Вы находитесь на странице: 1из 29

The Relation of Pyrolysis Processes to Charcoal Chemical and Physical Properties

Robert J. Evans National Renewable Energy Laboratory


Symposium on Black Carbon in Soils & Sediments; Formation, Stabilization, Abundance and Environmental Function Joint meeting of The Geological Society of America & The Soil Science Society of America October 5-9, Houston TX

Acknowledgments
Early work on Pyrolysis with Tom Milne, SERI/NREL H2/C/NH3 Concept with Danny Day, Eprida
Funded in part by the DOE Hydrogen Program Integrated USDA/DOE project led by Robert Brown, ISU

Charcoal and soil carbon studies with Kim Magrini, Heidi Pilath, and Stefan Czernik, NREL
Funded by NREL Discretionary Funds

Activated Carbon for metals adsorption with Eun-Jae Shin, Jim Ranville, and Andy Herring, Colorado School of Mines
Funded by the Colorado Institute of Technology

Nitrogen Chemistry in Char formation with Mark Nimlos, Luc Moens, Mike Looker, NREL
Funded by Phillip Morris

Outline
Introduction
Biomass and charcoal Pyrolysis

Charcoal formation
Stoichiometric and thermodynamic potential Biomass pyrolysis pathways

Char Characterization Nitrogen effects Charcoal production


Optimum conditions Technologies

Summary

Lignocellulosic Biomass
Average elemental composition: CH1.4O0.6
Cellulose: 38% - 50%
Most abundant form of carbon in biosphere Polymer of glucose

Hemicellulose: 23% - 32%


Polymer of 5- and 6-carbon sugars Xylose is the second most abundant sugar in the biosphere

Lignin: 15% - 25%


Complex aromatic structure p-hydroxyphenylpropane building blocks

Extractives: 1% - 5%

Pyrolysis of Biomass
Thermal decomposition occurring in the absence of oxygen Above 300C polymeric building blocks undergo crosslinking, depolymerization and fragmentation Smaller molecules are released as gases and vapors
can react with residual solids producing more condensed structures (Pyrosynthesis)

Always produces solid (charcoal), liquid (water and organics), and gaseous (CO, CO2, CH4, H2)
Proportions and composition dependent on feedstock and process conditions.

What is Charcoal?
Charcoal is a solid product of pyrolysis of biomass carried out at temperature above 300C.
Is black in color, retains morphology of original feedstock, burns without flame. Is not a pure carbon or a single compound. Elemental composition: C, H, O, N, S, ash Proximate analysis: fixed carbon >70% , volatiles, ash Has been produced for thousands years.

Picture from Wikipedia

Char 1/2

Char 1/2-1% H3PO4

Charcoal Yields
Stoichiometric:
CH1.4O0.6 CH0.2 + 0.6H2O
53.0% (100% of C)

Thermodynamic:
Cellulose: C6H10O5 3.74C + 2.65H2O + 1.17CO2 + 1.08CH4
27.7% (62.4% of C) Antal, M,J. and Gronli, M, Ind.Eng.Chem.Res 2003, 42, 1619-1640

Practical:
CH1.4O0.6 charcoal + gas + liquid
10-35% (15-60% of C)

Slow Heating of Biomass


Temperature <200C Solid Phase Drying Gas Phase H 2O Acetic acid, MeOH Labile Deoxygenation Organics, H2O, gas Aromatics, HCs, H2O, gas

230C-250C Retification 250C-280C Torrefaction 300C-500C Devolatilization >500C Carbonization

TGA of Poplar Wood


heating at 10C/min to 600C in nitrogen

Beechwood xylan Aspen lignin

Cellulose (cotton linters)

TGA of Biomass Polymers


heating at 10C/min to 600C in nitrogen

Beech wood xylan Aspen lignin

Cellulose (cotton linters)

Biomass Pyrolysis Processes


Char CARBONIZATION low temperature long residence time FAST PYROLYSIS moderate temperature short residence time GASIFICATION high temperature long residence time 35% Liquid 30% Gas 35%

12%

75%

13%

10%

5%

85%

Biomass Pyrolysis Pathways


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

Low P

High P Primary Liquids Condensed Oils


(phenols, aromatics)

Liquid Phase

Tars

High P Solid Phase

Biomass

Charcoal

Coke

Soot

Pyrolysis Severity
Evans, R.J. and Milne, T.A., Energy & Fuels 1987, 1, 123-137.

TGA weight loss behavior for selected char and activated carbons.

