Fast Pyrolysis and B

Upgrading

Robert C. Brown

Iowa State University

and

Jennifer Holmgren

UOP
Fast Pyrolysis

•

Rapid thermal decomposition of o

compounds in the absence of oxyproduce liquids, char, and gas

–

Dry feedstock: <10%

–

Small particles: <3 mm

–

Short residence times: 0.5 -

2 s

–

Moderate temperatures (400-500 

oC)

–

Rapid quenching at the end of the pr

–

Typical yields

Oil: 60 -

70%

Char: 12 -15%Gas: 13 -

25%
Source: Piskorz, J., et al. In Pyrolysis 

from Biomass, Soltes, E. J., Milne, T. Eds., ACS Symposium Series 376, 19

Moisture content, wt% Particle size, μm (max) 

Temperature Apparent residence time Product Yields, wt %, m.f.

Water 

Gas 

Bio-char Bio-oil 

Bio-oil composition, wt %, 

Saccharides Anhydrosugars Aldehydes Furans Ketones Alcohols Carboxylic acids Water-Soluble – Total Above Pyrolytic Lignin Unaccounted fraction 

Bio-Oil

Pyrolysis liquid (bio-oil) from flash pyrolysis is a low viscosity, dark-brown fluid with up to 15 to 20% water
Multiple reaction pathw

pyrolysis of cellulo

Cellulose

Fast

Slow

Alkali-catalyzeddehydration

Char + water

Levo

Hydr

Depolymerization
Fast Pyrolysis

•

Advantages

–

Operates at atmospheric pressure an

temperatures (450 C)

–

Yields of bio-oil can exceed 70 wt-%

•

Disadvantages

–

High oxygen and water content of py

makes them inferior to conventional hfuels 

–

Phase-separation and polymerization 

and corrosion of containers make stoliquids difficult
Several Kinds of Fast P

Reactors

•

Bubbling fluidized bed

•

Circulating fluidized beds/trans

•

Rotating cone pyrolyzer

•

Ablative pyrolyzer

•

Vacuum pyrolysis

•

Auger reactor
Bubbling Fluidized 

Gas, CVapor

F

F

Fl

Biomass

Feeder

•

Heat supplied externally 

to bed

•

Good mass & heat 

transfer

•

Requires small biomass 

particles (2-3 mm)
Circulating Fluidized Bed/T

Reactor

G

Fluidizing gas

Biomass

Feeder

Pyrolyzer

Sand & ch

Ho

San

•

Hot sand circulated 

between combustor and pyrolyzer

•

Heat supplied from 

burning char

•

High throughputs 

but more char attrition
Rotating Cone Pyroly

Hot Sand

Biomas

•

Sand and biomass 

brought into contact within rotating cone

•

Compact design and 

does not need carrier gas

•

Requires very small 

biomass particles and is hard to scale-up
Ablative Pyrolyze

•

High pressure of particle 

on hot reactor wall achieved by centrifugal or mechanical motion

•

Can use large particles 

and does not require carrier gas

•

Complex and does not 

scale well

Spinnin

Disk

Pressure 

Applied 

to Wood 
Vacuum Pyrolysis

•

Biomass moved by 

gravity and rotating scrappers through multiple hearth pyrolyzer with temperature increasing from 200 C to 400 C

•

Can use larger 

particles and employs little carrier gas

•

Expensive vacuum 

pump and difficult to scale-up

Scrapper 

Driver Bioma

Char

Multiple hearth 

vacuum pyrolysis 

reactor
Auger Reactor

Biomass

Auger 

driver

Hot 

sand

Auge

reacto

•

Hot sand and 

biomass mixed by auger

•

Suitable for small 

scale

•

Requires hot sand 

heating and circulation system
Relative Merits of Various 

Property Status Biooil

wt%

Complexity Feed size Iner

gas 

need

Fluid bed

Demo

7

5

Medium Small High 

CFB

Pilot

7

5 High Medium High 

Entrained None 65 High Small High Rotating cone

Pilot 65 High V small Low

Ablative Lab

7

5 High Large

Low 

Auger Lab 65 Low Small Low Vacuum Demo 60 High Large

Low 

The darker the cell color, the less desirable the process.

