1

Bio-oil plant design

CHAPTER ONE
1.1 INTRODUCTION
The demand for energy is growing faster due to rapid industrialization & social growth.
Convectional energy source such as coal, oil, & natural gas, have limited reserves that are
expected not to last for an extended period. Consequently, energy management will be difficult
for the coming generation. In addition, environment-related problems associated with
conventional energy sources are continually increasing. Over the last half century, a trend toward
continuous increasing in an average atmospheric temperature has been observed, totally half
degree centigrade (Goyal et al.2005) this trend may lead to natural calamities such as excessive
rainfall & consequent flood, droughts, & local imbalance. With increasing energy demand, the
energy demand, the emerging alternative & renewable energy resources are expected to play an
increasing role in the future energy consumption, at least in order to reduce the environmental
concern.
In contrast to convectional energy source, non-conventional energy source such as wind,
sunlight, water, & biomass have been used since ancient times. Biomass is now being considered
as an important energy resource all over the world & is being meet a Varity of energy needs,
including generating electricity, fueling vehicles, & providing process for industrial facilities.
Among all the renewable source of energy, biomass is unique as it effectively stores solar energy,
liquid & gaseous fuels. Biomass is fourth largest source of energy in the world, according for
about 15% of the worlds primary energy consumption & about 38% of the primary energy
consumption developing countries (Chen, Andries,&Spliethoff 2003)
As we know our country, Ethiopia is not lucky to get the fossil fuel need for the different
industries found in the country by itself. But, it has a good availability of biomass & good
weathering condition for plantation of different types of biomass. One thing that we all agree for
this problem is due to the economic condition, lack of skilled man power & technology are the
main one. So, as a chemical engineer we have to think an alternative ways just to minimize the
fuel problem of our country based on the problems to apply different technologies concerning
biomass application to fuel. Therefore, we tray to perform our project on production of bio-oil

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Bio-oil plant design

which produce from biomass & serves as an alternate source of fuel for different industries as
energy source for their boilers, kilns etc in replace of fossil fuel specially mazute.
1.2 Definition
Bio-oil is an organic liquid fuel produced from the fast pyrolysis of biomass. In addition to
bio-oil, a high quality char and a combustible gas are produced at approximately 70%, 17% and
13% respectively. It is also viscous liquid with has the same elemental composition as biomass.
It has a pungent smoky odor. Bio-Oil contains several hundred different chemicals with a wideranging molecular weight distribution.
Fast pyrolysis of biomass is a process in which biomass material is rapidly heated to high
temperature in the absence of air (specificallyO 2) the decomposition of biomass in to a
combination of - liquid, solid char & non-condensable gas .the liquid fuel from biomass that can
produced from this fast pyrolysis is named as bio-oil. Bio-oil is used as an energy source & a
feedstock for chemical production. Bio-oil as clean fuel for generating power (green power) &
heat
Use for- small stationery diesel engines
-gas turbines
-boilers, kilns
The use of renewable energy sources is becoming increasingly necessary to mitigate
global warming. Recently much research has been focused on identifying suitable biomass
species, which can provide high-energy outputs, to replace conventional fossil fuels. For this
reason our project aim is to produce a bio-oil as an alternate energy source & studying how to
increasing the yield of bio-oil production from fast pyrolysis.
There are a number of technologies that have been developed to convert biomass to other
usable products such as bio-ethanol, bio-methanol, bio-diesel & bio-oil. Unique from all of the
previously mentioned bio-fuels is Bio-Oil. Bio-Oil, is an oxygenated compound containing
carbonyls, carboxyls, and phenolics, and is soluble in water. It is made by the degradation of
biomass in the absence of oxygen by a process called fast pyrolysis. Besides of this the produce
bio oil is clean burning liquid fuel. Bio-oil is CO2 (neutral), &green house gases neutral.

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Bio-oil plant design

Pyrolysis
It is thermal decomposition occurring in the absence of oxygen, leading to the formation
of liquid, gases & a highly reactive carbonaceous char. It is the heating of biomass in an inert
atmosphere & generally starts at 300Oc & continues up to 600oC-700oC
1.3 Objective
General objectives of this project are doing:
1. Plant design of the production process
2. Study of its applicability in manufacturing industries & detailed discussion on its use for
various applications like for boiler, fertilizer, resin, & its upgrading.
3. Study the environmental impact & healthy analysis of the plant with its safety for the
production process.
Specific objective
1. Indicate bio oil is one of our alternate sources of fuel especially for those large industries
they use kilns, boilers in replace of fossil fuel (mazut).

1.4 Methodology of data collection

For this project our data collection system mainly depends on one source, we use in all
place for the necessary datas for our work is:
1. from literatures: we use many references (literatures books) that can help as for success of
our work depends on their truth by comparing with other source we use it.

Chapter two

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Bio-oil plant design

2. Literature survey
2.1 Introduction
2.1.1 Biomass conversion process
Biomass can be converted in to useful forms of energy using various processes. The
choice of conversion process depend on the type & the quantity of the biomass feedstock, the
desired from of energy, that is, end use requirements, environmental standards, economic
conditions, & specific factors like (the country conditions) for the plant to be installed.
The two main processes for the conversion of biomass are
1. Thermochemical process &
2. Biochemical/biological process.
There are some key fundamental differences between thermal and biological conversion:
Biochemical/biological process gives single or specific products such as ethanol or methane,
And also it is slow process it takes hours, days, weeks or years. Thermochemical process gives
multiple and often complex products, and catalysis is often used to improve the product quality
or spectrum, and it takes short process time seconds or minutes. based on the above reasons we
mainly concern on the thermochemical conversion process for finding lest cost alternative
energy source from biomass for the boiler and kiln application for those industries they use
fossil fuel as a source for their boiler.
2.1.1.1 Themochemical conversion process
The themochemical conversion process involves heating of biomass at high
temperature. There are two basic approaches. The first is gasification of biomass & its
conversion to hydrocarbons. The second approach is to liquefy biomass directly by hightemperature pyrolysis, high-pressure liquefaction, ultra-pyrolysis, high-pressure, or supercritical
extraction. Various thermochemical conversion processes & can classify as follow:

Combustion- Combustion is the burning of biomass in air. It converts the chemical

energy stored in the biomass into heat, mechanical power, or electricity using different
process equipment, for example, stoves, furnaces, boilers, steam turbines, turbo generators,
etc. Combustion produces hot gases at temperatures around 800 to 1000C.

Gasification: Gasification is the conversion of the biomass into a combustible gas mixture
by the partial oxidation of the biomass at high temperature, in the range of 800 to 900C.

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Bio-oil plant design

Pyrolysis: Pyrolysis is the heating of biomass in an inert atmosphere. Pyrolysis generally

starts at 300C and continues up to 600700C. The biomass is converted into useful liquid,
gaseous, and solid products.

Liquefaction: is a low temperature, high pressure termochemical process using a catalyst

with the addition of hydrogen and produce a remarkable liquid product. High pressure is
employed to assure good heat transfer, or to maintain a liquid-phase system at high
temperatures. Interest in liquefaction is low because the reactors and fuel feeding systems
are more complex and more expensive than for the pyrolysis and gasification processes
(Demirbas 2001).