Physical Characteristics of Char & AC


Lodgepole Pine (20 kPa if P is not stated) Ned 1/8 Lead 1/8 Ned 1/2 Ned 1/2 1% H2SO4 Ned 1/2 1% H3PO4 Vail 1/2 100 kPa Vail 1/2 3% KOH Ned Sawdust Ned Sawdust 100 kPa Yield (%) Char 22.6 23.3 25.1 35 33.8 26.7 22.0 26.5 AC 35 (8) 42.9 49 (12) 69 (24) 71 (24) 59.6 (16) 32.0 48.1 (11) 41.3 (11) BET SA (m2/g) Char 3.9 3.9 3.3 3.7 3.6 2.1 5.7 10.7 AC 806 828 896 532 452 619 418 726 685

Elemental Analysis
Wt.% C H O* Ash H/C O/C

Raw Sawdust

49.

6.3

43

1.01

1.54

0.66

C-LPP 1/2 Nd

76

4.3

19

0.92

0.68

0.18

AC-LPP 1/2 Nd
*by

92

1.7

4.5

2.3

0.22

0.04

difference

DRIFTS of Lodgepole Pine (Pinus contorta) sawdust

DRIFTS of sawdust char produced at 400 C and 20 kPa pressure

DRIFTS of sawdust activated carbon produced at 700 C with steam

FTIR Matrix + Proline Char


0.20

Pro+Glu+Cell+Pect (1:1:2:2)
3050 (C-H st, aromatic)

1575 (arom. C-C st)

1454 (arom. C-C st) 820 (arom. C-H oop)

1610 (N-H bnd & C=O st, acid)

0.15

d) 550 C
Kubelka-Munk

3550 (O-H st)

2200 (C= N st)

1737 (C=O st)

2910 (C-H st, aliphatic) 0.10

c) 350 C

0.05

b) 170 C a) RT
0.00 4000 3500 3000 2500 cm
-1

1030 1370 (C-O st) (C-H bnd) 2000 1500 1000

DRIFT spectra of chars heated to 550C. in the region of the CN stretch. The black trace is for the carbohydrate matrix, the blue trace is proline mixed with the matrix, the red trace is tryptophan mixed with the matrix and the green trace is asparagine mixed with the matrix.

Proline + Glucose + Cellulose + Pectin Staged Pyrolysis, mol %


16% C 45% H 40% O 0% N 170 C 27% Conversion
o

22% C 51% H 26% O 1% N 350 C 59% Conversion


o

35% C 56% H 7% O 2% N 550 oC 40% Conversion

29% C 170 oC 47% H 24% O 73% 1% N Conversion

33% C 350 oC 48% H 18% O 41% 1% N Conversion

49% C 550 oC 42% H 4% O 60% 3% N Conversion

62% C 30% H 5% O 3% N

Enhanced Charcoal Formation


Charcoal is a product of both primary (char) and secondary (coke) reactions Increasing yields requires minimizing the carbon losses in the form of gases and liquids and promoting the desired pathways: primary solid-phase dehydration, decarboxylation, and decarbonylation reactions secondary conversion of pyrolysis vapors to solids Acid and Base Catalysis

Charcoal Yields
Charcoal yields depend on feeedstock and on process conditions: Lignin, protein, and ash content Pyrolysis temperature Process pressure Vapor residence time Particle size Heating rate Heat integration (biomass burn off)

Heat for Charcoal Production


<280C 280C-350C >350C Endothermic (evaporation) Exothermic (char formation) Endothermic (devolatilization)

Heat for the process can be provided: directly as the heat of reaction by flue gases from combustion of by-product and/or feedstock directly to the reactor by flue gases through the reactor wall

Charcoal Production
Batch processes:
Earth pits and mounds Brick, concrete, and metal kilns Retorts

Yield
>10% 20-25% 30%

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

Novel processes:
Flash carbonization 40-50%

Flash Carbonization
Batch operation; 10 tons/day charcoal. Biomass loaded to a canister then heated up to 350C at 0.7 MPa for 30-90 min. Charcoal yield 40-50% (70-80% fixed carbon). Catalytic afterburner for tars eliminates smoke from reactor effluents. Capital cost $200,000.
HNEI Flash Carbonization Demonstration Reactor

Summary
Charcoal is a product of primary and secondary reactions occurring during pyrolysis of biomass. High yields of charcoal are favored by:
high lignin, ash, and nitrogen content low temperature, high pressure, large particle size low heating rate and long vapor residence time

Speculative concepts for soil applications: Biocarbon surface area enhancement may be important for optimizing the soil interface
Vacuum pyrolysis and steam activation may give enhanced properties eve if yield is lower Incorporation of nutrients (NPK) can influence char yield and properties and increase agronomic impact Highly sorptive chars could be integrated in agricultural chemical management A first application of bio-carbon in water quality applications could be feasible

Questions
It's no trick to get the right answer when you have all the data. The real creative trick is to get the right answer when you have only half of the data in hand and half of it is wrong and you don't know which half is wrong. When you get the right answer under these circumstances, you are doing something creative. Melvin Calvin, Following the Trail of Light: A Scientific Odyssey