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 Chemical Intermediates Phenolics Adhesives Furfural Fatty acids Acetic Acid Carbon black Paints Dyes, Pigments, and Ink Detergents Etc. Food and Feed

Biomass Feedstock
Trees Forest Residues Grasses Agricultural Crops Agricultural Residues Animal Wastes Municipal Solid Waste

Conversion Processes
- Gasification - Combustion and Cofiring - Pyrolysis - Enzymatic Fermentation - Gas/liquid Fermentation - Acid Hydrolysis/Fermentation - Other

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

Combustion

Gasification

Pyrolysis & Pyrolysis Hydrothermal

Heat

Fuel Gases (CO + H 2)

Liquids

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 (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) CH1.2O0.2, Manure (350C) 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

Prox ima te (w t% as received) Ash Vola tile Ma tte r Fixe d Ca rbon Moisture HHV, Dry (Btu/lb) Ultima te, w t% a s receive d Ca rbon Hydrogen Nitroge n Sulfur Oxyge n (by diff) Chlorine Ash 47.05 5.71 0.22 0.05 41.01 <0.01 1.16 43.98 5.39 0.62 0.10 39.10 0.25 4.75 32.00 5.48 6.64 0.96 34.45 1.14 19.33 32.12 2.85 0.24 4.79 0.71 0.07 51.91 1.16 81.99 13.05 4.80 8382 4.75 75.96 13.23 6.06 7782 18.65 58.21 11.53 11.61 6310 52.01 35.26 6.11 9.61 4971

Corn Stover

Chicken Litter

Black Liquor

Eleme nta l Ash Analysis, w t% of fue l as re ce ive d Si Fe Al Na K Ca Mg P As (ppm) 0.05 --0.02 0.02 0.04 0.39 0.08 0.08 1.20 --0.05 0.01 1.08 0.29 0.18 0.18 0.82 0.25 0.14 0.77 2.72 2.79 0.87 1.59 14 <0.01 0.05 <0.01 8.65 0.82 0.05 <0.01 <0.01

Representative Biomass and Coal Properties

Biomass 1 Name Classification Proximate Analysis, wt% Dry Moisture Volatile Matter Fixed Carbon Ash Ultimate Analysis, wt % Dry C H N Cl O S Ash H/C Atomic Ratio HHV, Dry, Btu/lb Wood

Biomass 2

Coal 1

Coal 2 Rosebud, MT sub B

Tar Sands Athabasca Bitumen

Red Corn Cob Grundy, IL. No 4 HvBb

25-60 77-87 13-21 0.1-2 50-53 5.8-7.0 0-0.3 .001-0.1 38-44 0-0.1 0.1-2 1.4-1.6 8,530- 9,050

16 ca. 80 -4 45 5.8 2.4 -42.5 0 4 1.5 7,340

8.16 40.6 45.47 13.93 68.58 4.61 1.18 0.12 6.79 4.76 13.93 0.8 12,400

19.84 39.02 49.08 9.16 68.39 4.64 0.99 0.02 16.01 0.79 9.16 0.81 11,684 83.6 10.3 0.4 -0.2 5.5

1.47 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 Pyrolysis Gasification 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

M D e e ta l tec tor

Dump Conveyor #1
Ma S e g n e t ic p ar ato r

Fe

eds

to c

Primary Hogger

Wood Pile

Radial Stacker
Radial Screw Active Reclaim Feeder

Truck Tipper

Secondary Hogger

Sc

ale

Disc Feeder

Rotary Airlock Feeder

Air Intake

Conveyor #2

Biomass Feedstock Handling Equipment

Existing Boiler System

System Boundary for Biomass Feedstock Handling System

Valve
Separator

Existing Boiler

Bin Vent

Mechanical Exhauster

Valve

Wood Silo

Collecting Conveyors

Biomass Co-Firing System Retrofit for 100 MW Pulverized Coal Boiler

Scale

Scale

Pressure Blowers

Direct Air Emissions from Wood Residue Facilities by Boiler Type (lb/MWh)
SO X Biomass Technology Stoker Boiler, W ood Residues (1,4) Fluidized Bed, Biomass (4) Energy Crops (Poplar) Gasification (a,b) 0.08 NO X 2.1
(biomass type not specif ied)

CO 12.2
(biomass type not specif ied)

PM-101 0.50

Comments
Based on 23 Calif ornia grate boilers, except f or SO2 (uncontrolled) Based on 11 Calif ornia f luid bed boilers.