Hydrogenation: hydrogenation is mainly employed for the production of methane by hydro

gasification.
Presently, more attention is focused on two kinds of processes, pyrolysis to produce

liquid fuel, and gasification to produce hydrogen, as these are environmentally benign and
produce a better quality product. The former process is discussed here in detail.( Ashok
Pandey:2009)

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Bio-oil plant design

(www.nrel.gov/docs/gen/fy04/36831e )

2.2 History
Fast pyrolysis is a fairly old technology which dates back to the 1950's. It was developed
to liberate a liquid fraction from tar sand or bituminous coal. At that time both the thermal
conversion reactors were developed together with proper liquid collection systems. Fast
pyrolysis was rediscovered in the 1980's as a technique to obtain liquids from biomass while
utilizing the same techniques as were applied for coal liquefaction.
Today's fast pyrolysis technology tested design from the 50s together with modern
materials, control system and energy integration techniques. Especially the latter is important
since biomass is much more hygroscopic compared to the non-polar coal feedstock. This means
that it's essential to integrate the drying operation with the bio-oil production process.
Advantages of a biomass liquefaction process is that is allows the conversion of an
ill defined granular material like biomass into a well defined liquid energy carrier. Since bio-oil
is obtained by a dry distillation process, the liquid is virtually free of ash. It can be stored,
pumped and atomized prior to any combustion process. For example, when wood is liquefied by

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Bio-oil plant design

the fast pyrolysis process, it results in 70 wt% bio-oil, 20 wt% char and 10 wt% fuel gas. Since
the pyrolysis process requires a small heating duty, a part of the fuel gas or char can be
combusted to supply the necessary heating duty.
Types of pyrolysis
The pyrolysis process may be endothermic, or exothermic, depending on the temperature
of reaction system. The process step includes drying the feed, grinding the feed to sufficiently
small particles for rapid reaction, pyrolysis reactor & the separation of the products (bio-oil). The
pyrolysis process is of the following types.
1. Slow pyrolysis
This is the convectional process whereby the heating rate is kept slow (approximately 57oC/min) (Ozbay et al. 2001). This slow heating rate lead to higher char yields than the liquid &
gaseous products. Different kinds of biomass, such as wood samples, safflower seed, sugarcane
Bagasse, sunflower seeds, municipal wastes, etc...are generally subjected to slow pyloysis.
2. Fast pyrolysis
Fast pyrolysis is considered a better process than convectional, slow pyrolysis, in this. The
heating rates are kept high, about 300 to 500oc/min & the liquid product yield is higher.
Fluidized-bed reactor are best suited for this process as they offer high heating rates, repaid
devolatizatione & also are easy to operate. Reactor such as entrained flow reactor, circulating
fluidized-bed, rotating reactors, etc. is used for this purpose.

3. Flash pyrolysis
This is improved version of fast pyrolysis, whereby high reaction temperature is obtained
within a few seconds. The heating rate is very high, about 1000oC/min with reaction times of few
to several seconds. This is carried out at atmospheric pressure. Entrained flow & fluidized- bed
reactors are the best reactors for this purpose. Because there is rapid heating of the biomass, for
better yields this process requires small particle size (-60+140 mesh) compare to other processes.
Flash pyrolysis can be categorized as:

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Bio-oil plant design

Flash hydro-pyrolysis: the pyrolysis carried out in the presence of hydrogen.

Solar flash pyrolysis: solar energy is used for the pyrolysis process. it stored in
conventional devices & is used to increase the temperature of reaction system.
Rapid thermal process: involves very short residence time of 30ms to 1.5s & is carried
out at temperature between 900-950oc.rapid heating eliminate side reaction in the system.
Vacuum flash pyrolysis: incorporates a vacuum in the pyrlysis system. This stop the
secondary decomposition reaction, gives high yield of liquid yield,& reduce gas
production.
Catalytic biomass pyrolysis: it is done improve the quality of the oil (the oil from
pyrolysis process is generally unsuitable for using in transportation.
Due to our concern of producing bio oil with higher yield & better economics (producing
with short time & lower heat supply) we choose fast pyrolysis for the production process.

Fast Pyrolysis
Rapid thermal decomposition of organic compounds in the absence of oxygen to
produce liquids, char, and gas, The quantity & the quality of the product depend on the various
parameters, such as reaction temperature, pressure, heating rate, reaction time, etc. char, organic
liquid, gases, & water are formed in varying amount, depend on particularly on the biomass
composition, heating rate, pyrolysis temperature & residence time in the pyrolysis reactor. Lower
process temperature & longer vapor residence time favor the production of charcoal; whereas
high temperature & long vapor residence time increase the gas yield. Moderate temperature &
short vapor residence time are optimum for higher yields.
The basic phenomena that take place during pyrolysis are as follow:
1. Heat transfer from a heat source, leading to an increase in the temperature inside the fuel.
2. Initiation of the pyrolysis reaction due to increased temperature, leading to release of the
volatiles & the formation of char.
3. Outflow of the volatiles, resulting in heat transfer between the hot volatiles & cooler
unpyrolysed fuel.
4. Condensation of some of the volatiles in the cooler parts of the fuel to product tar.

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Bio-oil plant design

General conditions for fast pyrolysis

Dry feedstock: <10%

Small particles: <3 mm
Short residence times: 0.5 -2 s
Moderate temperatures (400-500oC)
Rapid quenching at the end of the process
Typical yields Oil: 60 -70%
Char: 12 -15%
Gas: 13 -25%

Advantages
Generally a simple, low-cost technology capable of processing a wide variety of
feedstocks producing gases, a bio-oil, bio-chemicals, and charcoal. A promising approach is the
production of a bio-oil that can be used to power ethanol, bio-diesel or other local industries
facilities, and a charcoal. The charcoal is incorporated into the soil to promote its fertility and
organic matter through synergistic processes between the soil, soil organisms, the roots fo the
plants, water and the CO2 and nitrogen in the atmosphere. Generally it has the following
advantages:

Reduction of emissions CO2, SO2 :

Emissions of chlorite and sulfur

Immediate application in heating installations.

Competitive price comparing with natural gas and diesel

Easy to store and to transport

Combined use of Bio Oil and mineral oil

Operates at atmospheric pressure and modest temperatures (450 C)

Yields of bio-oil can exceed 70 wt-%

Disadvantages
High oxygen and water content of pyrolysis liquids makes them inferior to conventional
hydrocarbon fuels
Phase-separation and polymerization of the liquids and corrosion of containers make storage of
these liquids difficult

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Bio-oil plant design

Users are unfamiliar with this material

Cost of bio-oil, which is 10% to 100% more than fossil fuel
2.3. Pyrolysis

Oil Applications

Bio-oil can be used as a substitute for fossil fuels to generate heat, power and / or
chemicals. Short-term applications are boilers and furnaces (including power stations), whereas
turbines and diesel engines may become available on the somewhat longer term. Upgrading of
the bio-oil to a transportation fuel is technically feasible, but needs further development.
Transportation fuels such as methanol can be derived from the bio-oil through synthesis gas
processes. Furthermore, there is a wide range of chemicals that can be extracted or derived from
the bio-oil. A general overview is depicted below

Bio-oil
Heat
chemical
-Boiler
-Furnace
(Kilns)

power
-Diesel engine

fuel
-Fuel via syn- gas

-Micro Turbine

-Fertilizer

-Resins
-Sugar
-Flavor
-Adhesives
-Feedstock for
chemical
industry

(Source:www.btgworld.com/index_nl.php)

The key advantage of liquids from biomass is that its production can be de-coupled from
any application. Pyrolysis oil can be a fuel as such or a feedstock for further processing. Efforts
on the processing of pyrolysis liquids are summarized in Table below. Detail application of bio
oil & its upgrading system discussed in the next chapter.

