Clase 3 MGarcia

BIOMASS THERMO-CHEMICAL
CONVERSION TECHNOLOGIES
LECTURER: MANUEL GARCIA-PEREZ , Ph.D.
Department of Biological Systems Engineering,

Washington State University
e-mail: mgarcia-perez@wsu.edu
Universidad Nacional de Colombia: Sede Medellin
December 3-14, 2018

A.- COURSE OUTLINE
COURSE GRADING: (OPTION 1)
Projects (60 %)
Project # 1 : Each team of three students will choose a biomass related with their research subject and
will study its thermal behavior at different heating rates using thermogravimetry under nitrogen. The
students will quantify the moisture content, the content of volatiles, fixed carbon and ash (5%) (LAB 1)
Project # 2 : Each team will measure the elemental composition (CHNS-O) of their biomass (5%) (LAB 2)
Project # 3 : Each team will measure the calorific value of their biomass (5%) (LAB 3)
Project # 4 : Each team will identify the nature of the compounds released during the thermal degradation
of the material selected using Pyrolysis – Gas Chromatography / Mass Spectroscopy (Py-GC/MS) (5 %)
(LAB 4)
Project # 5: Use the Friedman and ASTM methods to obtain kinetic constants from data obtained by
Thermogravimetry (10 %)
Project # 6: To carry out mass and energy balances of a thermochemical reactor (gasification or
pyrolysis) (10 %)
Project # 7: Use of kinetic constants obtained to estimate the total pyrolysis times of the biomass
particle processed (10 %)
Project # 8: Size the thermochemical Reactor (5 %)
Project # 9: Final Report and Defense (5 %)
Homeworks (10 %)
Homework # 1: (5 %)
Homework # 2 (5 %)
Exams (30 %)
First Exam: Questions related with Topics 1 and 2 (15 %)
Second Exam: Questions related with Topics 3 and 4 (15 %)
OUTLINE OF OUR PREVIOUS LECTURE
A. Fast Pyrolysis
B. Gasification
LECTURE OUTLINE
A. Combustion
A.- COURSE OUTILNE
Biomass Resources and Energy Situation

1.- Introduction
Introduction to Biomass Thermochemical Conversion Technologies
Biomass Composition (Cellulose, Hemicellulose, Lignin, Extractives

2.- Biomass and Ash)
Chemistry
Experimental Methods to Quantify Biomass Components. Primary
Thermochemical Reactions of biomass components.
3.- Analytical Themogravimetric Analysis (TG) and Differential Scanning

Pyrolysis and Study Calorimetry (DSC)
of Thermochemical
Reactions Pyrolysis GC/MS, Elemental and Proximate analyses, Calorific Value,
Thermochemical reactors
4.- Design and evaluation of biomass themo-chemical conversion technologies
Kinetics of Characterization and

Mass and Heat and Mass Hydrodynamics of Fluidized
Primary and Energy Transfer in Beds, Heat and Mass uses of
Secondary Thermochemical
Balances Biomass Transfer in Fluidized Beds
Thermochemical Particles Products
Reactions
A.- COMBUSTION (OVER 1500 oC)
2500
Constant Volume Adiabatic Flame

2000
Pyrolysis Combustion
Temperature [ oC]
1500
FAST PROCESSES
NEAR EQUILIBRIUM
1000
800
Gasification oC
500
REACTIONS CONTROLLED
BY KINETICS
0
Torrefaction
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2
1/ f
Combustion > 1500 oC, Gasification 600 – 1400 oC, Fast Pyrolysis 350
– 600 oC, Torrefaction: 220 – 300 oC
ADIABATIC FLAME TEMPERATURE VS. EQUIVALENT RATIO (f)

Common Gas-Solid Reactors used in Thermochemical Conversion
Screw
Moving beds Fluidized beds Rotary drums
conveyers
Biomass (Auger
Steam ,
Reactors)
nitrogen,
oxygen or air
Gas
Biomas
s Gas
Biomass
Heat
Solid Steam ,
nitrogen, oxygen
or air
Gas
Gas Heat Biomass
Steam ,
nitrogen, oxygen Solid
or air Heat
Solid
Steam ,
Heat
nitrogen, oxygen Solid
or air
Combustion is a chemical reaction between fuel and oxidizer involving significant release of energy
as heat. Total World Energy production from biomass combustion is of 50,000 MWe.
Complete oxidation of biomass to CO2 and H2O with production of heat (equivalent ratio (f smaller
than 1), temperatures (over 1,500 oC)
Commercially available, emissions problems, low electrical efficiency at small scale (η ≤ 30 %)