(total particulates) (biomass type not specif ied)

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)

0.05

1.10 to 2.2

0.23

0.01
(total particulates)

(s ugge s te d value (0.66 to 1.32 w /SNCR; based on SOx numbers 0.22 to 0.44 w ith SCR) f or Stoker and FBC, adjusted by a f actor of 9,180/13,800 to account f or heat rate improvement)

Combustor f lue gas goes through cyclone and baghouse. Syngas goes through scrubber and baghouse bef ore gas turbine. No controls on gas turbine.

Coal Technology Bituminous Coal, Stoker Boiler (f) Pulverized Coal Boiler (d) Cofiring 15% Biomass (d2) Fluidized Bed, Coal (f) 4-Stroke NG Reciprocating Engine (g) Natural Gas Turbine (e) Natural Gas Combined Cycle (c,e)

20.2 1 wt% S coal 14.3 12.2 3.7 (1 w t% S coal

Ca/S = 2.5)

5.8 6.89 6.17 2.7

2.7 0.35 0.35 9.6

0.62 0.32
(total particulates)

PM Control only (baghouse) A verage US PC boiler (typically:baghouse, limestone FGC) ?

0.32 (total
particulates)

0.30

Baghouse f or PM Control, Ca sorbents used f or SOx

Natural Gas Technology 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 Water-steam injection only Water-steam injection only

0.009
(0.0007 w t% S)

1.72 0.91
(0.21 w / SCR)

0.4 0.06

.09
(total particulates)

0.004

0.14
(total particulates)

NOx Emissions - Life Cycle Total and Plant Operating Emissions

total NOx
7

operating plant NOx

NOx emissions (lb/MWh)

6 5 4 3 2 1 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

1.0
Fossil Energy In

Avoided Carbon Emissions

1,627 10 Landfill and Mulching Transportation 3 Construction

Electricity Out 28.4

Power Plant 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 Gasification - Electricity Combustion - CHP

Gasification - CHP 6

Purchased Electricity Purchased Steam

15% Cofiring CHP 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 Electricity (cents/kWh) and Steam ($/1000 lb) Costs Gasification 75 MWeq 8 Direct Combustion 100 MWeq

Gasification 150 MWeq

6 Purchased Electricity Purchased Steam

15% Cofiring 105 MWeq Incremental Cost

-2 -2 -1 0 1 Feed Cost ($/MBtu) 2 3 4 5

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 For Fuels and Chemicals

Gasification Cleanup Synthesis

PRODUCTS Hydrogen Alcohols FT Gasoline FT Diesel Olefins Oxochemicals Ammonia SNG

Biomass

Pyrolysis

Conversion or Collection

Purification

Hydrogen Olefins Oils Specialty Chem

Other Conversion *

Separation

Purification

Hydrogen Methane Oils Other

* Examples: Hydrothermal Processing, Liquefaction, Wet Gasification

Thermochemical Conversion
Of Biomass and Black Liquor
Product Bio-Oil
Changing World Technologies Gas Product: PNNL Wet Gasification (CH4/H2)
Dry Ash

Syngas
Slag

High Pressure

GTI (O2) Carbona (O2) HTW O2) Foster Wheeler (O2)

Chemrec (O2) Noell

10-25 MPa Feed: Biomass

1- 3 MPa Feed: Biomass

MTCI-also Black Liquor FERCO (Indirect) MTCI (Indirect) Pearson (Indirect) TUV (Indirect) For CHP:TPS (Air) Carbona (Air) Lurgi (Air) Foster Wheeler (Air) EPI (Air) Prime Energy (Air)

2 3 MPa Feed: Black Liquor

Low Pressure
0.2 MPa

ENSYN Dynamotive BTG Fortum

Chemrec (Air)

Low (300-600C)

Medium (700-850C) Temperature

High (900-1200C)

Primary Processes Vapor Phase

CO, CO2, H2O Primary Vapors

Secondary Processes
Light HCs, Aromatics, & Oxygenates Olefins, Aromatics CO, H2, CO2, H2O