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Bio-oil plant design

HEAT
Combustible but not flammable Once ignited, it burns with a stable self-sustaining flame.
Higher particulates and CO, lower NOx

Application

Purpose

Gasification and
further processing

- Investigation of ash deposits

- Steady state combustion
- Burner design and optimization
- diesel engine for stationary operation
- Producing clean fuel gas

Combustion
Engine Turbine
Chemical Upgrading
Physical Upgrading
Chemicals

- Producing clean syn-gas at high

pressure for further syn-gas processing
(methanol)
- Producing hydrotreated oil (HDO)
- Hydrothermal processing of oils
- Extraction / separation / isolation of
chemicals

Table-1- application of bio-oil (Source:www.btgworld.com/index_nl.php)

2.4 Pyrolysis oil properties

Property of bio oil
The properties of bio-oil can encompass a broad range of parameters because of the
complex nature of this material. Even if one is able to perfectly reproduce all of the processing
conditions necessary to produce bio-oil, the biomass feed, itself, can influence the nature of the
final product. Not only are there differences between types of biomass species but also where a
particular species is grown can affect things such as the composition of mineral matter present.
Given this non-uniformity in the starting material and the high temperature reactive environment
to which the prompt biomass vapor fragments are exposed during pyrolysis, it is not unusual to
see variations in many of the physio-chemical properties of bio-oil. For some applications, the
small variations will be of little consequence, but in situations where it is desirable to use bio-oil
in devices that have been designed to operate on hydrocarbon fuels, some of these properties will

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Bio-oil plant design

make operation difficult or simply not feasible. Various types of compound are found to be
present in bio-oil, According to the National Renewable Energy Laboratory, approximately 400
types of organic compounds can be present in bio-oil.
Bio-Oil Chemical Composition
Bio-Oil is a mixture of oxygenated compounds, it contains various chemical functional
groups such as carbonyls, carboxyls, and phenolics. Bio-Oil is made up of the following
constituents: 20-25% water, 25-30% water insoluble pyrolytic lignin, 5-12% organic acids, 510% non-polar hydrocarbons, 5-10% anhydrosugars and 10-25% of other oxygenated
compounds (DynaMotive, ). The compositions of Bio-Oil from three feedstocks are listed in
Table

Table: DynaMotive Bio-Oil Properties (10DynaMotive, 3)

The first, bagasse, is the outer stalk that remains after the juice has been obtained from
sugar cane. The next feedstock, Pine/Spruce 53% wood and 47% bark refers to a mixture
containing only the two types of tree, with 53% coming from wood and 47% coming from bark.
Finally, Pine/Spruce 100% all the wood comes from Pine and Spruce, and that no bark is
included.
Bio-Oil Physical Characteristics

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Bio-oil plant design

Like chemical composition, the physical properties of Bio-Oil also vary depending on the
feedstock. It is an acidic, viscous, water-soluble liquid. Table lists the properties of Bio-Oil
produced of the three different feedstocks.
Table: DynaMotive Bio-Oil Properties (10DynaMotive, 3)

Some of the characteristics listed in the above Table, such as the water content, solids
content, and viscosity create issues when using the Bio-Oil as a fuel. Although the water content
(hydrophilic) lowers NOx, and improves Bio-Oils flow characteristics, it also means that BioOil is immiscible in petroleum fuels (hydrophobic), and lowers the heating value of the fuel. The
solids entrained in the Bio-Oil principally contain fine char particles that are not removed by the
cyclones. Solids content in the Bio-Oil must be less than 0.1% or there is a possibility of injector
blockage or turbine erosion (Osamaa). The density of the liquid is about 1200 kg/m3, which is
higher than of fuel oil, and significantly higher than of the original biomass. The viscosity of the
oil varies from as low as 25 cP up to 1000 cP depending on the water content, and the original
feedstock. The viscosity of Bio-Oil may become problematic as the Bio-Oil is stored over time,
as unfavorable reactions take place that make the liquid too viscous to be a viable fuel.

Water has both ve and + ve effects on properties,

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Bio-oil plant design

Lowers heating value and flame temperature,

Increase ignition delay and decreases combustion rate compared to diesel fuels,
Reduces viscosity helps pumping and atomization,
Gives a more uniform temperature profile in the cylinder of a diesel engine and lowers
NOx emissions
Oxygen content

Oxygen content of bio-oils is usually 45-50 wt.% (wet)

Oxygen is in most compounds identified (>300). The most abundant is water. The other
major groups are hydroxyaldehydes, hydroxyketones, sugars, carboxylic acids, phenolics.

Increase in temperature cracks vapors, reduces organic yield, leaves organics with less
oxygen.

Oxygen is the main reason for differences between hydrocarbon fuels and bio-oil,

Oxygen gives a low heating value and immiscibility with hydrocarbon fuels.

The oxygenates cause ageing or instability

Due to large amounts of oxygenated components present, the oil has a polar nature and does
not mix readily with hydrocarbons. The degradation products from the biomass constituents
include organic acids (like formic and acetic acid), giving the oil its low pH of about 2 to almost
4. Water is an integral part of the single-phase chemical solution. The (hydrophilic) bio-oils have
water contents of typically 15 - 35 wt.%. Typically, phase separation does occur if the water
content is higher then about 30 to 45 %. The heating values: the higher heating value (HHV) is
below 19 MJ/kg compared to 42 - 44 MJ/kg for conventional fuel oils. The low heating value
(LHV) of bio-oils is in the range of 14 to 18 MJ/kg, similar to that for biomass, and is only 40 to
45% of that for hydrocarbon fuels.( Ashok Pandey:2009)
On a volumetric basis Bio-Oil has 55% of the energy content of diesel oil and 40% on a
weight basis. The solids entrained in the Bio-Oil principally contain fine char particles that are
not removed by the cyclones. As can be seen, the solids in the Bio-Oil have been reduced to
levels of approximately 0.1% by weight.

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Bio-oil plant design

Table-3-Typical Properties of Bio-oil Compared to Diesel Fuel

PARAMATER
Calorific value MJ/Kg
Kinematics viscosity cst
Acidity PH
Water wt%
Solid wt%
Ash wt%
Alkali (Na + k )
Summary

BIO-OIL
15-20
3- 9 @ 80oC
2.3-3.3
2.-25
<0.1
<0.02
5-100

Diesel
42.0
2- 4 @20oC
5
0.05%
(combined)
0.01
<1

Bio-oil has a major advantage of being storable and transportable with potential as an
energy carrier,
Bio-oil has been successfully used as boiler fuel,
Bio-oil is commercially used in a gas turbine,
Bio-oil shows promise in diesel engines,
Bio-oil shows promise for some chemicals,
Use of bio-oil as an energy carrier for large scale synthesis of transport fuels etc. is very
interesting,

2.5 Significance to Ethiopian economies

Bio oil has a lot of advantage for our country, if the plant is built here, since it
replace the fossil fuel that we bought from abroad therefore, it can save foreign currency,
besides of this:

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Bio-oil plant design

Economically it is small plant to plant, based on our country economic level, to use
this alternate energy source.
Most of our company can easily cover their fuel need with a minimum cost, for their
boiler, kiln.from low cost, & easily available biomass.
Our county also can use this bio oil for the fertilizer, resin & many other chemicals
by upgrading this oil.
Besides this oil use for gas turbines, & diesel engines of varies application, it can
also use as a source for electric city & via upgrading can use as fuel.
Using this also has a positive effect to our environment, since we produce from
renewable source, & the product oil; also has less effect to the environment.