Lab: 1 – 20 kg h-Pilot: 2

0 – 200 kg 

Demo: 200 – 200

Adapted from PYNE IEA Bioenergy http://www.
Which will domina

TECHNOLOGY STRENGTH

Strong Average

Weak

MARKET ATTRACTIVENESS High Low

Adapted from PYNE IEA Bioenergy http://www.pyn
Fast Pyrolysis Sys

Mill

Air

Bio-

Hopper

Fluidizing 

gas

Flue 

gas

Vapor, 

gas, char 

products

Cyclone

Combustor

Pyrolysis 

gases

Lignocellulosic

feedstock

Pyrolysis

reactor Char

Motor Feeder
Scale

$0

$1,000$2,000$3,000$4,000$5,000$6,000$7,000$8,000

0.0 1.0

2.0 3.0

Bio

mass In

p

u

t (

millio

n US t

o

n

s/y

r

Capital Cost (million 2005 US dollars)

0

5

0 100 150 2

Diesel O

u

t

p

u

t (

millio

n U

S g

allo

n

s/y

Sm

all ga

sific

ation (

m

ultipl

e u

nits 110,

0

0

0

U

S to

n/yr) + s

m

all F

T m

ulti

ple u

nits

Sm

all pyrolysi

s (

m

ultipl

e u

nits 110,

0

0

0

U

S to

n/yr) + l

arge FT

L

arge gasification

+ l

arge FT

$400,000 pbpd

$100,000 pbpd

Adapted from: Bridgwater, ACS Meeti

ng, Washington, D
Suitable Feedstoc

•

Wide variety of feedstocks can 

•

Fibrous biomass usually emplo

•

Wood higher yielding than herb

biomass
Storage & Transport

•

Distributed preprocessing allow

and storage as liquid

•

High acidity requires storage in 

steel or plastic

•

Stability problems need to be s
Post Processing to Mot

•

Direct application of bio-oil

•

Hydrocracking of bio-oil

•

Gasification of bio-oil

•

Fermentation of Bio-oil
Bio-Oil Burned in Diesel E

•

Bio-oil used as directly as diesel fu

•

Only suitable for stationary power 

Pyrolyzer

Bio-Oil 

Recovery

Bio-Oil 

Storage

Fibrous 

biomass

Bio-oil vapor

Cyclone

Bio-Oil

Char
Bio-Oil Hydrocrackin

•

Directly converts biomass into liquid bio

carbohydrate derivatives, and water) an

•

Bio-oil catalytically converted into hydro

(green diesel)

PyrolyzerCarbohydr

aqueou

Bio-Oil 

Recovery

Phase 

Separation

Steam 

Reformer

Fibrous 

biomass

Bio-oil vapor

Hydr

Cyclone

Lignin

Char
Bio-Oil Gasification

•

Bio-oil and char slurried together to reco

the original biomass energy

•

Slurry transported to central processing 

gasified in an entrained flow gasifier to s

•

Syngas is catalytic processed into green 

liquids)

Pyrolyzer

Bio-Oil 

Recovery

Slurry 

Preparation

Pump

Fibrous 

biomass

Bio-oil vapor

Cyclone

Bio-Oil

Char
Bio-Oil Fermentatio

Fermenter

Fiber

Pyrolyzer Anhydrosugar

&

other carbohydrate

Bio-Oil 

Recovery

Phase 

Separation

Detoxification

Hot water 

extraction

Pentose

Fiber byproduct Bio-oil vapor Fe

Cyclone

Char
Energy Efficienc

•

Conversion to 75 wt-% bio-oil tr

energy efficiency of 70%

• If carbon used for energy sourc

heat or slurried with liquid) then approaches 94%

Source: http://www.ensyn.com/info/23102000.
Co-Products

•

Gas (CO, H2, light 

hydrocarbons)

–

Can be used to heat 

pyrolysis reactor

•

Char: Several potential 

applications

–

Process heat

–

Activated carbon

–

Soil amendment
Potential Co-Products fro

P

roducts of pyrol

ysis for several different pretrea

tments of corn

No 

Pr

e

tre

a

tmen

t

Aci

d

Hydrolysis

Ac

Products (Wt% maf)

Char 15.8 13.2 Water

2.57 10.6 

Organics 59.1 67.2 Gases

22.6

9.02

Organics (Wt %)

Cellobiosan trace 4.55 

Levoglucosan 2.75 17.69 

Hydroxy-acetalde

h

y

d

e 11.57 5.97 

Formic acid 2.61 TraceAcetic acid 3.40 1.51 Acetol 4.53 traceFormaldehyde 2.75 1.63 Pyrolytic ligni

n 33.40 16.89 
Quality Assuranc

•

Bio-oil quality issues:

