Chapter 6

Torrefaction and Pyrolysis

6-1 Torrefaction principal
6-2 Pyrolysis principal
6-3 Pyrolysis and carbonization
6-4 Fast pyrolysis
6-5 Reactor
6-6 Bio-oil

1
 Disadvantages of Biomass

Biomass is characterized by its

high moisture content
low calorific value
hygroscopic nature
Low grindability
large volume or low bulk density
nonhomogeneity

These result in a low conversion efficiency as well as

difficulties in its collection, grinding, storage and
transportation.
2
 Torrefaction

Torrefaction pertains to a thermal pretreatment of biomass

where raw biomass is heated in an inert atmosphere at
temperatures of 200-300 °C for several minutes to hours
for the purpose of upgrading solid biomass fuel.
Nitrogen is the commonly used carrier gas to provide a
non-oxidizing atmosphere.
Since torrefaction is conducted at conditions similar to
those of pyrolysis which usually takes place between 350
and 650 °C, torrefaction has also been called mild
pyrolysis.

3
Advantages of Torrefaction
Torrefaction is a mild pyrolysis process where
biomass is thermally degraded in an inert
atmosphere at temperatures of 200-300 °C to
produce biochar (torrefied biomass).

Light 200-235 °C

Mild 235-275 °C
Torrefaction

Severe 275-300 °C

4
 Advantages of Torrefaction

Benefits accomplished by torrefaction include:

higher calorific value or energy density per unit mass;
lower atomic O/C and H/C ratios and moisture content;
higher hydrophobicity or water-resistivity;
lower biodegrdation;
improved grindability and reactivity;
more uniform properties of biomass.

5
Torrefaction

6
The reduction in the hygroscopic behavior
of torrefied woods can be assigned to the
following reasons:

(1) the degradation of hemicelluloses and

amorphous cellulose results in removing
-OH and -COOH groups and further
decreasing hydrogen bonding with water
after torrefaction;
(2) tar condenses inside the pores, thereby
obstructing the passage of moist air
through the solid and then avoiding
water vapor condensation;
(3) the apolar character of condensed tar
on the solid also prevents the
condensation of water vapor inside the
pores

7
 Hygroscopic and Hydrophobic

➢ When biomass undergoes torrefaction, the hydroxyl

groups will be partly destroyed through dehydration. This
prevents the formation of hydrogen bonding so that the
torrefied biomass becomes hydrophobic.
➢ The lower saturated moisture content in torrefied biomass
could also result from tar condensation inside the pores,
obstructing the passage of moist air through the solid, and
then avoiding the condensation of water vapor.
➢ The apolar character of condensed tar on the solid also
prevents the condensation of water vapor inside the pores.

8
 2h

Weight (%
30

20

Grindability 10

0
1 2 3 4
No.
0
(a) 220 C (b) 250 0C
60
60

50 0.5 h
0.5 h 50 1h
1h 1.5 h
40 1.5 h 2h
40
Weight (%)

2h

Weight (%)
30
30

20
20

10
10

0
1 2 3 4 0
1 2 3 4
No. No.
0 0
(b) 250 C (c) 280 C
60 ⚫ Four-blade cracker 60
0.5 h
⚫ Rotation speed of 24,000 rounds per minute (rpm) for one minute 1h
50 ⚫ Three different sieves0.5
1h
h
(i.e. 100, 200 and 325 mesh)50 1.5 h
2h
1.5 h
2h
40
9
40
)
)
 Higher Heating Value

Material Volatile matter Fixed carbon Higher heating value

(wt%) (wt%) (MJ kg-1)

Raw biomass 67-88 0.5-20 15-20

Torrefied biomass 34-85 13-45 16-29

Coal 0.5-50 46-92 25-35

Renewable and Sustainable Energy Reviews 2015;44:847-866. 10

 Volatile Matter vs. Fixed Carbon

100

Raw biomass
Torrefied biomass

80
⚫ Devolatilization
⚫ Carbonization
VM (wt%)

In
60 cr
ea
sin
gt
or
re
fa
40 cti
on

20
0 10 20 30 40 50
FC (wt%)
Renewable and Sustainable Energy Reviews 2015;44:847-866. 11
 van Krevelen Diagram
 O
HHV (MJ/kg ) = 33.86  C + 144.4   H −  + 9.428  S
 8
2.5

2
Atomic H/C ratio

n
it o
fac
rre
1.5 to
ing
as
cre
In
1

0.5
0 0.2 0.4 0.6 0.8 1
Atomic O/C ratio
12
 Application of Torrefied Wood
Biochar has been produced and utilized for several
thousand years and is well known as charcoal
(when produced from woody biomass).