Chapter-3
3. process selection
3.1 raw material selection

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Bio-oil plant design

The term biomass generally refers to any living matter available on the earth. However, in
the present context only plant materials would be considered as bio-mass. Plants produce
carbohydrates through the process of photosynthesis using CO2, water, mineral, sunlight, &
chlorophyll. Carbohydrates, which make up bulk of tissues, trap the solar energy in their
chemical bonds. It is these energy rich bonds, when broken via different process that produce
energy (Goyal et.al.2006).
Biomass recourses that can be used for energy production cover a wide range of a
material, which include wood &wood waste, agricultural crops & their west by- products, waste
from food processing, municipal waste, aquatic plant & algae, etc. plant based biomass can be
divided in to three major categories,

Residues from agricultural production

Forest production

Energy crops
Energy crops include short rotation woody crops, herbaceous woody crops, grasses,

starch crops, sugar crops, oilseed crops, etc. the choice of biomass for the production of energy
& the types of process to be used for its conversion depends on the chemical & physical
properties of the large molecules from which it is made. The major components present in any
biomass are:

Cellulose

hemicelluloses

lignin
In most kinds of biomass, cellulose is generally the largest fraction, about 40 to 50% by

weight, followed by hemicelluloses about 20 to 40%. Besides these, biomass also has other
components (Brig water, 1999). Due to its renewable & environmentally friendly nature, the use
of biomass for production of energy results in a net reduction in green house gas emission.
Further more, biomass-derived fuels have negligible sulfur content &, therefore, do not
contribute to the emission of sulfur dioxide, which cause acid rain. The combustion of biomass
produces less ash than coal combustion. Moreover, the ash produced can be used as soil additive
on farms.

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Bio-oil plant design

There is a lot of biomass feedstock for the production of bio-oil. Currently most bio-oil
plants use bagasse, wood, & many different types of woods (mixed type). The following Table
lists show the composition of bio oil from three different feedstocks. The first, bagasse, is the
outer stalk that remains after the juice has been obtained from sugarcane. The next feedstock, the
pine/spruce 53% wood & 47 % bark. The last one is pine/spruce it is 100% wood.

Table 4- Bio-Oil Properties from different feedstock (DynaMotive,)

For this project for the production of bio oil we select bagasse as a raw material for the
production process. By considering a lot of advantages of it comparing to others, one thing that
we have to know is the bio oil produced from bagasse has the lowest fuel heating value compare
to the bio oil produced from other biomass. But when we compare the significant chemical &
physical property of bio oil it is more adventitious than the others. The most significant
properties for us to select it are:
It is easily available for our country, from sugar factory.
the bagasse it has contain small amount of water content compare to others, this also
give a great advantage for the plant in minimizing the (cost & energy) that we use in
drying the biomass.

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Bio-oil plant design

Like the physical property of biomass, the chemical property of the bio-oil also plays a
great role in comparison.
-

It has low viscosity

It has low water content

It has a slit greater PH value. All of these properties are near to the standard
desire property of bio-oil. Therefore by considering the above reasons we select
it.

3.2 Pyrolysis reactor selection

The heart of fast pyrolysis process is the reactor. Although it probably represents at most
only about 10-15% of the total capital cost of an integrated system, almost all research and
development has focused on the reactor. The rest of the process consists of biomass reception,
storage and handling, biomass drying and grinding, product collection, storage and, when
relevant, upgrading.
The critical issue is to bring the reacting biomass particle to the optimum process
temperature and minimize its exposure to the intermediate [lower] temperatures that favor
formation of charcoal. One way this objective can be achieved is by using small particles,
another possibility is to transfer heat very fast only to the particle surface that contacts the heat
source. This heat transfer process directly concerns the reactor & it has a significant effect on the
energy utilization on the process.
The process of pyrolysis is endothermic, requiring a substantial heat input to raise the
biomass to reaction temperature, although the heat of reaction is insignificant. Heat transfer in
commercial reactors is a significant design feature. Summarizes the main methods of providing
the necessary heat

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Bio-oil plant design

Fig-1-methods of heat transferring to pyrolysis reactor

We have several Kinds of Fast Pyrolysis Reactor option for the production of bio-oil. The basic
ones are the following including the basic property:

Bubbling fluidized bed

Circular fluidized bed reactor
Rotated con pyloyzer
Ablative pyloyzer
Vacuum pyrolysis
Auger reactor

Bubbling fluid beds

Bubbling fluidized bed reactors have been used in petroleum and chemical processing for over fifty
years and therefore have a long operating history. As reactor designs, they are characterized as
providing high heat transfer rates in conjunction with uniform bed temperatures, both being
necessary attributes for fast pyrolysis. By selecting the appropriate size for the bed fluidizing media,
the gas flow rate can be established such that gas/vapor residence time in the freeboard section above
the bed can be set to a desired value, generally between 0.5-2.0 seconds. Experience has shown that
an operating temperature of 500 -550C in the bed will usually result in the highest liquid yields at
about 0.5 sec residence time, however larger systems can operate at a somewhat lower temperature
and a longer residence time. The temperatures may also vary depending on the type of biomass being
processed.

simple construction and operation

good temperature control
very efficient heat transfer to biomass particles due to high solids density

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Bio-oil plant design
easy scaling
well understood technology
good and consistent performance with high liquid yields: of typically 70-75%wt. from

wood on a dry feed basis

heating can be achieved in a variety of ways. Residence time of solids and vapors is

controlled by the fluidizing gas flow rate and is higher for char than for vapors.
char acts as an effective vapor cracking catalyst at fast pyrolysis reaction temperatures

so rapid and effective char separation/elutriation is important

small biomass particle sizes are needed to achieve high biomass heating rates of less

than 2-3 mm
good char separation is important - usually achieved by ejection and entrainment

followed by separation in one or more cyclones

heat transfer to bed at large scale has to be considered carefully due to scale-up
limitations.
Circulating fluid beds (CFB)
In CFB the first reactor operates in pyrolysis mode while the second one is used
to burn char in the presence of the sand and then transfer the hot sand to the
pyrolysis vessel. Such an option has advantages but also is more challenging
because of solids transport and temperature control (overheating of sand in the
combustor) in the system. Sand flow rate is also 10-20 times greater than the
biomass feed rate and there is a high energy cost in moving this sand around
the loop.

good temperature control can be achieved in reactor,

residence time for the char is almost the same as for vapors and gas,
CFBs are suitable for very large throughputs,
well understood technology,
hydrodynamics more complex,
char is more attrited due to higher gas velocities; char separation is by cyclone,
closely integrated char combustion in a second reactor requires careful control,

22
Bio-oil plant design

heat transfer at large scale has to be proven.