–

Moisture content

–

Particulate content

–

Sulfur and nitrogen content

–

Stability
Equipment Mainten

•

Potential problems with pyrolys

equipment

–

Bed agglomeration

–

Clogging of condensers

–

ESP performance

•

Catalytic reactors

–

Poisoning by sulfur and chlorine

– C

o

kin

g
Waste Streams

•

Main products (gas, char, bio-o

for all mass of biomass feedsto
Technical Barrie

•

Preparing dry, finely divided bio

particles

•

Maintaining high bio-oil yields

• Improving bio-oil stability •

Determining optimal scale of fa
Alternative Fuels: Ta

Alternative Fuels: Ta

 Alternative fue

Alternative fue

– < 100 gm 

< 100 gm 

– GTL, DM

GTL, DM

not there 

ere 

 Several other a

Several other a

(not shown for 

(not shown for 

 Engine manufa

Engine manufa

more efficient a

more efficient 

addition to hyb

addition to hyb

– Variable D

Variable D

–

“Part Hom

Part Hom

combustio

combustio

–

“Combine

Combine

– Improve f

Improve f

Source: CONCAWE / EU CAR / Source: CONCAWE / EU CAR / EU Comm’n, Dec 2003

WTW Energy /GHG Emissions Clusters WTW Energy /GHG Emissions Clusters 

0

50

100150200250300350400

0 200 400 600 800 1000

Energy, MJ/km

GHG, CO2 Equivalent, gm/km

Hydrogen Hydrogenfrom coal, FC from coal, FC

DME from NG

FAMECon

ventional entional 

EtOHHydrogen from

Gasoline & Diesel Gasoline & Diesel bio, ICE bio, ICE

GTL from NG

Green Diesel Green Diesel

Gasoline & Diesel in Advanced Gasoline & Diesel in Advanced ICE

’

s Set 

Set 
Biorenewables and Petr

Biorenewables and Petr

Feeds: Relative Availa

Feeds: Relative Availa

0

1020304050

Current Current Potential Potential

Liquid Transport Fuels Liquid Transport FuelsDieselAvailable Oil/Grease Available Oil/Grease

Cellulosic Waste Cellulosic Waste

MBPD

MBPD

Global 

0

2468

10

Curr

Curr

MBPD

12

14

Available Cellulosic Biomass Cou

Available Cellulosic Biomass Cou

Significant Impact in Fuels 

Significant Impact in Fuels 
Py Oil Portfolio Oil Portfolio

Solid

Cellulosic

Biomass

Pyrolysis Oil/

Lignin Hy

Power 

Dies

Gasol
Lignin Molecular Structu
Treating Technologi

Treating Technologi

Hydrotreating Hydrotreating

•

H

y

drotreating is the key process 

to meet quality specifications for refinery fuel products 

•

Removes sulfur, nitrogen, olefins, 

and metals using hydrogen

•

H

y

drogen addition als

o improves 

the quality of distillate fuels (poly aromatics, cetane, smoke point)

•

Treating feedstocks for other 

processing units
Conversion Technolog

Conversion Technolog

Hydrocracking Hydrocracking

•

H

y

drocracking upgrades heavy 

feeds including gas oils and cycle oils into lighter, higher value, low sulfur products

•

High pressure is used to add 

hydrogen and produce premium distillate products

•

Naphtha products normally are 

low octane and are upgraded in a reformer

•

Product volume is 10-20% 

higher than the feedstock
Distillates Selectivity

Activity

New 

New 

Max 

Diesel Distillates Distillates

Flexible Flexible 

Hydrocracking Catalyst P

Hydrocracking Catalyst P

HC-150

HC-215

HC-115

DHC-32

HC-33

DHC-8

HC-43

Cur

Cu

DHC-39

DHC-41

HC

Distillate Selectivity Decreases with Incr

Distillate Selectivity Decreases with Incr
YE for Hydrocracking Hydrocracking Pyro

Pyro

Feed Wt% b

Pyrolysis Oil Pyrolysis Oil 100

4-5

1530851-52

2

H2

Products Products

Lt ends Lt endsGasoline Gasoline 1

Diesel 2Water, CO Water, CO2
Gasoline Production from Gasoline Production from 

($40/bbl crude) ($40/bbl crude)

Feed $/D 

Pyrolysis Oil Pyrolysis Oil 40,500

H

2 25,680 

19,30352,52012,000

Utilities Utilities

-4,800

Net 12,843

Products Products

Lt Hydrocarbons Lt Hydrocarbons Gasoline Gasoline 

Diesel 

$ 4.2 million/year
Hydroprocessing cos

Hydroprocessing cos

Effect of Scale Effect of Scale

H

D

T C

a

pit

al C

ost vs C

a

$0.