Waste water
treatment
Soil
amendment

Energy storage
Energy production Building and Carbon
construction sequestration

While biochar plays a role as a long-term sink for atmospheric

CO2 in carbon sequestration process, CO2 emissions could be reduced
by up to 84%.

13
 Pyrolysis

➢ Thermochemical decomposition of organic material at

elevated temperatures in the absence of oxygen

➢ The pyrolysis temperature is between 350 and 650 °C,

and the pressure is between 0.1 and 0.5 MPa. It is one of
the processes involved in charring wood.

➢ In general, pyrolysis of organic substances produces gas

and liquid products (bio-oils) and leaves a solid residue
richer in carbon content.

14
Pyrolysis

15
 Pyrolysis

Pyrolysis reactions can be categorized into slow

pyrolysis, intermediate pyrolysis and fast pyrolysis,
depending on reaction temperature and residence time
of gas stream.

The yields of gas, liquid and solid from these pyrolyses

are different from each other.

16
 Comparison
Product (wt%)
Reaction
Liquid Char Gas
Slow pyrolysis
30% (water
Low or intermediate temperature and 35% 35%
70%)
long residence time
Intermediate pyrolysis
50% (water
Intermediate temperature and 25% 25%
50%)
residence time
Fast pyrolysis
75% (water
Intermediate temperature (〜500℃) 12% 13%
25%)
and short residence time (＜2 s)
Gasification 5%
High temperature (＞800℃) and （water 10% 85%
long residence time 5%）
17
 Slow Pyrolysis
Four-stage reaction
100〜120℃: drying stage, moisture is removed from the
top of reactor.
120〜280℃: main gases include N2, CO and CO2, acetic
acid and methanol are distillated and removed from reactor.
280〜350℃: exothermic reactions occur which result in the
liberation of ketone, aldehyde, phenol, ester, CO2, CO, CH4,
C2H6 and H2 from biomass.
＞350℃: all volatiles are removed and hydrogen is
important in the product gas. CO can also be found. Char is
the main component in the residual solid. Ash is also
retained.
18
 Fast Pyrolysis

Fast pyrolysis is a high temperature process in which the

feedstock is rapidly heated in the absence of air, vaporizes
and condenses to a dark brown mobile liquid which has a
heating value of about half that of conventional fuel oil.

The essential features of a fast pyrolysis process are:

very high heating and heat transfer rates that requires a
finely ground biomass feed;
carefully controlled temperature of around 500°C;
rapid cooling of the pyrolysis vapors to give the bio-oil
product.
19
Fast Pyrolysis Process
(Fluidized Bed)

20
Bubbling Fluidized Bed

Bubbling fluid beds

have the advantages of a
well understood
technology that is simple
in construction and
operation, good
temperature control and
very efficient heat
transfer to
biomass particles arising
from the high solids
density.

21
Circulating Fluidized Bed (CFB)

In CFB, the residence time

of char is almost the same as
for vapors and gas, and the
char is more attrited due to
the higher gas velocities.
This can lead to higher char
contents in the collected bio-
oil unless more extensive
char removal is included.
CFBs are potentially suitable
for larger throughputs.

22
 Ablative Pyrolysis Reactor

The underlying principles are the use of high applied pressure

of the biomass particle to be pyrolyzed onto a hot surface at
not more than 600°C while moving it at a high speed
(>1.2 m/s) relative to the hot reactor surface.
Dried biomass particles of up to 6.35 mm are fed into the
nitrogen purged reactor from a sealed purged screw feeder.
Four asymmetric blades rotating at speeds up to 200 rpm
generate a mechanical pressure on the particles, pressing the
particles onto the heated reactor base, typically heated to
600°C. The mechanical action of the blades causes the
particles to pyrolyze (thermally erode) under the conditions
of high relative motion to the heated reactor surface.
23
Ablative Pyrolysis Reactor

The product
vapors and gases
are removed from
the reactor with
the diluting
nitrogen and the
char is removed
in a cyclone.

24
 Ablative Pyrolysis Reactor
Aston University has developed an ablative plate reactor in
which pressure and motion is derived mechanically,
obviating the need for a carrier gas. Liquid yields of
70-75 wt% on dry-feed basis are typically obtained. A second
generation reactor has recently been built and commissioned
and has been patented (Fig. 6).

25
 Rotating Cone Reactor

Initial experiments were carried out

mainly with a cone temperature of
600°C and a cone rotational speed of
900 rpm. The reactor interior was
subsequently modified to reduce the
operational volume from 0.25 m3 to
0.003 m3. The reactor outside the
cone quickly becomes filled with
sand and char, restricting
experimental runs to 10 min. The
liquids are collected in a
condenser/quench system.
26
Rotating Cone Reactor

27
 Vacuum Moving Reactor

The feedstock is conveyed over two horizontal plates

which are heated by a mixture of molten salts that are
maintained at a temperature of 530 °C. The hot salts are
heated by means of a burner which is supplied with the
non-condensable gases produced during the pyrolysis
process. When heated, the organic matter in the feedstock
decomposes into vapors which are rapidly removed from
the reactor by means of a vacuum pump. These vapors are
then directed to two condenser units in which the heavy
and light oils are recovered together with an aqueous phase.
The residual solid products are cooled at the reactor outlet.