FLUE GAS
BOILER
BIOMASS
STORAGE SUBSTATION ELECTRICITY
TURBINE
DRYER
GENERATOR
DRYER AIR
EXHAUST BOILER
MAKE-UP WATER
BLOWDOWN
Direct-fired biomass electricity generating system

schematics. (Rankine cycle)
The combustion of solid biomass is fully established and already widely

used in biomass applications. The combustion properties of biomass are
well understood. The most popular combustors for biomass applications
are stoker-fired, fluid beds, and suspension fired furnaces.
In stroker-fired combustors the feed burns as it moves through the

furnace while resting on a stationary or moving grate.
Fluid bed designs burn the feed in a turbulent bed of inert material that is
fluidized by combustion air flowing through it from underneath. Although
the grate-fired combustors are the norm for older biomass fired plants,
fluid bed combustors are rapidly becoming the preferred technology for
biomass combustion because of their low NOx emissions. Fluidized bed
boilers have been commercially available for over 20 years, at capacities
ranging from 15 to 715 MW input. Bubbling fluid bed tend to be limited to
the lower size range, while circulating fluid beds are reported over the
entire capacity range. Over 110 fluid beds are operating in U.S. All with
performance guarantees from the vendor.
Principal combustion technologies for biomass
Van Loo S, Koppejan J: The handbook of Biomass Combustion & Co-firing. Earthscan, 2008
Fluidized bed combustion (FBC) systems burn the wood fuel on a high temperature bed
of finely divided inert material, such as sand, that is agitated by air blown from beneath
the bed. Solid fuel is introduced into the chamber via an airlock, where the fuel particle,
where the fuel particle burn while suspended in the bed. A stream of gases passes
upwards through a bed of free flowing granular materials in which the gas velocity is large
enough that the solid particles are widely separated and circulated freely throughout the
bed. During overall circulation of the bed there will be transient streams of gas flowing
upwards in channels containing few solids and clumps or masses of solids flowing
downwards. The fluidized bed looks like a boiling liquid. The bed is usually sand or
limestine. Overfire is normally introduced in the disengaging zone ( freeboard)
Bubbling fluidized bed furnace
Circulating fluid bed: If the air flow of a bubbling fluid bed is increased, the air bubbles
become larger forming large voids in the bed and entraining substantial amounts of solids.
This type of bed is referred to as turbulent fluid bed. In a circulating fluid bed the turbulent
bed solids are collected, separated from the gas and returned to the bed, forming a solid
circulation loop. A circulating fluid bed can be differentiated from a bubbling fluid bed in
that there is no distinct separation between the dense solid zone and the diluted solids
zone. Circulating fluid bed densities are about 560 kg/m3 compared to a bubbling bed
density of 720 kg/m3 . To achieve the lower bed density air rates are increased from the 1.5
– 3.7 m/s of bubbling bed to about 9.1 m/s. The residence time of the solids in a
circulating fluid bed is determined by the solids circulation rate, the attrition of the solids,
and the collection efficiency of the solids separation device.
Circulating Fluid Bed:

Stoker Combustors
Stoker combustors improve on operation of the pile burners by providing a moving grate
which permits continuous ash collection, this eliminating cyclic operation characteristic of
traditional pile burners. In addition, the fuel is spread more evenly, normally by
pneumatic stoker and in thinner layer in the combustion zone fiving more efficient
combustion. Stoker fired boilers were first introduced in the 1920s for coal and in the late
1940s the Detroit stoker installed the first travelling grate spreader stoker for wood. In the
basic stoker design the bottom of the furnace is a moving grate which is cooled by under-
fire air. Underfire air defines the maximum temperature of the grate and thus the
allowable moisture content of the feed. Staged combustion processes were developed in
the 1980’s to meet the tighter NOx emission limits. For 40 % excess air the overfire air gas
been increased to 50 %, lowering the maximum temperature in the furnace.
Classification of grade combustion technologies