0

$5.

0

$10.

0

$15.

0

$20.

0

$25.

0

$30.

0

$35.

0

0

5000 10000 15000 2000

0

Ca

p

a

city, BP

D

Capital Cost, $MM (2006)

U

nit size

(bpd)

C

ost, 

$M

M

C

ost/ 

1000 

bpd

$M

M

30000 $28.

9 $ 

0.9

6

27500 $27.

4 $ 1.0

0

25000 $25.

9 $ 1.0

4

22500 $24.

3 $ 1.0

8

20000 $22.

7 $ 1.13

17500 $20.

9 $ 1.19

15000 $19.1 $ 1.2

7

12500 $17.1 $ 1.3

7

10000 $14.

9 $ 1.4

9

7500 $12.

6 $ 1.6

8

5000 $9.

9 $ 1.9

7

2500 $6.

5 $ 

2.6

0
Size of Hydroprocessing 

Size of Hydroprocessing 

2000 bp

2000 bp

2500

bbl/day

38.

3

M gal/y

ea

174072 tonnes/yr 65%267803 tonnes/yr 734 tonne/

day 

Dynamotive Dynamotive

’

s Planned Planned 

200 tpd Plant

D

ynamotive'

s 200 t

onne/day fa

cility (

planned production)

200 tonne/day

biom

a

s

s process

e

d

200000

k

g/day

65%

% conversion biomass to pyroly

sis

oil

130000

k

g/day biooil

1.2

kg/liter density of pyroly

sis oil

108333 liter/day

28622 gal/day

681

bbl/

day

H

ydropr

o

c

e

s

sing unit

30,000 b

30,000 b

(typical r

(typical r

30000

bbl/day

459.

9

M gal/year

2088866 tonnes/yr 65%3213640 tonnes/yr 8804 tonne/day 
Example: Example: 

Potential from logging re

Potential from logging re

41 Million dry tons logging residue available (Billion 

10% % water of biomass for pyrolysis unit

46 Million tons of logging residue feed

65% % conversion to pyrolysis oil

29.6 million tons of pyrolysis oil

6519 M gallons of pyrolysis oil from logging residue

425271 bbl/day

 ~14 30,000 bpd hydroprocessi

~14 30,000 bpd hydroprocessi

– Estimated cost: $405 MM Estimated cost: $405 MM

 ~170 2500 bpd hydroprocessin

~170 2500 bpd hydroprocessin

– Estimated cost: $1105 MM Estimated cost: $1105 MM
Distributed Pyrolysis Plants; Centra

Distributed Pyrolysis Plants; Centra

Gasifier

P

P

P

P

P

P Biomass

Gasification

Natural G

as

DME

Methanol

H

2

GTL, BTL

Synthesis Gas Reforming

 Key Decision: What are we pl

Key Decision: What are we pl

transport? transport?
Technical Barrier

Technical Barrier

 Securing a consistent Securing a consistent py Oil fee

Oil fee

 Logistics Logistics  Balance of distributed vs. centr

Balance of distributed vs. centr

 Catalyst and process Catalyst and process 

invention/development/commer

invention/development/commer
Summary Summary

 Vegetable oils, grease and pyrolys

Vegetable oils, grease and pyrolys

feasible feedstocks for convention

feasible feedstocks for convention

refineries refineries

– Other feedstocks and processing op

Other feedstocks and processing o

promising promising

– Increased volumes of biobased feed

Increased volumes of biobased feed

• Consistent source of pyrolysis oil or ot

Consistent source of pyrolysis oil or ot

biomass biomass

 Biorenewable processing options i

Biorenewable processing options i

not limited to refinery integration not limited to refinery integration

– Stand alone units possible Stand alone units possible

• Biorefi Biorefineries; Biofeedstock Biofeedstock source

• Portable H Portable H2
Acknowledgement

Acknowledgement

DOE, Project DE DOE, Project DE

-FG36

-05GO1

05GO1

Contributors Contributors 

 MTU– David Shonnard Shonnard NREL – Stefan Czernik Czernik

– Richard Bain Richard Bain

Contribu

Contribu

 PNNL – D

D

– D

D

 UOP – To

T

– Te

T

– D

D

– M

M

– Jo

Jo

Project Manager: Rich Marinang

Project Manager: Rich Marinang