28
Vacuum Moving Reactor

29
Properties of Bio-oil

30
 Bio-oil Characteristics

Pyrolysis oil typically is a dark brown liquid.

Depending on the initial feedstock and the mode of fast
pyrolysis, the color can be almost black through dark
redbrown to dark green, being influenced by the
presence of micro-carbon in the liquid and chemical
composition.
Hot vapor filtration gives a more translucent red-brown
appearance owing to the absence of char. High nitrogen
content can impart a dark green tinge to the liquid.

31
 Bio-oil Characteristics

Aging is a well known phenomenon caused by

continued slow secondary reactions in the liquid
which manifests as an increase in viscosity with time.
It can be reduced or controlled by the addition of
alcohols such as ethanol or methanol. In extreme
cases phase separation can occur.
It is exacerbated or accelerated by the presence of
fine char.

32
 Properties of Bio-oils
Water: Water is miscible with the bio-oil up to around
30±45% and bio-oil is not miscible with fossil fuels.
pH: The degradation products from cellulose include organic
acids such as formic and acetic acids which give the bio-oil
its low
Density: the density of pyrolysis liquid is very high at around
1.2 kg/l.
HHV: The heating value of bio-oil is about 17 MJ/kg at 25%
wt water which is about 40% that of fuel oil/diesel in weight.
The viscosity of crude bio-oil can vary over a wide range
from as low as 10 cp at ambient temperature to as high as
10,000 cp or more from oil stored in poor conditions for long
periods. 33
 Bio-oil upgrade

Emulsification

Hydrogenation

Catalyzed cracking

Esterification

34
Upgrading of and
Ref : Renewable pyrolysis oilEnergy
Sustainable from Reviews
biomass40 (2014) 69–79
 Bio-oil Upgrading

Bio-oils can be upgraded in a number of ways physically,

chemically and catalytically.
The most important properties that may adversely affect
bio-oil fuel quality are incompatibility with conventional
fuels from the high oxygen content of the bio-oil, high
solids content, high viscosity, and chemical instability.
Hot-vapor filtration can reduce the ash content of the oil to
less than 0.01% and the alkali content to less than 10 ppm,
much lower than reported for biomass oils produced in
systems using only cyclones. This gives a higher quality
product with lower char.

35
 Bio-oil Upgrading

Polar solvents have been used for many years to homogenize

and reduce the viscosity of biomass oils. The addition of
solvents, especially methanol, showed a significant effect on
the oil stability. The rate of viscosity increase (“aging”) for
the oil with 10 wt.% of methanol was almost twenty times
less than for the oil without additives.
Pyrolysis oils are not miscible with hydrocarbon fuels but
they can be emulsified with diesel oil with the aid of
surfactants. Emulsions of 5-95% bio-oil in diesel to makes
either a transport fuel or a fuel for power generation in
engines that does not require engine modification to dual fuel
operation. A drawback of this approach is the cost of
surfactants and the high energy required for emulsification.
36
 Bio-oil Upgrading

Hydrotreating: hydro-processing rejects oxygen as water by

catalytic reaction with hydrogen. The process is typically
high pressure (up to 20 MPa) and moderate temperature (up
to 400 C) and requires a hydrogen supply or source. The
process can be depicted by

C1H1.33O0.43 + 0.77H 2 → CH 2 + 0.43H 2O

37
 Bio-oil Upgrading

Zeolite cracking: zeolite cracking rejects oxygen as CO2

given below:

C1H1.33 O 0.43 + 0.26O 2 → 0.65CH 1.2 + 0.34CO 2 + 0.27H 2 O

Steam reforming: with the aid of catalysts (Ni, Cr, Pt, Pd, Rh,
Ru), bio-oils can react with steam to produce hydrogen
C1H1.33O0.43 + 1.57H 2O → CO2 + 2.235H 2

38
 Applications of Bio-oil

Bio-oil can substitute for fuel oil or diesel in many static

applications including boilers, furnaces, engines and
turbines.
There are a range of chemicals that can be extracted or
derived including food flavorings, specialities, resins, agri-
chemicals, fertilizers, and emissions control agents.
Upgrading bio-oil to transportation fuels is not economic,
although technically feasible.

39
Applications of Bio-oil

40
End

41