Like in the case of gasifiers, combustion chambers can also be classified by the
direction at which the solid and gases move.
A.- COMBUSTION (OVER 1500 oC) (Other designs)
Travelling grade furnace fed by Vibrating grade fed by spreader stokes

spreader stokes
Horizontally moving grade Cigar burner
Considerable effort is focused on the development of clean and

efficient wood burning and other biomass combustion appliances
for heating and cooking. Developments in stove design for these
types of application are the subject of active discussion and debate
around the world.
Brown R. Thermochemical Processing of Biomass. Conversion into Fuels, Chemicals and Power. Wiley 2011
Stoves
The catalytic combustor improves emissions performance by continuing to react combustion products to lower
temperatures (around 260 oC)
Classification of wood-stoves depending on primary air flow paths
Stoves
Primary air
splitter
Primary air 1
Primary air 2
Air jets
Secondary air
After burner
zon e
Combustion air
Stoves
Wood combustion with over-fire Under Fire boiler
boiler
Stoves
Microprocessor controlled down-draught boiler for wood logs
Pellet Stove
More sophisticated stoves have
been developed for residential
and small commercial and
industrial heating applications.
These often involve automatic
control and the use of
preprocessed fuels, such as
pellets, to maintain good control
over the combustion and reduce
emissions. Small biomass
systems typically emit
considerable amounts of CO,
particulate matter (PM),
polycyclic aromatic
hydrocarbons (PAHs) and other
products of incomplete
combustion.
Brown R. Thermochemical Processing of Biomass. Conversion into Fuels, Chemicals and Power. Wiley 2011
Wood pellet burners
(1) Underfed burner
(2) Horizontally fed burner
(3) Overfed burner
A.- CONCLUSIONS
The main thermo-chemical conversion technologies to be studied in this course are:
TORREFACTION: Pre-treatment method carried out at 225-300 °C in absence of

oxygen. The biomass become completely dried and loose its tenacious and fibrous
structure. The grindability and the calorific value of biomass is improved
significantly.
PYROLYSIS : Process in the absence of air/oxygen carried out at temperatures

between 350 and 600 oC. This process can be controlled to maximize either the
production of charcoal or liquid products.
GASIFICATION: Process that converts carbonaceous materials, such as biomass, into

gases rich in carbon monoxide and hydrogen by reacting the raw material at high
temperatures with a controlled amount of oxigen and/or steam. The resulting gas
mixture is called synthesis gas or syngas (700 – 1400 oC).
COMBUSTION : Complex sequence of exothermic chemical reactions between a the

biomass and an oxidant (usually air) to produce heat (Temperatures over 1400 oC) .
B.- WOOD AND BARK
Scale down through biomass from the organismal to the molecular level
(A) populus sp (B) poplar wood (C) cross section of a poplar sample. Cell types: X- xylem element, F: wood fiber R: ray
parenchyma (D) transmission electron microphotograph of a poplar xylem (E) artistic representation of the plant cell wall
macromolecular structure, red, cellulose microfibrils, yellow hemicellulose and pectins green: lignin, blue structural proteins.
(F) artistic representation of plant cell wall polymers (from top) cellulose hemicelluloses, lignin and protein
Source: Haas T.J., Nimlos M.R., Donohoe B.S.: Real-time and post-reaction microscopic structural analysis of biomass
undergoing pyrolysis. Energy & fuels 2009, 23, 3810-3817.
B.- WOOD AND BARK
Softwood (coniferous woods or gymnosperms )

Trees belong to seed-bearing plants
Hardwood (angiospermae)
More than 520 coniferous (softwood) and 30,000 aniosperms (hardwood) tree species are known.
Softwoods Hardwoods
Http://dcwi.Com/~bmills/trees/trees.Htm
B.- WOOD AND BARK
The macroscopic structure of wood

Wood is composed of elongated cells, most of which are oriented in the longitudinal direction of
the stem. They are connected with each other through openings, referred as pits.
These cells vary in their shape according to their functions, provide the necessary mechanical
strength to the tree and also perform the function of liquid transport as well as of reserve food
supplies.
Cross section of white oak tree trunk