Fig-2- bubbling fluidized bed reactor & circular fluidized bed reactor
Rotating cone
centrifugation drives hot sand and biomass up a rotating heated cone,
vapors are collected and processed conventionally,
Char and sand drop into a fluid bed surrounding the cone from where they are lifted to a

separate fluid bed combustor where char is burned to heat the sand which is then
dropped back into the rotating cone,
char is burned in a secondary bubbling fluid bed combustor. The hot sand is re-

circulated to the pyrolyser

carrier gas requirements in the pyrolysis reactor are much less than for fluid bed and

transported bed systems, however, gas is needed for char burn off and for sand transport,
complex integrated operation of three subsystems is required: rotating cone pyrolyser,

riser for sand recycling, and bubbling bed char combustor,

liquid yields of 60-70% on dry feed are typically obtained.
Ablative pyrolysis
high pressure of particle on hot reactor wall, achieved due to centrifugal force or

mechanically
high relative motion between particle and reactor wall,

23
Bio-oil plant design
reactor wall temperature should be less than 600C.
large feed sizes can be used,
inert gas is not required, so the processing equipment is smaller, [in case of

mechanically applied pressure]

the reaction system is more intensive,
reaction rates are limited by heat transfer to the reactor, not to the biomass,
the process is surface area controlled so scaling is more costly,

the process is mechanically driven so the reactor is more complex.

Vacuum pyrolysis
not a true fast pyrolysis process as solids residence time is very high,
it can process larger particles than most fast pyrolysis reactors
there is less char in the liquid product due to lower gas velocities
there is no requirement for a carrier gas
liquid yields of 35-50% on dry feed are typically obtained with higher char yields than

fast pyrolysis systems; conversely, the liquid yields are higher than in slow pyrolysis
technologies because of fast removal of vapors from the reaction zone
the process is relatively complicated mechanically.
From all of the above by considering the important property we select circulating
fluidized bed reactor (CFB) for our plant. the figure below also indicate both the
technological strength & market attractiveness of the basic reactors, as we observed circular
fluidized bed reactor has show a good strength & attractiveness compare to the others.
Besides of this we observe the following advantages over the others.
CFBs it can take in relatively big biomass particle compare to others with achieving
good biomass heating rate; this also can minimize the cost & energy that we afford
for the grinding of the biomass.
It is also a good technology & more efficient than others for the proper usage of char
for the process energy usage.

24
Bio-oil plant design

Fig-3- pyrolysis reactor comparison by market & technology strength (http://www.pyne.co.uk)

3.3 Auxiliary equipment selection
For the production of bio-oil using fast pyrolysis besides of the above common equipments,
we mostly call the auxiliary equipments like the drier, grinding machine, hopper, storage tank,
etc
For the bagesse to dray the moisture content to the desired value we select rotary drier it is
mostly applicable by many company for bagasse drying & for the size reduction we use hammer
mill with the specific performance that give what we desire in size for based on the reactor
performance.

3.4 Process description

Although the fast pyrolysis process is more accurately called thermolysis, the two
terms are used interchangeably. Since pyro means fire in Greek and thermo means heat,
thermolysis more closely describes the process, which involves heating biomass through indirect
heat. The term fast refers to the residence time of the biomass in the reactor. Slow pyrolysis
produces more solid char, while fast pyrolysis yields more gas and liquid. The reactor design,

25
Bio-oil plant design

temperature, and residence time determine the yields of the products and to some extent, their
qualities.
In the fast pyrolysis process, indirect heat, followed by cooling, is used to convert biomass
at 400-800C into CO2, CO, and CH4 gases (medium heating value gases), Bio- Oil liquids and
solid char. A flow diagram of the process is shown in Figure below. The conversion of biomass to
Bio-Oil occurs in the absence of oxygen in the pyrolysis reactor shown in the diagram. Oxygen
is excluded to prevent the biomass or its products from combusting.( for our process we use a N2
gas as a fluidizing medium) Gasification is different from fast pyrolysis, or thermolysis, because
it is a combustion process in which enough oxygen, through air, is supplied for the carbon and
hydrogen in the fuel to form a rich mixture of CO and hydrogen in the product gas. The product
gas from gasification will contain up to 60% nitrogen and have a lower heating value of 107 to
484 Btu/ft3 whereas the heating value of fast pyrolysis gases range from 484 to 807 Btu/ft3
(www.wgtuk.com/ukDefinitionGas.html).
The products exit the pyrolysis reactor in a gas state that includes vapors, aerosols, and a
suspension of small solid particles. A cyclone separates most of the solid particles from the
vapors, where they are then deposited to the char collector. The gases are then condensed in a
quench system, which converts most of the vapor into liquid Bio-Oil.The non-condensable
gases are recycled to supply the energy needed in the process, while the Bio-Oil and char can be
sold as commercial products (DynaMotive.com/biooil).

General Process requirements

Feedstock preparation
Fast pyrolysis
Char separation
Quenching system

Feedstock Preparation

26
Bio-oil plant design

The feedstock (bagasse) most of the time before feed to the reactor it need some
preparation.
The first one is drying, to reduce the feed stock bagasse moister content to less than 10%
moisture content ,in order to minimize the water content in the bio-oil. because water reduces
heating value, reduces viscosity, may cause phase separation. mostly the bagasse contain
40-45% moisture but for the pyrelysis process its better to drop the water content,
Using rotary dryer to less the 10% moisture content by using the hot air as dying
medium that is recovered from the condenser .

Second one is grinding. Grinding: Biomass has low thermal conductivity, so very high
heating rates require very small particle sizes to heat them very quickly,
the feedstock should reduced to small particles to ensures rapid heat transfer rate in the reactor
The bagasse feed stack mostly its better to minimize the particle size 0.5mm -5mm
we, using hammer milling to reduce the size of bagasse to 2mm average particle
diameter.

Dried and ground feedstock is stored in a hopper near the pyrolysis reactor. It is moved
using a variable screw-feeder to a constant speed screw-feeder that transfers it rapidly to the
thermolysis reactor.These three steps take place before the feed enters the pyrolysis reactor.

Pyrolysis Reactor
A circulating fluidized bed pyrolysis reactor is used to convert the prepared biomass into
three components: small particles of solid char (aerosols), bio-oil, and non-condensable gases.
Silica sand is used as the inert material inside the reactor, which can withstand temperatures up
to 1500C and aids in heat transfer (Piskorz, Dec. 29, 1998.) Since the other two conversion
products other than bio-oil are not our primary desire product therefore the operation
temperature of this circular fluidized bed reactor can make and operate condition temperature we
take it 480 -5000c. (detail description see selection chapter 4) since the pyrolysis process in a
CFBR take place with in a very sort shirt seconds, in the absence of oxygen (in order to prevent
formation of combustion ) so we use, permanently recovery (recycle) non-condensable gas if the
recovery non-condesensable gas is not sufficient we can use N2 (gas) as an alternative rather than

27
Bio-oil plant design

using air like gasifier in order to fluidize the bagasse particle. The temperature range of
pyrolysis reactor is usually set for 450 to 500C. Operating below 400C in the reactor will
quickly result in the Bio-Oil clogging pipes due to its nature of depositing on surfaces Transfer
lines are also maintained above 380C to prevent clogging caused by condensation.
The process of pyrolysis is endothermic, requiring a substantial heat input to raise the
biomass to reaction temperature, although the heat of reaction is insignificant
(www.icheme.org/literature/conferences/gasi/Gasification%-Bridgewater.pdf . )The fluidized gas
in to the CFBR is better if it inter at Temperature of 5000c to facilitate and maintain the reactor
heat at the operating temperate, the inert sand that are found in the reactor and circulate between
the reactor, cyclone and combustor, besides of this the sand bed can give a heat to the reactor just
as when out from combustor and into the circular fluidizing bed reactor since after a few second
the conversion take a place and the product gas fluidizing gas and sand out at the top of the
reactor. The operation in the pyrolysis reactor cant able to control with its reaction kinetics
since. Its operation process for conversion is in a very short time. So we can only control by its
temperature (heat).
The hot mix of solids, liquids and gases are sent to a bank of high efficiency cyclones where
the solids (e.g., ash and char) are separated from the gases and bio crude liquids.

