Pyrolysis, Char and Energy

Fernando Preto CanmetENERGY, Natural Resources Canada

The Canadian Biochar Initiative, Inaugural Meeting December 12, 2008, Ste Anne de Bellevue

About CanmetENERGY
CanmetENERGY is the science and technology arm of the Energy Technology and Programs Sector of Natural Resources Canada

CanmetENERGY assists industry to develop cleaner, energy-efficient and cost-effective biomass conversion processes.

The Biomass & Renewables Group focuses on optimizing the performance of biomass energy technologies and developing new products and technologies for sustainable development.

Charcoal or Biochar
Pyrolysis produces charcoal, which is called biochar when buried in the ground Carbon from the waste biomass is retained in biochar and permanently sequestered in the soil, effectively removing that carbon from the atmosphere. The carbon in a ton of biochar is equivalent to 3 to 3.5 tons of CO2. Biochar is not only a carbon sink, it increases soil fertility increasing cat-ion exchange and water retention capacity in soils, while reducing nutrient leaching and providing a "coral reef" for soil microorganisms thereby significantly increasing productivity and crop yield. http://www.biocharengineering.com/

Charcoal or Biochar
If charcoal is used for energy can it be called biochar? Ultimate goal is still to optimize solid carbon retention (char production) whether the objective is to use it as a fuel/feedstock or as soil remediation What is the best way to optimize char production?

What is Pyrolysis?
Pyrolysis is the thermal decomposition of biomass (organic material) at elevated temperatures, in the absence of oxidants such as air or oxygen. Pyrolysis of solid biomass produces solid (char) and vapour containing the products of decomposition. Part of the vapour can be condensed to produce a liquid (bio-oil). The distribution between solid, liquid and noncondensable gases depends on the biomass and conditions of pyrolysis (temperature and time).

Charcoal Production & Use

Pyrolysis in late medieval foundry processes Georgius Agricola, De Re Metallica Libri XII, MDLVI English translation 1912 by Herbert Hoover

Pyrolysis: The Future

GHG Neutral; Improved Fuel Properties; Value Added Byproducts

Ensyn Dynamotive ABRI Tech Alterna Organic Power Titan Agritherm

Activated Carbon

Resins

Food Flavoring

Bio-Fuel

Char Production

How can we optimize char production?

Pyrolysis Stages
Temperature
<200C 230C-250C 250C-280C 280C-500C 500C-700C >700C

Process (Overlap)
Drying Depolymerization Torrefaction Devolatilization

Major Products
H20 Acetic acid, Methanol, CO2, CO Extractives, CO2, CO Organics, Tars, CO2,CO

Heat
IN IN IN OUT IN IN

Dissociation/Carbonization CO, H2 Gasification H2, CO

Time to Complete Pyrolysis as f(size)

X. Wang et al 2006

Yields vs Residence Time

40 35 30 25 20 15 10 5 0 2.5 secs
T=500 C

Yield %

Liquid Gas Solid

5 secs

20 secs

Vapour Residence Time

Charcoal Yield as f(size)

X. Wang et al 2006

Product(s) Yield as f(Temperature)

X. Wang et al 2006

Product Distribution
Mode Conditions Moderate temperature, short residence time Low temperature, very long residence time Liquid Char Gas

Fast pyrolysis

75%

12%

13%

Slow Pyrolysis

30%

35%

35%

Gasification

High temperature, long residence time.

5%

10%

85%

A.V.Bridgwater

Yield of Traditional Charcoal Processes

Batch processes:
Earth pits and mounds Brick, concrete, and metal kilns Retorts >10% 20-25% 30%

Continuous processes:
Retorts (Lambiotte) Multiple hearth reactors (Herreshoff) 30-35% 25-30%

FAO Rinsing Retort

Pyrolysis: Industrial Research in Canada

Ensyn Dynamotive ABRI Tech Alterna Organic Power Titan Agritherm

Maximizing Charcoal Yield

Alterna, McBride, BC

Organic Power, Chilliwack, BC

Courtesy NREL

Maximizing Charcoal Yield

Maximizing Charcoal Yield

Low pyrolysis temperature (<400C)

(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 (low thermal conductivity of biomass results in slow heat and mass transfer rate within particles)

What is impetus for using charcoal/biocarbon as industrial energy?