A: outer bark (dry dead tissue)
B: Inner bark (phloem) (living tissue) Bark
C: cambium (living cells, cambial zone)

D: sapwood (lighter in color)
E: heartwood (dark-colored) (Wood or
xylem)
F: pith
G: wood rays
The pith is a dark stripe in the middle of the stem or

branches. It represents the tissues formed during the first
year of growth.
The sapwood conducts water from the roots to the foliage
Annual growth rings
B.- WOOD AND BARK
The cell wall is built up by several layers:
(1) Middle Lamella (ML) Binds the cells together
(2) Primary Wall (P)
(3) Outer Layer of the Secondary Wall (S1)
(4) Middle Layer of the Secondary Wall (S2)
(5) Inner Layer of the Secondary Wall (S3)
Petersen R: the chemical composition of wood (book chapter)

B.- WOOD AND BARK
Layers of wood Distribution of cellulose hemicellulose and

cell lignin in cell walls and their layers
Basu P: Biomass gasification and pyrolysis. Practical design and theory. Elsevier 2010
B.- WOOD AND BARK
nm
Cellulose
Cross-sectional model of the ultrastructural organization of the cell wall

components in wood.
O’sullivan A.C.: Cellulose: the structure slowly unravels. Cellulose (1997) 4, 173-207
B.- CELLULOSE
Cellulose is the main constituent of wood approximately 40-50 % of the dry

substance in most wood species is cellulose located predominantly in the
secondary cell wall.
1
1 4 4
4 1
Cellulose is a linear polysaccharide which is composed of between 10,000 to

15,000 glucose units linked by ether bonds (b 1-4 glycosidic bonds).
Bundles of cellulose molecules arrange together to form microfibrils, in

which highly ordered (crystalline) regions alternate with less ordered
(amorphous) regions.
Petersen R: The chemical composition of wood (book chapter)

B.- CELLULOSE
Source: Mcdonald A: Lecture: Structure & chemistry of biomass constituents lecture

(BAE504/CHE581)
B.- CELLULOSE
CELLULOSE CAN BE AMORSPHOUS OR CRYSTALLINE
Six polymorph structures of cellulose have been documented in the

literature (I, II, IIIi , IIIii, IVi and IVii).
Recently, evidence for two polymorphs of cellulose I has been offered.

what was previously thought to be one polymorph (I) (native cellulose)
have been found to be a mixture of two polymorphs (Ia and Ib).
The Ib phase (higher plants) has a larger number of intermolecular

hydrogen bonds than the Ia phase (primitive organisms).
All chains in native cellulose microfibrils are oriented in the same direction,
that is, they are parallel.
The proportion of ordered and disordered regions of cellulose vary

considerably depending on the origin of the sample. Cotton cellulose is
more crystalline than cellulose in wood.
REFERENCE: O’Sullivan A: cellulose: The structure slowly unravels.

Cellulose (1997) 4, 173-207.
B.- CELLULOSE
The crystallinity of wood is defined as the weight fraction of crystalline

material – crystalline cellulose – in wood. The cellulose crystallinity is
defined as “g of crystalline cellulose / 100 g cellulose”
Methods to quantify cellulose

crystallinity
X-ray diffraction
13C-NMR CP/MAS (Carbon- 13 cross polarization /
magic angle sample spinning )
FT-Raman spectroscopy
FTIR spectroscopy
Woody materials crystallinity: 60-70 g/100 g

cellulose
Crystallinity determined by X-ray diffraction is smaller than the crystallinity of

cellulose determined by NMR, the portion of lignin and hemicellulose affect the
XRD value
B.- CELLULOSE
CRYSTAL STRUCTURE OF CELLULOSE Ib

Axial projection Planar projection
Hydrogen bond
Van der Intrachain

Waals hydrogen bonds
forces
O5 C2
O2
C6 C5
O3 O6 C3
O3
Intrachain hydrogen bonds: O5 O2 C2 O5
O 6 – o2
O 3 – o5
Interchain hydrogen bonds: Interchain

hydrogen bonds
O 3 – o6
C.- HEMICELLULOSE
Hemicelluloses are mixtures of polysaccharides synthesized in wood

almost entirely from glucose, mannose, galactose, xylose,
arabinose, 4-O-methylglucoronic acid, and galacturonic acid
residues. Generally, hemicellulose are of much lower molecular
weight than cellulose and some are branched. Hemicelluloses are
soluble in alkali and easily hydrolyzed by acids.
Conformation of hemicellulose
monomers.
Petersen R: The chemical composition of wood (book chapter)

