FAST PYROLYSIS

BIO-OIL

09/12/2010
GRUOP 9 BioRefinery Engineering

Jie Fu
Shimme Sharma
Hardik Savani
Oscar Abrica

FAST PYROLYSIS BIO-OIL

FAST PYROLYSIS BIO-OIL
S UMMARRY
The depletion of conventional fuel has encouraged scientists to find out a substitute to
replace it. Biomass like sawdust is a good renewable energy source in order to satisfy
the demand up to some extent. Sawdust has been found to be most efficient when
compared to other biomass that could be used in fast pyrolysis. Tons of sawdust is
collected daily and turned into valuable bio-oil using the process of fast pyrolysis. A
cyclone reactor is used to carry out the process because of its excellent heat transfer
efficiency and a very short residence time. Optimum temperature used in this process
is around 500
o
C to obtain maximum yield of bio-oil.

2


3


Content
Fast Pyrolysis Bio-Oil


Introduction 04
What is Bio-Oil
What is Fast Pyrolysis Process
Physical and Chemical Properties of Bio-Oil
Selecting the Raw Material 06
Typical Raw Material characteristics

Plant Location 06
Geography of our Plant
Transportation and Costing

Fast Pyrol ysis Process 07

Description of the Process
Operating Conditions
Mass Balances
Energy Consumption

Fast Pyrol ysis Plant Cost 11

Equipment Costs
Capital Cost

Bio-Oil Applications 12

Bio-Oil Uses
Advantages
Challenges
Up-Grading Bio-Oil

Results and Conclusion 13

References 14



4


BIO-OIL (PYROLYSIS)

Introduction

At present, the renewable energy production is becoming more important aspect in
order to satisfy the environmental concern over conventional fuels and its contribution
to green house effects. The study data shows that biomass has contributed to the worlds
10-14% of the total energy supply.
Wood, agricultural wastes and other forms of biomass are some of the main
renewable energy sources to produce required energy.
[a]
[2]
Biomass is any biological
matter that can be used to produce energy. Its composition basically includes celluloses,
hemicelluloses, lignin and some minor amounts of other organics which makes it useful
as a renewable energy source. Its conversion to energy takes up two approaches:
biochemical (fermentation and anaerobic digestion) or thermochemical (combustion,
gasification and fast pyrolysis). Pyrolysis has been widely used for its ability to produce
liquid products.

[1,7]
Pyrolysis is a process where biomass is heated at very high temperature (usually
between 400-700
o
C) in the absence of oxygen to produce a solid phase called charcoal
(carbon and ash), non-condensable gases and a condensable vapour called pyrolysis oil
(bio-oil).
[2]
It involves reactions like depolymerisation, hydrolysis, oxidation,
dehydration and decarboxylation.
[6]


Pyrolysis process takes up two approaches: one is slow or conventional pyrolysis
and the other is fast or flash pyrolysis. Fast pyrolysis process is preferred over slow
pyrolysis because of its ability to produce high liquid yield and low solid yield with a
very short residence time. The most important advantage of fast pyrolysis is that the
major product is in liquid form which can be easily stored and transported.

[4]
Reactors used to carry out pyrolysis are divided according to the size of the particles
and their characteristic residence times.


[8]

Table 2: Comparison of different reactors
Types of reactor Particle size Residence time
Fixed bed Large 10
3
to 10
5
s
Vortex (Cyclone) Small 5 x10
-3
to 10 s
Fluidized bed Medium 10
2
to 10
4
s


[8]
Cyclone reactor has excellent heat transfer efficiency and a very short residence
time (lower than a few seconds). In addition, solid by-products and unreacted particles
5


can be automatically separated from gaseous products at the same time. The major
advantage of using this reactor in fast pyrolysis is that it can carry out five essential
reactions of pyrolysis process in the same vessel. These reactions include: (i) Fast
heating of the raw materials; (ii) Chemical decomposition of the components; (iii)
Efficient friction of the particles against the walls which eliminates the products; (iv)
Further reactions of the primary products; (v) Cleaning of the evolved gas
(simultaneous separation of char and ash at the bottom).

Bio-Oil is a dark brownish viscous organic liquid made up of complex oxygenated
compounds that bears some resemblance to fossil fuel. However, the heating value of
bio-oil is lower than that of fossil fuel because of its high oxygen content.

[2]
The molecular composition of bio-oil varies significantly with the type of biomass
and the pyrolysis conditions used. Its major components are water, water soluble
compounds like acids, alcohols, ketones, aldehydes, substituted furans derived from
cellulose and hemicelluloses, and water insoluble compounds like phenolic and cyclic
oxygenates derived from lignin fraction of biomass.