OPG Coal Power Production

Courtesy OPG

Maximizing Charcoal Yield

Courtesy OPG

Maximizing Charcoal Yield

Fuel Properties Density & Grindability

Courtesy OPG

Biomass Fuel Density is Low

Equivalent Energy Content

Straw

Wood

Coal

Grindability: Pulverizer Performance

Biomass is Plastic not Brittle

Charcoal or Biochar
Charcoal is brittle and not plastic pyrolysis breaks down the hemicellulose matrix and depolymerizes cellulose Heating Value 28-32 MJ/kg Energy Density 9-11 GJ/m3

Species Migration: S, N

J. Hrbek et al 2006

Species Migration: Cl, K

J. Hrbek et al 2006

CanmetENERGY Study:
The Combustion Characteristics of Charcoal and a Strategy for the Development of Biocoal Formulations for use in Utility Boilers The objectives of this study were to investigate: The combustion characteristics of commercial charcoal and determine how it would behave in a utility boiler. Determine if there exists more optimal charcoal formulations for use in utility boilers
Acknowledgements: R. Dureau, B. Clements, A. Palmer, L. Giroux

Hardgrove Index

Charcoal

Eastern HVBit 58

Alberta Sub C 38

Rocky Mountain MVB 85

HGI

115

Ignition Temperature

Charcoal Ignition Temperature (oC)

Eastern HVBit 521

Alberta Sub C 532

Rocky Mountain MVB 627

317

Comparative Proximate Analysis

Units Biocoal #1 Wood Eastern HVBit 8.3 6.4 31.6 53.7 30.5 Alberta Sub C 25.1 11.6 26.6 36.7 17.8 Rocky Mountain MVB 9.0 12.0 23.0 54.0 28.8

Moisture Ash Volatile Matter Fixed Carbon HHV

Wt% Wt% Wt% Wt% MJ/kg

3.13 1.68 12.26 82.93 32.1

35.7 0.56 77.7 49.7 19.5

Comparative Ultimate Analysis

Units C H N S O Ash Moisture Wt% Wt% Wt% Wt% Wt% Wt% Wt% Biocoal #1 85.43 2.63 0.392 0.012 6.73 1.68 3.13 Wood 49.7 6.0 0.1 0.1 43.6 0.56 35.7 Eastern HVBit 72.7 4.8 1.6 2.3 3.9 6.4 8.3 Alberta Sub C 45.6 2.9 0.6 0.2 13.9 11.6 25.1 Rocky Mountain MVB 64.0 3.8 1.0 0.2 10.0 12.0 9.0

Comparative Ash Analysis

Units SiO2 Al2O3 Fe2O3 CaO Na2O K2O MgO TiO2 SO3 P2O5 BaO SrO Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt% Biocoal #1 3.68 1.35 2.10 57.3 1.41 8.97 8.41 0.06 2.97 5.23 0.28 0.155 Eastern HVBit 34.2 18.1 43.7 1.2 0.5 1.5 0.6 1.1 0.9 Na Na Na Alberta Sub C 51.8 23.1 3.3 13.8 2.1 0.8 0.8 0.9 4.7 Na Na Na Rocky Mountain MVB 42.0 20.0 5.0 15.0 0.2 1.0 2.3 1.0 13.5 Na Na Na

Ash Issues Require Further Study

Energy Density
Charcoal Wood Coal 9-11 GJ/m3 8-10 GJ/m3 25-40 GJ/m3

Energy density is still an issue as volume of fuel becomes a limiting factor for existing feed systems

Future Directions for Char Energy

Torrefaction Char-Oil Slurries Charcoal Pellets Charcoal Gasification

Pyrolysis Stages
Temperature
<200C 230C-250C 250C-280C 280C-500C 500C-700C >700C

Process (Overlap)
Drying Depolymerization Torrefaction Devolatilization

Major Products
H20 Acetic acid, Methanol, CO2, CO Extractives, CO2, CO Organics, Tars, CO2,CO

Heat
IN IN IN OUT IN IN

Dissociation/Carbonization CO, H2 Gasification H2, CO

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?

Char-oil Slurries
Energy Density 25-28 GJ/m3

Pelletizing Charcoal?

Charcoal Gasification

Charcoal produces cleaner syngas than wood

Thank You!

Questions?
Fernando Preto
preto@nrcan.gc.ca Tel: 613-996-5589

http://canmetenergy.nrcan.gc.ca/