C.- HEMICELLULOSE
Hemicellulose monosaccharides
Source: Mcdonald A: Lecture: Structure & chemistry of biomass constituents lecture (BAE504/CHE581)
C.- HEMICELLULOSE
Partial structure of a common hardwood hemicellulose (O-acetyl-4-O-

methylglucuronoxylan)
Acetate groups Acetate groups
3
1 1 4
1 4
4 2
4-O-methylglucoronic 1
acid residue
The entire molecule consists of about 200 b-D-Xylopyranose residues linked

in (1-4) Glycosidic bonds.
Approximately 1 of 10 of the xylose residues has a 4-O-methylglucoronic
acid residue bonded to the main chain through the hydroxyl at the 2 ring
position.
Approximately 7 of 10 of the xylose residues have acetate groups bounded to
either the 2 or the 3 ring position.
Petersen R: the chemical composition of wood (book chapter)
C.- HEMICELLULOSE
Percentages of polysaccharides in the different layers of the fiber wall

D.- LIGNIN
Lignin is a phenolic substance consisting of an irregular array of

variously bonded hydroxy- and methoxy-substituted
phenylpropane units.
The precursors of lignin biosynthesis are:
P-Coumary Alcohol Coniferyl Alcohol Sinapyl Alcohol
(Guaiacylpropane units) (Syringylpropane units )
Minor precursor of Predominant precursor of

Precursor of
softwood and softwood and precursor of
hardwood lignin
hardwood lignins hardwood lignin
D.- LIGNIN
These alcohols are linked in lignin by ether and carbon-carbon bonds.
C-C
bond
Trace amounts
(less than 1 %)
Ether bond
Partial structure of softwood lignin

D.- LIGNIN
Structure of carbon skeleton

of the lignin monomeric units
Types of linkages and dimeric structures

C C
C C C
bC O C C
C
bC 5
C C
C
aC O C C C
aC O
5 5
O
O O
a-O-4 b-5 O
b-O-4 O 5-5
C
C C
C C C
C C bC
1
O bC Cb
C C
C C
4
5
O
O O
O O
4-O-5 b-1 b-b
D.- LIGNIN
Lignin composition
Source: Mcdonald A: Lecture: Structure & chemistry of biomass constituents lecture

(BAE504/CHE581)
D.- LIGNIN
LIGNIN STRUCTURAL REPRESENTATION

BROADBELT’S METHOD
Experimental ● Experimental data used
Characterization directly as inputs into
computational
structure model
Gel permeation ● Use stochastic method

• Py-GC/MS
chromatography for generating
• DFRC
“libraries” of lignin
• Thioacidolysis
structures (Yanez et al
• FTIR
Molecular Weight 2016, Dellon et al 2017)
• Various NMR
techniques ● No such thing as “one”
lignin structure
Degree of
Monomers Bond Types
Branching – Better approach is
to build ~103-106
molecular
representations
Yanez, et al. Energy Fuels (2016), 30, 5835-5845.
Dellon, et al. Energy Fuels (2017), 31, 8263-8274.
D.- LIGNIN
LIGNIN STRUCTURAL REPRESENTATION
STOCHASTIC STRUCTURE MODELING

Parameter Target (%) Computed
H monomer 2 1.91
G monomer 63 62.26
S monomer 35 35.82
Mn 3690 4258.95
Mw 5510 5401.10
β-O-4 60 60.01
α-O-4 5 5.12
β-1 15 15.16
β-β 10 10.22
β-5 6 5.99
4-O-5 2 2.19
5-5 2 1.32
E.- EXTRACTIVES
The extraneous components (extractives and ash) in wood are the

substances other than cellulose, hemicelluloses, and lignin. They do
not contribute to the cell wall structure and most are soluble in
neutral solvents.
The extraneous material soluble in neutral solvents – constitute 4-10