[1]
Bio-oil is an acidic liquid with pH ranging between 2-4 making it highly unstable
and corrosive. Hence, it is usually transported and stored in stainless steel containers.
Specific gravity of bio-oil is about 1.10-1.25, which means it is heavier than water, fuel
oil, and bulk density of biomass. It has a viscosity that ranges from 40 cP to 100 cP
usually depending on the water content and the original feedstock. As bio-oil consists of
large amount of oxygenated compounds, it tends to be polar and therefore does not
readily mix with hydrocarbons. It has a tendency to phase separate when the water
content in it reaches above 30 percent.

[3]
[20]

Table: 1 Properties of Pyrolysis Oil from sawdust
PHYSICAL PROPERTIES TYPICAL VALUE
Moisture content 15%-30%
pH 2.5
Specific gravity 1.1-1.2
Elemental analysis
C
H
O
N
Ash

55%-58%
5%-8%
35%-40%
0.0%-0.2%
0.0%-0.2%
High heat value 6878-11175 Btu/lb
(16-26 MJ/kg)
Char 1%-10%
Viscosity
(104
0
F and 25% water)

40-100cP





6



Raw Material: Why sawdust?

Generally, there are so many kind of biomass can be used as raw material to produce
bio-oil, from high-valued crop seeds to relatively low-valued waste straws, from aquatic
organisms to terrestrial plants. Here we choose sawdust as raw material to produce bio-
oil not only depending on its relatively extensive and continuous sources but also
considering these properties: bio-oil yields, calorific value, moisture and density. There
is a general comparison among some raw materials.

[14]

Table: 3 Different Raw Material Properties
Rice husk Corn stalk Cotton
stalk
Sawdust
Bio-oil yields (wt%) 51.0 56.0 57.0 65.0
Calorific value (MJ/kg) 16.4 16.8 17.2 17.4
Moisture (wt%) 27.2 26.9 26.7 24.0
Density(kg/m
3
) 1120 1140 1155 1180

Compared with other similar biomass (high lignin cellulose content), sawdust has a
relatively high density and low moisture content. But most important thing is that the
bio-oil yield from sawdust is distinctively bigger than other types. It indicates that with
the same raw material and energy input, we can get more bio-oil from using sawdust.

Plant Location:

Our proposed plant is located about 6 kilometres from Nadiad and 13 kilometers
from Anand (Gujarat, INDIA). In addition, a nearby city called Vasad where many
timber industries are situated could also provide around 35-40 tons/day saw dust.
Approximately, around 105-110 tons/day of saw dust can be obtained from the timber
industries situated within 15 kilometers radius of this area. Based on the quantity of saw
dust available, we have proposed our plant at this location.

Transportation facilities and costing:

Among several modes of transport available in INDIA, trucks have been the most
effective mode of transport in industrial sectors. Based on the geographical location of
our proposed plant and the condition of roads available, the most suitable trucks are in
the size of 17 tons capacity. The maximum weight carried out by this truck is around 8
tons of raw materials and the average travelling cost is $ 0.45 per kilometer.

7


Producing Bio-Oil from sawdust using fast pyrolysis:

(d) Computer Software FlowSheet
100 tons of sawdust are gathered everyday as raw material to produce bio-oil
(pyrolysis oil), using the fast pyrolysis technique within a cyclone-reactor continuously.
The efficiency of sawdust converted into bio-oil is approximately 70%, with 15%
syngas and 10% charcoal as by-product.
Given that an anaerobic atmosphere is required during the decomposition period,
sand (SiO2) is heated in a different tank and therefore used as heat transfer medium
(fluidized bed technique), to heat sawdust from ambient temperature to the temperature
required, which is 500 within the cyclone-reactor.
After biomass is decomposed and turns into vapours form, there are some
separations methods involved, to separate bio-oil and syngas. The proccess is optimized
by using the syngas and charcoal as fuel for heating the sand, furthermore, there are
some energy recovery stages within the whole procces.


Pre-treatment of sawdust:
Before undergoing the fast pyrolysis, sawdust is pretreated in a storage tank (volume
225m
3
; height: 2m; diameter: 12m). Pretreatment of raw material includes both
8


reducing the diameter and drying moisture within the sawdust. Theoretically, the
smaller the size and the less humidity sawdust have, the higher efficiency is from
sawdust to bio-oil.
Hence, 45 tons of sawdust is being grinded to less than 5mm diameter and heated to
100 for 10 hours using hot flue gas generated from our process. The humidity of
sawdust will be less than 8 wt% before it is processed. The process is repeated with
45tons sawdust.