Tertiary Processes
PNAs, CO, H2, CO2, H2O, CH4 CO, H2, CO2, H2O

Low P Liquid Phase Primary Liquids

Condensed Oils (phenols, aromatics)

High P

Low P Solid Phase Biomass Charcoal Coke Soot

High P

Pyrolysis Severity

Mixed Oxygenates

Phenolic Ethers

Alkyl Phenolics

Heterocyclic Ethers

PAH

Larger PAH
o

400

500

600

700

800

900

C o n v e n t io n a l F la s h P y r o l y s is o (4 5 0 - 5 0 0 C ) A c id s A ld e h y d e s K e to n e s F u ra n s A lc o h o ls C o m p le x O x y g e n a te s P h e n o ls G u a i a c o ls S y r in g o ls 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 .

H i- T e m p e r a t u r e F la s h P y r o ly s is o (6 0 0 - 6 5 0 C ) B enzenes P h e n o ls C a te c h o ls N a p h t h a le n e s B ip h e n y ls P h e n a n th re n e s B e n z o fu ra n s B e n z a ld e h y d e s

C o n v e n t io n a l S te a m G a s if i c a t io n o (7 0 0 - 8 0 0 C ) N a p h th a le n e s A c e n a p h t h y le n e s F lu o r e n e s P h e n a n th re n e s B e n z a ld e h y d e s P h e n o ls N a p h th o fu ra n s B e n z a n th ra c e n e s

H i- T e m p e r a t u r e S te a m G a s if ic a t io n o (9 0 0 - 1 0 0 0 C ) N a p h t h a le n e * A c e n a p h t h y le n e P h e n a n th re n e F lu o r a n t h e n e P yre n e A c e p h e n a n t h r y le n e B e n z a n th ra c e n e s B e n zo p yre n e s 226 M W PAH s 276 M W PAH s

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

Biomass Low Pressure Gasification Shift Conversion Compression

Feed Preparation & Handling

Oxygen CO2 Product

High Pressure Gasification

Hot Gas Cleanup

Reforming

Compression

Acid Gas Removal

Synthesis

LP Indirect Gasification

Cold Gas Cleanup

Compression & Reforming

LP Indirect Gasification

Catalytic Conditioning & Reforming

Compression

Biomass
Biomass
Cyclone

Freeboard

Gas, Tar, Water Pyrolysis C + CO2 = 2CO C + H2O = CO + H2 C + O2 = CO2 4H + O2 = 2H2O Reduction Combustion Ash Air
C + O2 = CO2 4H + O2 = 2H2O C + CO2 = 2CO C + H2O = CO + H2 Pyrolysis

Gas, Tar, Water

Ash Fluid Bed

Combustion Reduction Ash Air

Plenum

Biomass

Air/Steam

Updraft Gasifier

Downdraft Gasifier

Fluid-Bed Gasifier

Flue Gas

Gasifier

Primary Cyclone

Secondary Cyclone

Fly Ash

Product Gas

Biomass

Biomass Furnace
Air/Steam

Char Recycle Gas

Bottom Ash

N2 or Steam Air Entrained Flow Gasifier

Circulating Fluid-Bed Gasifier

Gasifier Types-Advantages and Disadvantages

Gasifier
Updraft

Advantages
Mature for heat Small scale applications Can handle high moisture No carbon in ash Small scale applications Low particulates Low tar Large scale applications Feed characteristics Direct/indirect heating Can produce syngas Large scale applications Feed characteristics Can produce syngas Can be scaled Potential for low tar Can produce syngas

Disadvantages
Feed size limits High tar yields Scale limitations Producer gas Slagging potential Feed size limits Scale limitations Producer gas Moisture sensitive Medium tar yield Higher particle loading

Downdraft

Fluid Bed

Circulating Fluid Bed

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

Entrained Flow

Table 2: Gas composition for fluid bed and circulating fluid bed gasifiers
Gas ifie r FERCO Car bona Pr ince ton M ode l Type Age nt Be d M ate r ial Fe e d Gas Com pos ition H2 CO CO2 N2 CH4 C2+ GCV , M J/Nm 3 26.2 38.2 15.1 2 14.9 4 16.3 21.70 23.8 9.4 41.6 0.08 0.6 5.4 29.4 39.2 13.1 0.2 13.0 4.4 17.2 19.1 11.1 28.9 27.8 11.2 2.0 9.2 Indir e ct CFB s te am olivine w ood chips Air FB air s and w ood pe lle ts Indir e ct FB s te am none black liquor PFB O2/s te am alum ina w ood chips IGT