Char separation
A cyclone is a cone like apparatus that uses centrifugal force to keep heavier particles
against the wall .Char is one of the co-products produced during the conversion of
biomass to bio- oil and act as a vapor cracking catalyst so rapid and effective removal is

essential. Cyclones are usual method of char removal. Fins pass through and collect in liquid
product. The removed char is collected and send to the combustor to heat the sand by its
combustion and the flue gas from the combustor is send to cyclone to clean it from ash and then
used for steam generation to produce electrical energy by using steam turbines.

Quenching system
When the cleaned gases exit the cyclone unit, they must be cooled to form the Bio-Oil and
non-condensable, recyclable product gases. This prevents further reactions from taking place.
The most detrimental reaction for Bio-Oil as a fuel is secondary cracking, which decreases the
liquid fuels yield. The pyrolysis reaction is rapidly quenched and the bio-crude vapors are
condensed in a series of two condensers. The first condenser is used to generate 515-psig steam

28
Bio-oil plant design
which is then sent to the steam drum .No bio-crude is condensed from this stage. In the second

condenser air is used as the cooling medium. The heated (200C) air is recycled back to the feedstock
dryer. Any remaining aerosols in the vapor stream are removed in a scrubber and wet ESP. The
recovered liquids are sent to Product Recovery. The cleaned vapors are sent to recycle, for recycle as
the fluidizing medium. For quenching purpose in the scrubber we use a cold Bio-Oil to cool the

condensable gas in to bio-oil liquid state. The quenching process uses direct contact heat transfer,
spraying Bio-Oil that was cooled in a heat exchanger onto the gases in scrubber to condense BioOil.
Electrostatic Precipitator
After the quenching process, the non-condensable gases and any Bio-Oil particles Left
over are sent through an electrostatic precipitator (ESP). The ESP uses electric charges to first
charge unwanted aerosol particles and then trap them using an oppositely charged plate. The
cleaner, non-condensable gas is then recycled back to the fluidized bed pyrolysis reactor and
combustor.

Composition of pyrolysis gas & char

The combustible gas from the pyrolysis process contains mostly CO, CO2, C2H2,

and C2H4 & CH4. Other components present are H2, propane, propylene, butane, C5, ethane,
etc the non-condensable gas can be used for obtaining energy (process energy) by combustion.
The char obtained contains around 85% elemental carbon & 3% hydrogen (handbook of plantbased biofuels By Ashok Pandey). The typical analysis of charcoal is given below in the table.
Charcoal (char) proximate & elemental analysis (wt %)

Proximate analysis
Laboratory scale

Pilot plant scale

Volatile matter

18.9

15.4

Fixed carbon

74.4

79.1

Ash

6.7

5.5

Elemental analysis

29
Bio-oil plant design

85.6

81.5

2.9

3.1

1.3

0.8

<0.1

<0.1

O +ASH (by difference)

10.2

14.6

(SOURCE handbook of plant-based biofuels By Ashok Pandey)

Table -5- char proximate & elemental analysis.
Use of char
The char obtained from the pyrolysis of biomass has several uses. As the yield of char
is between 20 & 26wt%, this solid fuel can be used in boiler where bagasse or other biomass is
presently burnt. This can also be converted in to brickets, or mixed with the biomass & can be
used as high efficiency fuel in boilers. It can be used as feedstock for the production of activated
carbon & for the gasification process to obtain hydrogen-rich gas. The char for our process is
collected and combusted to contribute heat to the process.

Technical challenges for bio-oil production

Bio oil production Requires fast heat transfer In this process the combustor is used to
burn char in the presence of the sand and then transfer the hot sand to the pyrolysis vessel. Such
an option has advantages but also is more challenging because of solids transport and temperature
control (overheating of sand in the combustor) in the system. And there is a high energy cost in
moving this sand around the loop. The movement of sand and particles through the system causes
abrasion of this char layer but mostly at the elbows and bends where there is more forceful
interaction between the particles and sand. Feed particles sized for a circulating bed system must
be smaller. In this type reactor the particle will only have 0.5-1.0 seconds (s) residence time in the
high heat transfer pyrolysis zone before it is entrained over to the char combustion section. For
relatively large particles this would not be enough time to transport heat to the interior of the
particle. This is especially true as a char layer develops on the outside surface, which acts as an
insulating layer preventing further penetration of heat. The incompletely pyrolyzed larger
particles will end up in the char combustor where they will simply be burned. Consequently, if

30
Bio-oil plant design
larger feed particles are used, the oil yield will be reduced due to combustion of incompletely

pyrolyzed particles. Particles in the 1-2 mm are the desired size range, to reduce the size of
particles it needs high amount of energy. Also the process requires low moisture content

feedstock (10%).

31
Bio-oil plant design

3.5 Bio-oil production using fast pyrolysis

BAGA
SSEE

(Air &
steam)

Bagasse
Hopper

Hot flue gas

steam drum

steam to

Exhaust

ESP

Dryer
Conden
ser

Cyclon
e

(Millin
g)
Hoppe
r

Conden
ser
2

Ash
Cyclo
ne

Pyroly
sis
Reacto
r

Scrub
ber
Char &
sand

Combus
tor

Char &
ash
Receive

H2O

Hot sand

PRODU
CT
BIOOIL
STORA
GE

AIR
N2

buffer

32
Bio-oil plant design

Chapter 4

4.Application of bio-oil
Introduction
Bio-oil has the potential for multiple applications. These can range from a variety of
combined heat and power options to the extraction of selected chemicals. Use as a substitute for
hydrocarbon fuels in conventional prime movers to produce electricity or generate steam has
been demonstrated but has not been commercially adopted. This is primarily due to lower cost
for petroleum-based fuels compared to bio-oils. However, in some applications with more
sophisticated prime movers such as internal combustion engines and turbines, quality issues with
the oil must still be addressed. Upgrading of bio-oils to higher value transportation fuels requires
de-oxygenation and reforming of most of the compounds present in the bio-oil. Because of the
large amount of oxygen present there will be a loss in mass (or volume) yield but this will be
balanced against higher heating values. In the previous section we tried to describe shortly the
application of bio-oil for the following general purposes:

Heat: for Boilers &Furnace (Kilns)

Power: for Diesel engine& Micro Turbine

Fuel: for Fuel via syn- gas

Chemical production: like for Fertilizer, Resins, Sugar, Flavor, Adhesives, & Feedstock
for chemical industry.