Fast Pyrolysis:

At the beginning of the process, sawdust is feed continuously by using a screw
feeder
[4]
to the cyclone-reactor
[10]

with a feed rate of 1.16 kg/s. Meanwhile, a flow of
heated sand (50050) is fed into the cyclone-reactor at 5 times the feed rate (5.8kg/s)
of sawdust.
Particles enter tangentially into the reactor and then are rapidly thrown against the
wall of cyclone-reactor. During this process, the contact of heated sand and sawdust
leads to increase in temperature of sawdust within a pretty short period of time (around
1 to 2 seconds). Then sawdust is transformed into bio-oil vapor, syngas and charcoal.

Within the cyclone-reactors high-speed rotating conditions and the driving force of
N
2 [4]

, solid components (charcoal, sand and unreacted sawdust are automatically
separated from the gaseous products (bio-oil vapor and syngas). Then the gaseous
components flow through the stainless steel pipe to a condenser, where vaporous bio-oil
is condensed using a reflux of cooling bio-oil and cooling water. Whereas, syngas is
recycled to the sand tank for heating the sand.
In addition, charcoal together with N
2

and unreacted sawdust is also recycled back
to the burner tank.
Heat Carrier:

Sand is heated in the burner tank using syngas, charcoal (coming from the cyclone-
reactor), and natural gas as fuel.
It is important to notice that the sand is always in movement, this ensures all the
sand particles within the reactor are heated. After sand is heated, flue gases are directed
to a second cyclone, where ashes are separated from the hot flue gas and collected at the
bottom. The flue gas is then used as a driving force to generate power through gas
turbine.
The flue gases coming out of gas turbine are of relatively high temperature, around
200-150. Therefore, instead of emitting them directly to the atmosphere, we recycle
them to dry the sawdust.
9



Cooling System:

The bio-oil vapor formed, is relatively high in temperature, hence need to be cooled
down to temperature below 50 as soon as possible to prevent it from undergoing
further reactions. Therefore, to gain bio-oil of high quality and quantity, immediate
cooling is a key factor.

Previously, immiscible liquid was used a quenching agent to cool down the bio oil.
According to recent research,
[13]

it is mentioned that previously made and cooled bio-
oil reflux can be used to cool down the bio-oil vapor because it saves both the energy
and the effort to separate bio oil from immiscible liquid. In addition, water is also used
as another cooling agent. As a consequence, energy is saved during the condensation
process and the steam generated from water during heat exchange, is used to generate
power through a steam turbine.
After the condensation process, bio-oil is transported to a storage tank. For the
process, both pipes and tank are made up of stainless steel due to the low pH and
corrosive properties of the bio-oil
[15]
.
The volume of tank which is used to store bio-oil
is 120m
3

(height: 2m; diameter: 9m).
Mass Balance per Day:

Mass input
Sawdust 100 tons
N2 346.587 kg
Air 895.104 kg

Mass output
Bio-oil 70 tons
Flue gas 16.242 tons (Which can be used to drive a gas turbine and then dry sawdust)

Mass consumed within system
Syngas 15 tons
Charcoal 10 tons
Volume of cyclone reactor: V=67m
Height3.5m; Diameter: 5m
3






10



Energy accounting:

Total Q needed to heat sand
C
P
Mass flow rate of sand R=5.8 kg/s
(SiO2)=830 J/kg
Initial temperature Ti=25
Targeting temperature Tt=100
Q
T
=C
P

R (Tt-Ti) =3610.5 kJ/s
Q provided by burning charcoal
Mass flow rate of sawdust Rs=1.16 kg/s
Proportion of charcoal produced from sawdust=10%
Mass flow rate of charcoal Rchar=Rs=0.116 kg/s
Average heating value of charcoal Ca=27.91 MJ/kg
Temperature of charcoal coming from cyclone Ti=300
Targeting temperature of charcoal Tt=550
Q provided by charcoal Qchar=CaRs(Tt-Ti)=3237.56kJ/s

Natural gas needed to burn charcoal
Q provided by burning natural gas to heat sand Qng=Q
T
Specific heating value of Natural gas Cng=54 MJ/kg
-Qchar=372.94 kJ/s
Mass flow rate of Natural gas Rng=QngCng=0.006906kg/s

Cooling water
Initial temperature of bio-oil vapor Ti=300
Targeting temperature of bio-oil Tt=50
Cp(water)=4.2kJ/kg
Cp(bio-oil)=23260kJ/kg
Mass flow rate of bio-oilRoil=1.16kg/s70%=0.812kg/s
Heat need to be removed from bio-oil vapor:
Q=Cp(bio-oil)Roil(Ti-Tt)=4721780 kJ/s
To simplify, assume that all bio-oil vapor is cooled by water
Rwater=Q (Cp(water)(Tt-Ti))~5 m
3

/s (Which can be used to drive a steam
turbine, and then directed to a cooling tower)