% of the dry weight of normal wood of species that grow in temperate
climates. They may be as much as 20 % of the wood of tropical
species.
Extractives are a variety of organic compounds including (1) fats, (2)

waxes, (3) alkaloids, (4) proteins, (5) simple and complex
phenolics, (6) simple sugars, (7) pectins, (8) mucilages, (9) gums,
(10) resins, (11) terpenes, (12) starches, (13) glycosides, (14)
saponins and (15) essential oils. Many of these function as
intermediates in metabolism, as energy reserves, or as part of the
tree’s defense mechanism against microbial attack. They contribute
to wood properties such as odor, and decay resistance.
E.- EXTRACTIVES
Chemical
families found in
extractives
E.- EXTRACTIVES
Source: Mcdonald A: Wood Chemistry Course. University of Idaho, 2010

E.- EXTRACTIVES

E.- EXTRACTIVES

E.- EXTRACTIVES

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BIOMASS THERMO-CHEMICAL

LECTURER: MANUEL GARCIA-PEREZ , Ph.D.

Department of Biological Systems Engineering,

Universidad Nacional de Colombia: Sede Medellin

December 3-14, 2018

Biomass Resources and Energy Situation

Biomass Composition (Cellulose, Hemicellulose, Lignin, Extractives

3.- Analytical Themogravimetric Analysis (TG) and Differential Scanning

4.- Design and evaluation of biomass themo-chemical conversion technologies

Kinetics of Characterization and

Constant Volume Adiabatic Flame

ADIABATIC FLAME TEMPERATURE VS. EQUIVALENT RATIO (f)

Common Gas-Solid Reactors used in Thermochemical Conversion

Commercially available, emissions problems, low electrical efficiency at small scale (η ≤ 30 %)

Direct-fired biomass electricity generating system

The combustion of solid biomass is fully established and already widely

In stroker-fired combustors the feed burns as it moves through the

Principal combustion technologies for biomass

Bubbling fluidized bed furnace

Circulating Fluid Bed:

Classification of grade combustion technologies

Travelling grade furnace fed by Vibrating grade fed by spreader stokes

Horizontally moving grade Cigar burner

Considerable effort is focused on the development of clean and

Classification of wood-stoves depending on primary air flow paths

Wood pellet burners

(1) Underfed burner

(2) Horizontally fed burner

(3) Overfed burner

The main thermo-chemical conversion technologies to be studied in this course are:

TORREFACTION: Pre-treatment method carried out at 225-300 °C in absence of

PYROLYSIS : Process in the absence of air/oxygen carried out at temperatures

GASIFICATION: Process that converts carbonaceous materials, such as biomass, into

COMBUSTION : Complex sequence of exothermic chemical reactions between a the

Softwood (coniferous woods or gymnosperms )

The macroscopic structure of wood

Cross section of white oak tree trunk

C: cambium (living cells, cambial zone)

The pith is a dark stripe in the middle of the stem or

The cell wall is built up by several layers:

(1) Middle Lamella (ML) Binds the cells together

(2) Primary Wall (P)

(3) Outer Layer of the Secondary Wall (S1)

(4) Middle Layer of the Secondary Wall (S2)

(5) Inner Layer of the Secondary Wall (S3)

Petersen R: the chemical composition of wood (book chapter)

Layers of wood Distribution of cellulose hemicellulose and

Cross-sectional model of the ultrastructural organization of the cell wall

Cellulose is the main constituent of wood approximately 40-50 % of the dry

Cellulose is a linear polysaccharide which is composed of between 10,000 to

Bundles of cellulose molecules arrange together to form microfibrils, in

Petersen R: The chemical composition of wood (book chapter)

Source: Mcdonald A: Lecture: Structure & chemistry of biomass constituents lecture

CELLULOSE CAN BE AMORSPHOUS OR CRYSTALLINE

Six polymorph structures of cellulose have been documented in the

Recently, evidence for two polymorphs of cellulose I has been offered.

The Ib phase (higher plants) has a larger number of intermolecular

The proportion of ordered and disordered regions of cellulose vary

REFERENCE: O’Sullivan A: cellulose: The structure slowly unravels.

The crystallinity of wood is defined as the weight fraction of crystalline

Methods to quantify cellulose

Woody materials crystallinity: 60-70 g/100 g

Crystallinity determined by X-ray diffraction is smaller than the crystallinity of