactor or export
Flue gas

BIOMASS
Sand+
Char
Hot BIO-OIL Gas
sand recycle
Air
Combustor
 CFB and Transported Beds
• 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.
 Rotating Cone (BTG)
Centrifugation
drives hot sand P article trajectory
and biomass up
rotating heated
cone;
P article
Vapors are
H eated
condensed; rotating
Char is burned cone
and hot sand is
recirculated.
 Vacuum Moving Bed
¾ Developed at Université Laval, Canada,
scaled up by Pyrovac
¾ Pilot plant operating at 50 kg/h
¾ Demonstration unit at 3.5 t/h
¾ Analogous to fast pyrolysis as vapor
residence time is similar.
¾ Lower bio-oil yield 35-50%
¾ Complicated mechanically (stirring
wood bed to improve heat transfer)
 Auger Reactor
• 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 (400ºC);
• Lower bio-oil yields
• Moving parts in the hot zone
• Heat transfer at larger scale may be a
problem
 Char Removal
• 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.
 Liquid Collection
• 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.
 Fast Pyrolysis Bio-oil
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
 Bio-oil Properties
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
Upgrading of Bio-oils
Physical Methods
¾Filtration for char removal,
¾Emulsification with hydrocarbons,
¾Solvent addition,
Chemical Methods
¾Reaction with alcohols,
¾Catalytic deoxygenation:
Hydrotreating,
Catalytic (zeolite) vapor cracking.
 Applications of Bio-oils

B io -o il
E x tra c t
B o ile r
U p g ra d e

H eat Chemicals
E le c tric ity T ra n s p o rt fu e l
 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?

9 Cost : 10% – 100% more than fossil fuel,

9 Availability: limited supplies for testing
9 Standards; lack of standards and inconsistent
quality inhibits wider usage,
9 Incompatibility with conventional fuels,
9 Unfamiliarity of users
9 Dedicated fuel handling needed,
9 Poor image.
Research Opportunities
 Technical Barrier Areas
Biomass Residues Hydrogen Fuels Export
Dedicated Crops & Bioproducts & Chemicals Electricity

Feed Gasification Gas Heat

Processing & Conditioning Syngas & Power
& Handling Pyrolysis & Separation Utilization Generation

Biorefinery
Residues

™ Feed Processing and Handling

™ Gasification / Conversion
™ Gas Cleanup and Catalytic Conditioning
™ Syngas Utilization
™ Process Integration
™ Process Control, Sensors, and Optimization
 Biomass Thermochemical Conversion
Primary Technical Barriers
Gasification Pyrolysis Black Liquor Gasification
• Feed Pretreatment • Catalytic Pyrolysis • Containment
- Feeder reliability • Oil Handling - Metals
- Feed modification - Toxicity - Refractories
• Gasification - Stability - Vessel design
- Tar & Heteroatom chemistry - Storage - Bed behavior/agglomeration
- Gasifier Design - Transportation • Mill Integration
- Catalysis • Oil Properties - Steam
• Gas Cleanup & Conditioning - Ash - Power
- Catalytic Conversion - Acidity - Causticizing
- Condensing Cleanup • Oil Commercial Properties • Fuels Chemistry
- Non-condensing Cleanup - Commercial Specifications - Carbon management
• Syngas Utilization - Use in Petroleum Refineries - Tars
- Cleanliness requirements - Sulfur management
- Gas composition - Alkali management
• Process Integration - Halogen management
• Sensors and Controls • Sensors and Controls
 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.