11



PYROLYSIS Bio-Oil Plan Cost

EQUIMENT COST (1000 US DLS)
Sawdust Storage Tank
$082.78
Bio-Oil Storage Tank
$108.22
Cyclone-Reactor
$071.74
Screw Feeder (Conveyor-
Solid 5m)
$010.82
Air Compressor
$064.61
Cyclone
$044.83
Centrifugal Pump
$002.86
Condenser
$039.13
Natural Gas Supply
(Annual)
$454.18
Nitrogen Supply (Annual)
$366.13
Water Supply (Annual)
$462.03
Sawdust
$950.95
Transportation (Annual)

$163.80
TOTAL COST $2822.08


12




Applications:

1. Several types of valuable chemicals like, Acetic acid, Propionic acid, Formic
acid, Calcium chloride, etc. can be separated from the bio-oil based on their
water solubility.
2. The whole product can be converted into useful chemical because of its most
abundant functional groups like carbonyl, carboxyl and phenolic group. Hence
we need not to separate the non-reacting part of the bio-oil.
3. It can be used as bio-fertilizer by reacting with urea and ammonia.
4. It can be used as insecticides and fungicides due to the presence of the chemical
compounds like phenolic and terpenoid.
5. It is also used as a wood preservative instead of creosote to protect wood from
fungal infection.
6. It can be used to improve the appearance of uneven skin like stretch marks, skin
burns, dried skin etc.
7. It can be used as a fuel when mixed with diesel with the aid of surfactants.
Since bio-oil cannot mix with hydrocarbon, surfactants can be used to emulsify
it with diesel fuel.

Advantages:

1. Have high flash point and therefore less flammable than diesel oil.
2. Exhaust fumes are less toxic with less carbondioxide and sulphurdioxide.
3. Since, it is derived from organic sources, is biologically degradable and less
damaging.
4. Direct application in various types of energy power station like boilers.

Challenges of Bio-oil

1. Production of bio-oil is still under research and development, hence, its cost is
slightly higher than the fossil fuel.
2. Availability of large amount of raw material per day remains a problem.
3. Bio-oil produced may have inconsistent quality which could affect its marketing.
4. Bio-oil produced is unstable and may require upgrading techniques like
hyrotreatment to make it stable, thus adding to the net cost of production.
5. Engine modification required in order to make bio-oil compatible to
conventional fuel.
6. Since bio-oil is a recent technology, the consumers are still unfamiliar with its
use.
13


7. Environmental health and safety issues need to be considered during its
production, transportation, and use.
8. The heating value of bio oil if half of that of petroleum fuel.

Upgrading of Bio Oil

One of the main disadvantage of using bio oil as a fuel is that it is highly oxygenated
with a low octane number which makes it difficult for transportation and storage.
Hydrodeoxygenation (a process of hydro-treatment) could be used to upgrade the bio oil
by adding hydrogen and eliminating oxygen. It produces a highly valuable hydrocarbon
(like cyclohexane and benzene) composed bio oil which would satisfy the standards of
transportation. The formation of saturated C-C bond and water in the reaction increases
the stability of bio oil by decreasing the acidity, moisture content, viscosity and
increasing the heating value. However, this process might be complicated and
expensive.

[9]


Marketing:
The bio-oil produced from fast pyrolysis could be sold to chemical industries, power
generating industries, fuel industries, cosmetic industries, and pharmaceutical industries.
Given our proposed location, many of these industries are situated within 50 km radius,
mainly in Ahmadabad and Baroda (the two major cities having most pharmaceutical,
petroleum and cosmetic industries).
Ash generated from the process could also be marketed to the fertilizer making
industries.

Result and conclusion:

Due to the high efficiency of fast pyrolysis technique, 70 tons of bio-oil can be
produced from 100tons of sawdust per day and the char and syngas produced are
recycled reducing the power cost. If the process is strictly carried out within the limits
of anaerobic atmosphere in cyclone reactor, high and fast heat to sawdust and rapid
condensing of bio-oil vapor, we might be able to achieve a highly efficient process.
Hence, with a certain upgrading, bio-oil will cherish a brighter future.






14






References

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United States Department of Agriculture FSA1052.
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properties of bio-oil produced at various temperatures from pine wood using an auger
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15


[20]

Bridgewater , AV, S. Czernik, J.Piskorz (2002). The status of biomass fast
pyrolysis. Vol: 2


Web-sources:

[a] http://www1.eere.energy.gov/maps_data/pdfs/eere_databook.pdf

[b] http://software.cstb.fr/ThOp/Applets/combustion/appletEn/CalcCombEn.html [Accessed 07
Dec 2010]

[c] www.btg-btl.com
[d] Computer Software FlowSheet