In this chapter we are trying to explain for some basic application of bio-oil, & in related to
the application in Ethiopia, besides of this we are also trying to indicate the significant effect on
Ethiopian industries using some chemicals that drive from bio-oil.

Gasification of bio-oil for synthesis gas production

Synthesis gas or syngas is a gas mixture containing hydrogen and carbon monoxide.
Syngas is mainly produced by gasification of natural gas, coal and occasionally from heavy oil
residues. The produced syngas, after cleaning and conditioning, can be easily used for synthesis
of fuels (alcohols such as methanol, or diesel through Fischer-Tropsch)

33
Bio-oil plant design

Nowadays the syngas is produced from fossil fuels, mainly coal and natural gas, but also
from heavy oil residues and naphtha. With the current developments towards sustainable
production of fuels and chemicals, biomass can play an important role as feedstock for the
production of synthesis gas. Currently syngas can produce from bio-oil in through different
methods. Currently the common method for syngas production is described below:
The two-stage gasification process
The two-stage gasification process consists of the following two steps

Gas

Biomas
s
Inert
gas

Fastpyrolysis

Biooil

Gasificati
on

Syng
as

Chemical
process

Produc
t

Char
Steam/O2

In the first stage biomass is pyrolysed to yield a maximum amount of bio-oil at atmospheric
pressure and temperatures of approximately 500oC. The by-products in this stage are gas and
char. The bio-oil is then pumped to the high-pressure gasification unit where it is thermally
gasified with steam (and optionally oxygen) to yield syngas. This route has many advantages
compared to conventional gasification routes for high-pressure down-stream processes.

Bio-Oil Gasification
Similar to the above, we can produse green diesel using gasification. since, Bio-oil can
be used as a fuel for gasification. When the gasifiers can be fed on bio-oil, mostly the issues of
concern are the pH (feed train) and alkaline ash content of the bio-oil. Hear we use both bio-oil
and char slurries together to recover the original biomass energy. Slurry transported to central
processing site where it is gasified in an entrained flow gasifier to syngas since, Syngas is
catalytic processed into green diesel.

34
Bio-oil plant design

Bio-oil gasification to produce green diesel (Robert C. Brown)

Bio-oil upgrading to hydrogen via steam

reforming
Hydrogen production from renewable bio-oil is an
attractive idea for fuel, energy, and agricultural applications.
Hydrogen is a common energy carrier and is prime matter
for numerous applications. Hydrogen can be directly used in
fuel cells in different kind of scenarios. Hydrogen can also
be used as a precursor of ammonia for use in fertilizers.
Bio-oil is mainly composed of two fractions: a
carbohydrate fraction (water soluble) and a lignin-derived
fraction (water insoluble). That derived from lignin fraction
(pyrolytic lignin) is considered a high-value product by itself. This lignin can be easily separated
and used as a direct precursor of gasoline-like products. The remaining water-rich carbohydrate
fraction can be steam reformed over a catalyst to generate hydrogen. One attractive scenario is to
use this hydrogen to catalytically upgrade the lignin products to fuels in the same centralized
facility.

35
Bio-oil plant design

Bio char as (fertilizer)

Bio char (also known as "agri-char") is a high-carbon rock resembling charcoal that is
produced through pyrolysis, the direct thermal decomposition of biomass in the absence of
oxygen. It can be used as a soil additive for numerous benefits, reduce climate change by
mitigating greenhouse gas emissions and sequestering atmospheric carbon in soil, and better
water quality by preventing chemical run-off. Biochar can also be used in tandem with the other
co-products of pyrolisis, bio-oil and syngas, to produce energy or for transportation fuel.
Biochar's has beneficial properties for soil also lend them to important agricultural applications.
Agricultural applications
biochar has numerous co-benefits when added to soil.

It can prevent the leaching of nutrients out of the soil,

Increase the available nutrients for plant growth,
Increase water retention, and
Reduce the amount of fertilizer required.
Additionally, it has been shown to decrease N20 and CH4 emissions from soil, thus

further reducing greenhouse gas emissions Biochar can be utilized in many applications as a
replacement for or coterminous strategy with other bio-energy production strategies. One is
switching from slash-and-burn to slash-and-char to prevent the rapid deforestation and
subsequent degradation of soils. Biochar can be used as a soil amendment to increase plant
growth yield, improve water quality, reduce soil emissions of greenhouse gases, reduce leaching
of nutrients, reduce soil acidity, and reduce irrigation and fertilizer requirements. These
properties are very dependent on the properties of the biochar, and may depend on regional
conditions including soil type, condition (depleted or healthy), temperature, and humidity.
Modest additions of biochar to soil were found to reduce N2O emissions by up to 80% and
completely suppress methane emissions. ( Betchkal/Flickr.)

36
Bio-oil plant design

Production of chemicals from pyrolysis oil

NB*, Production of chemicals from pyrolysis oil. (SOURSE: Patent Application 20080312476)
Background
Renewable sources of chemicals are of increasing importance. They are a means of
reducing dependence on imported oil for conversion to plastic precursors and provide a
substitute for basic chemical precursors. Renewable resources can provide for basic chemical
constituents to be used in many industries, such as chemical monomers for the making of plastics
and biomass is a renewable resource that can provide some of the needs for sources of chemicals
and fuels.
The economics depend on the ability to produce large amounts of biomass on marginal
land, by increasing the yield per acre, or in a water environment where there are few or no other
significantly competing economic uses of that land or water environment. The economics can
also depend on the disposal of biomass that would normally be placed in a landfill.
Generally, the process for producing precursor chemicals from bio-oil for use as purified
chemical feedstocks. Bio-oil comprises a substantial amount of oxygenates that have value as
chemical feedstocks instead of burning the bio-oil as fuel. The process comprises separating the
bio-oil into a water soluble stream and water insoluble stream comprising pyrolytic lignin,
lignocellulosic materials, and lignocellulosic bio-polymer derivatives. The water soluble stream
is concentrated by removing the water, thereby creating a concentrated organic phase. The
concentrated organic phase is passed to a catalytic reactor to upgrade the organic compounds. In
an alternate embodiment, the water insoluble phase is hydrotreated to increase the yields of
oxygenates.
DETAILED DESCRIPTION
In the process for producing chemical precursors from bio-oil, the bio-oil is first
separated into a non-aqueous stream comprising pyrolytic lignin and an aqueous stream
comprising water soluble oxygenates. The water aqueous stream can make up 50 to 80% of the
bio-oil. The aqueous phase is then concentrated by removing the water thereby creating a
concentrated organic phase. And finally, the concentrated organic phase is passed to a catalytic
reactor to upgrade the organic compounds.

37
Bio-oil plant design

The separation of the pyrolytic lignin from the aqueous stream can occur in the
pyrolysis step if proper processing conditions are found. The separation can be performed with a
gravimetric filtration process, where the denser lignin phase settles and the lighter aqueous phase
is removed. The separation step can include adding water to enhance the recovery of oxygenates
in the bio-oil by dissolving the oxygenates to increase recovery. After separating the aqueous
phase from the pyrolytic lignin, the process concentrates the dissolved organic compounds by
removal of water. The concentrating can be performed by a number of processes, including, but
not limited to, evaporation, distillation, extraction, membrane separation, adsorption separation,
or some combination.
The process further comprises separating the concentrated organic phase into a
plurality of intermediate product streams. Chemicals of value for use other than as a fuel
present in the organic phase include ketones, alcohols, phenols, carboxylic acids, and
carbohydrates. There are many valuable oxygenates in the concentrated organic phase, and the
separation of the organic phase can produce a stream comprising aldehydes, a stream comprising
organic acids, a stream comprising ketones, a stream comprising phenols, and a stream
comprising non-aromatic alcohols.
-

Examples of recoverable chemicals in the aldehyde stream include formaldehyde,

acetaldehyde, hydroxyacetaldehyde, and glyoxal.