Typical Gas Heating Values

Gasifier Inlet Gas Product Gas Type Product Gas HHV MJ/Nm Partial Oxidation Partial Oxidation Indirect Air Oxygen Steam Producer Gas Synthesis Gas Synthesis Gas Natural Gas Methane 7 10 15 38 41
3

Biomass
Oxygen Sulfur Ash Alkali

Coal

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

H/C Ratio Heating Value Tar Reactivity

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- BURLINGTON, VT

350 TPD

Community Power Corporations BioMax 15 Modular Biopower System

Carbona Project: Skive, Denmark

TAR CRACKER GASIFIER BIOMASS FUEL FEEDING GAS COOLER ASH GAS COOLER GAS TANK STACK

HEAT RECOVERY POWER AIR GAS ENGINE(S) ASH HEAT

Contribution to Hydrogen Price for BCL Low Pressure Indirectly-Heated Gasifier System (2,000 tonne/day plant; $30/dry ton feedstock) Capital Operating Costs Biomass feedstock Feed handling & drying Gasification & gas clean up Syngas compressor Reforming & shift conversion PSA Heat exchange, pumps, & BOP By-product steam credit -10% -5% 0% -5% 5% 10% 15% 20% 25% 30% 35% 40% 45% 6% 7% 10% 8% 11% 22% 41% Feedstock By-Product Credit 41% Process Electricity

Contribution to Hydrogen Price for BCL Low Pressure Indirectly-Heated Gasifier System (2,000 tonne/day plant; $53/dry ton feedstock) Capital Operating Costs Biomass feedstock Feed handling & drying Gasification & gas clean up Syngas compressor Reforming & shift conversion PSA Heat exchange, pumps, & BOP By-product steam credit -10% -5% 0% -4% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50% 55% 4% 6% 8% 6% 8% 17% 31% Feedstock By-Product Credit 55% Process Electricity

Life Cycle GWP and Energy Balance for Advanced IGCC Technology using Energy Crop Biomass
Future, wide-spread potential

Waxes Diesel

Olefins Gasoline

MTBE
isobutylene acidic ion exchange

Fe, Co, Ru

Formaldehyde
Ag

i-C4

Isosynthesis

ThO2 or ZrO2

Syngas CO + H2
) os 3 ) 4 (Bu Ox CO ) 3P 3) 3 o( CO Ph HC o( )(P HC h(CO R

Cu/ZnO
, Co

ca CH rbon y 3O H latio Co +C n ,R O h, Ni

Mixed Alcohols

Fischer-Tropsch

Acetic Acid

H2O WGS Purify

N2 over Fe/FeO (K2O, Al2O3, CaO)

hom Co ologa tion

Al2O3

d l 2O pe /A do nO li3 /Z 3 ka r 2O Cu l 2O Al /C ; A O nO O/ Zn u/Z /Co C O Cu oS 2 M

3

Methanol
U ect Dir

zeolites MTO MTG

Olefins Gasoline

Rh
sis

se

e th yn

DME

NH3

H2

Ethanol

Aldehydes Alcohols

M100 M85 DMFC

REFINERY FUEL GAS OVERHEAD DRUM GAS PLANT

LPG

ISOMERIZATION UNIT

REGULAR GASOLINE PREMIUM GASOLINE

H2 CRUDE TOWER

CATALYTIC REFORMING

SOLVENTS

AVIATION FUELS RAW KEROSENE HYDROTREATING H2 TREATING AND BLENDING DIESELS

RAW DIESEL

HYDROTREATING

HEATING OILS

CRUDE OIL LIGHT GAS OIL FLUID CATALYTIC CRACKING COKER GAS OIL HEAVY GAS OIL

GAS PLANT

ALKYLATION UNIT

LUBE OILS

GREASES SULFUR TREATMENT ASPHALTS HYDRO CRACKING INDUSTRIAL FUELS HYDROTREATING DELAYED COKER GASOLINE TO REFORMER REFINERY FUEL OIL DECANT OIL COKE

