CanmetENERGY Bioenergy Group- Biocarbon R&D Activities

Canadian Carbonization Research Association First Working Meeting on Bio-based Carbon for the Iron and

Steel Industries

June 12-13 2012 Presented by

Andrew McFarlan

Introduction This initial working meeting was organized in order to bring researchers together to discuss R&D and current understanding on the potential to replace coal and coke used in the iron and steel industries with bio-based carbon.

Specific questions to be discussed include:

How should biomass materials be prepared for steel and coke?

Determining the appropriate conversion process of raw biomass to

char in order to increase its carbon content in the char to 80% or

greater

Technologies aimed at removing residuals and chemical

characterization of residuals such as CaO, Na2O, K2O in the char

Which biomass sources are best suited to steel and coke operations?

Identifying potential sources of biomass given availability, as well as

required physical and chemical properties of the resultant char.

Char Production

How can we sustainably produce bio-based carbon for the iron and steel industries?

Pyrolysis Stages

Temperature Process (Overlap) Major Products Heat

<200ºC Drying H20 IN

230ºC-250ºC Depolymerization Acetic acid, Methanol, CO2, CO IN

250ºC-280ºC Torrefaction Extractives, CO2, CO IN

280ºC-500ºC Devolatilization Organics, Tars, CO2,CO OUT

500ºC-700ºC Dissociation/Carbonization CO, H2 IN

>700ºC Gasification H2, CO IN

Pyrolysis Product Distribution

A.V.Bridgwater

Mode Conditions Liquid Char Gas

Fast pyrolysis Moderate temperature,

short residence time 75% 12% 13%

Slow Pyrolysis Low temperature, very long residence time

30% 35% 35%

Gasification High temperature, long residence time.

5% 10% 85%

Optimal Conditions For Charcoal Production vs. Fast Pyrolysis Biochar

• Low pyrolysis temperature (<400ºC) (but also lower fixed carbon content) • High process pressure (1 MPa) (higher concentration of pyrolysis vapor increases

rate of secondary reactions) • Long vapor residence time (extended vapor/solid contact promotes secondary

coke forming reactions) • Low heating rate (slower formation and escape of organic vapors) • Large biomass particle size – large charcoal particles (low thermal conductivity of biomass results in slow

heat and mass transfer rate within particles)

ABRI Tech Mobile Fast Pyrolysis Unit

CanmetENERGY Fast Pyrolysis R&D 2011/13

Focus on developing in-house research-scale fluidized

bed and ablative designs

10 kg/h feed, < 1 s residence time

Recycle pyrolysis NCG as fluidizing medium

two reactors with identical ancillary equipment

Fluidized Bed

Ablative

Torrefaction

As is the case for charcoal Torrefied wood pulverizes easily

Heating value is 19-24 MJ/kg (vs 18-20 for wood)

Energy density is 15-18 GJ/m3 (vs 8-10 for wood)

Torrefaction yield > 80%

Dry fuel

Does not absorb water

Water-proof high energy pellets?

Current State of Torrefaction

At this point only results

from pilot plants using

woody biomass are

available. Demonstration

plants are starting to come

on-line and they will have to

be optimized for product

consistency, quality, energy

yield, and production costs.

Current CanmetENERGY R&D Activities in Biomass Torrefaction: CEATI PROJECT No. SOIG-11-03: SCOPE

Process conditions to torrefy agricultural based biomass feedstock.

Develop a technically acceptable and economic source of fuel while

accounting for variables such as feedstock, particle size, temperature

and residence time, etc.

Effect of raw feedstock preparation (e.g. chemistry improvement, fuel

washing, size reduction, additives, binders, etc.) on the resulting fuel

quality Issues with post-torrefaction densification (e.g. pelletizing,

briquette-making, handling, dusting, storage, etc).

Establishment of fuel characteristics (e.g. durability, ash fusion

temperatures, hydrophobic properties, etc).

Costs of processing and torrefying agricultural biomass feedstock into

a fuel product.

Identification of locally and regionally available sustainable biomass resources

Assessment of raw biomass conversion technologies

Process modelling and integration of biomass components into oil-sands operations.

Project objectives

Integration of Renewable Biomass Products

into Oil-sands Processing to Reduce Emissions

“Greening the Oil Sands”

Proposed biomass co-utilizations in oil sands operations

Raw

Biomass Torrefaction

Pyrolysis

Blending /

primary

upgrading

Combustion

Gasification/ syngas

Reforming

/ WSTC*

F-T

process

Bio-oil upgrading

(secondary)

Char

Haul &

Densification

District level

collection

Pelletization

Process

heat

H2

O < 5-7%

Activated carbon for

waste water treatment

Bitumen upgrader

Bio-oil

*water splitting thermo-chemical cycle

3-stage Biomass Haul & Densification

D D D D D

D D D D D

D D B D D

D D D D D

D D D D D

A sample district composed of square fields

D: Biomass Densification through pyrolysis or torrefaction

B: Bio-oil Blending or primary upgrading at district level

stage 1: Raw biomass

stage 2: Bio-oil or torrefied biomass

stage 3 : Blended / upgraded bio-oil or

Pellets to bitumen upgrader

Bitumen upgrader

upgradergridsquare rrrHaulTotal.

PRO II Thermodynamic model of Torrefaction

• Successful mass balance of C, H, O.

• Close agreement between predicted & experimental

values of torrefied biomass properties.

10

15

20

25

HH

V (

MJ

/kg

)

Willow Wheat

Straw

Switch

Grass

Loblolly

Pine*

Reported vs calculated

Calculated

Reported

0

0.2

0.4

0.6

0.8

1

Willow Wheat Straw Switch

Grass

Loblolly Pine

Predicted Torrefaction yield

Mass Yield

Energy Yield

* Unlike Willow, Wheat Straw and Switch Grass, reported data for

Loblolly Pine was taken for wet torrefaction

LHV of bio oil is on a wet basis

0

5

10

15

20

Ace

tic A

cid

Pro

pion

ic A

cid

Met

hoxy

phen

ol

Eth

ylph

enol

Form

ic A

cid

Pro

pyl-B

enzo

ate

Phe

nol

Toluen

e

Furfu

ral

Ben

zene

Wat

er

Component

Co

mp

os

itio

n (

wt%

dry

ba

sis

)

Reference case

Case 1 (Predicted)

Case 2 (Predicted)

Reference case Predicted

Case 1 Case 2

Bio-oil yield (wt%, dry biomass) 60 55 48

LHV, MJ/kg 17.5 17.7 18.1

PRO II Thermodynamic model of Pyrolysis

Pyrolysis Oil Combustion Pilot Facility

Combustion Test Py-oil Combustion Test June 23, 2011

0

100

200

300

400

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800

900

1000

1100

9:3

4:5

2

9:3

9:3

8

9:4

4:2

4

9:4

9:1

0

9:5

3:5

6

9:5

8:4

2

10

:03

:28

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Time

Fuel flow rate (kg/hr)

Chamber temperature (°C)

Fuel density (kg/m3)

Further Development

Nozzle design / Flame Stability

Controls incl. flame sensor

Ignition Control

Emissions (VOC, D/F)

Cold Start

Corrosion vs quality/upgrading

Acknowledgements

Fernando Preto

René-Pierre Allard

Guy Tourigny

Ben Bronson

Murlidhar Gupta

René Pigeon

Sebnem Madrali

Ed Hogan

Thank You