TAR

FUEL GAS

VACUUM UNIT

ATMOS RESID HDT

COKE TREATED NAPHTHA (TO REFORMER) TREATED DIESEL TREATED RESID

Conceptual Petroleum Refinery

BIOMASS

FEED PREP

GASIFICATION

CLEANUP & CONDITIONING

SYNGAS

Ethanol From Biomass

Thermochemical Syngas Biochemical Ethanol

BIOCONVERSION

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 chemicals & polymers

$3.3 billion

Steam, BL Gasifier Power & Wood Residual Chemicals Gasifier Combined Cycle System Process to manufacture Liquid Fuels and Chemicals

Pulp $5.5 billion

Cyclone

Freeboard

Product Gas

Gas Cleanup Exhaust

Ash Fluid Bed Biomass Plenum Air/Steam

Compressor Cooling Air

Isothermal Pre-reformer

HRSG

Fluid-Bed Gasifier

Carbonate Fuel Cells

Process Water DC/AC Inverter Air Burner A.C. Output

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 FAST PYROLYSIS 75% 12% moderate temperature short residence time CARBONIZATION 30% 35% low temperature long residence time 5% 10% high temperature long residence time

Gas 13%

35%

GASIFICATION

85%

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.

Operational Pyrolysis Units

Fluid beds 400 kg/h at DynaMotive 20 kg/h at RTI Many research units 1000 kg/h at Red Arrow (Ensyn) 20 kg/h at VTT (Ensyn) 350 kg/h (Fortum, Finland) 200 kg/h at BTG (Netherlands) 3500 kg/h at Pyrovac 200 kg/h at ROI

CFBs

Rotating cone Vacuum Auger

Bubbling Fluid Bed Pyrolysis

GAS For fluidization or export BIOMASS Fluid bed reactor CHAR For reactor or export BIO-OIL

Gas recycle

Fluid Bed Heating Options

Vapor product 1 Hot wall Wood feed 2 Recycled hot sand 3 Hot fluidizing gas Char+air 5 Hot tubes 4 Air addition

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

Pyrolyzer GAS To reactor or export Flue gas

BIOMASS Sand+ Char Hot sand

BIO-OIL
Air Combustor

Gas recycle

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 and biomass up rotating heated cone; Vapors are condensed; Char is burned and hot sand is recirculated.
P article trajectory

P article H eated rotating cone

Vacuum Moving Bed

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)

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 (400C); 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
Filtration for char removal, Emulsification with hydrocarbons, Solvent addition,

Chemical Methods
Reaction with alcohols, Catalytic 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 E le c tric ity

Chemicals
T ra n s p o rt fu e l

Bio-oil Cost
Different claims of the cost of production: Ensyn BTG $4-5/GJ ($68-75/ton) $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

Technical Barrier Areas

Biomass Residues Dedicated Crops

Hydrogen & Bioproducts

Fuels & Chemicals

Export Electricity

Feed Processing & Handling

Gasification & Pyrolysis

Gas Conditioning & Separation

Syngas Utilization

Heat & Power 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
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

Pyrolysis
Catalytic Pyrolysis Oil Handling - Toxicity - Stability - Storage - Transportation Oil Properties - Ash - Acidity Oil Commercial Properties - Commercial Specifications - Use in Petroleum Refineries

Black Liquor Gasification

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
1. 2. 3. 4. 5. 6. 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. Bridgewater, A.V. (2003). A Guide to Fast Pyrolysis of Biomass for Fuels and Chemicals, PyNe Guide 1, www.pyne.co.uk Brown, R. C. (2003). Biorenewable Resources: Engineering New Products From Agriculture, Iowa State Press, ISBN:0-8138-2263-7. Higman, C. and M. van der Burgt (2003). Gasification, Elsevier Science (USA), ISBN 0-7506-7707-4. Probstein, R. F. and R. E. Hicks (1982). Synthetic Fuels, McGraw-Hill, Inc., ISBN 0-07-050908-5. Van Loo, S. and J. Koppejan (eds.) (2002). Handbook of Biomass Combustion and Co-firing, Twente University Press, ISBN 9036517737.