Examples of recoverable organic acids include formic acid, acetic acid, propionic acid,
and larger organic acids. Examples of recoverable phenols include phenol and cresols.

Examples of recoverable ketones include acetol and cyclopentanone.

Examples of recoverable alcohols include methanol, ethanol, and larger alcohols and
glycols.
The concentration of the organics in the aqueous phase can be mixed with the separation

processes used to isolate individual constituents, or groups of constituents.

In one embodiment, the bio-oil can be pretreated by hydrotreating the bio-oil prior to
separation. The pretreatment can increase the yield of water soluble chemicals by mild reaction
of some of the lignin. The hydrotreating comprises contacting the bio-oil with a hydrotreating
catalyst that is stable to alkali and alkaline earth metals. An alternative step in the pretreatment is
to treat the bio-oil to remove alkali and alkaline earth metals, followed by mild hydrotreating of
the bio-oil.

38
Bio-oil plant design

Adhesives from bio-oil

Phenol-formaldehyde resin represents an important type of adhesives, employed in the
production of wood based panels of superior water resonance (exterior use products). They are
mainly the products of the reaction between phenol & formaldehyde; witch is catalyzed by alkali
to provide a thermosetting polymer called a reole.
Phenol is a petrochemical toxic substance & the increased oil price together with the need of
reduction on fossil fuels & promoting environmental friendly products have encouraged the
development of alternative resin feedstocks derived from renewable resources.
The potential use of bio-oil is replacing a part of the phenol needed in the formula of a phenolformaldehyde resin. A successful l phenol substitution should be: less toxic phenol, considerable
lower cost than petroleum dived phenol. Bio-oil produced from biomass can fulfill the two
requirements.
Methodology of the production process is by substituting up to 50% of the phenol needed
in the formula with bio-oil & the pyrolysis oil can used in the manufacturing of phenolic resin
for various panel types with positive result, & can be used as an alternative renewable resource
for making phenol based plastic resin.(source: A.R.I :adhesive research institute: Thessaloniki)

Upgrading Bio-oil Properties to Higher Value Products

As noted in the previous section, bio-oil quality can be improved to move it into a different
grade and therefore command a higher price for the producer. We have generally two ways of up
greading methods.
1. Physical upgrading techniques
2. Chemical upgrading techniques

Physical upgrading techniques

It is simplest and least expensive methods involve adding solvents or limited amounts
of water to bring the bio-oil into the desired viscosity range. If solvents such as alcohols are
used, added benefits accrue by adjusting the heating value and gaining improved long term
storage properties. Solids in the form of ash and attrited fluidizing media can be removed by
filtration, either hot (vapor phase) or after the oil has been condensed. This processing step will
add complexity and additional operating costs to the final product. We should point out that
while filtration has been demonstrated, both approaches have inherent difficulties that will
require additional development before they can be considered commercially viable. These
physical upgrading techniques can improve the quality of the neat, as produced, bio-oil but will

39
Bio-oil plant design

still require the designer of end use equipment to make significant modifications to address the
chemical properties of bio-oil, including acidity and low heating values because of high oxygen
content.
Chemical upgrading techniques
If bio-oils could be upgraded chemically to produce a product that looked more like
petroleum hydrocarbons then the end use device would require little to no modification. This
would be the fastest way to gain acceptance of biomass-based fuels into the existing
infrastructure. This approach essentially involves de-oxygenation and subsequent reforming of
the remaining hydrocarbons. Two basic approaches have been explored for chemical upgrading
of these oils:
1. catalytic cracking and
2. catalytic hydrotreating
In the first upgrading process the biomass pyrolysis upgrade using zeolite cracking
catalysts. in this process Oxygen is rejected in the form of H2O, CO2, and CO and the remaining
hydrocarbons are re-arranged to form mostly aromatic type hydrocarbons because of the shape
selectivity of zeolite catalysts for these types of hydrocarbons.
Generally upgrading using catalytic cracking can have the following advantages over the
other methods: Can operate at atmospheric pressure, It doesnt need any H2 gases & can produce
more hydrocarbons. Bio-Oil Hydrocracking:
Directly converts biomass into liquid bio-oil (lignin, carbohydrate derivatives, and water)
and char
Bio-oil catalytically converted into hydrocarbon fuel (green diesel)

Fig-Bio-Oil Hydrocracking process

40
Bio-oil plant design

An alternate approach using catalytic hydrotreating showed more promise. and

others have been developing this approach to chemical upgrading. Early work using low-activity
sulfided catalysts, showed that it was necessary to carry out the hydrotreating in two steps. The
first step (at lower temperature) initially stabilized the more reactive lower molecular weight
compounds, which was followed by higher temperature more aggressive hydrotreating of the
more stable phenolic compounds. As compare to the catalytically cracking this process it need
high pressure

Direct application of bio-oil for Boilers

Bio-Oil is an effective substitute for diesel, heavy fuel oil, light fuel oil, or natural gas in
essentially any type of boiler where these fuels are fired or contemplated to be fired. These are
relatively simple applications requiring basic modifications limited mainly to fuel nozzles and
transport systems. For the purpose of giving heat in Boiler & Kilns, bio-oil can be used directly
to the equipment to produce heat. It doesnt need any upgrading, may be some boilers need a
modification to use bio-oil as a heating source. Therefore bio-oil can replace some diesel in
boiler.

Significance effect of bio-oil derived chemicals in Ethiopian

industries
Although, there are many chemicals that can derived from bio-oil. We mainly concern on
the phenol-formaldehyde plastic resin, since all plastics factorys in our country they purchase
their raw material from abroad. Because our country has no petroleum source, as we know that
all plastic raw materials are petrochemical derives.
Producing phenol-formaldehyde from bio-oil is good news for those countries like Ethiopia;
their biomass sources are large but have no source of petroleum. Therefore it is a good method of
producing such types of plastic resin using alternate source that are found in our country, besides
of this the resin produce from bio-oil can have less price & toxic, this means our country can
save the currency.

41
Bio-oil plant design

Using Bio-oil as a source of heat for boiler & kilns

Direct applying bio-oil for the boiler & kilns has no alternative in its advantage for
industries found in our country, because bio-oil can easily produces in small scale & can produce
this alternate energy source for their factories rather than using fossil fuel that cost high many.
E.g. Zeway caustic soda factory the kiln can use around 17 litters of ( mazute ) fossil fuel based
heat generation media just to start up the kiln (i.e. it consume a large amount of energy &
forgeries currency) therefore it is advisable for those industries to come in to this new
technology & can minimize there cost.
From those bio-oil derived chemicals & from various types of application of bio-oil,
using bio-oil as a heat source for boiler & kilns & using bio-oil derived plastic resins are the best
ways for the industries of our country & we think this two applications are more advantageous
than the other application of bio-oil when we compare based on the cost it costs for the
application. Besides of this two important pointes using bio-char as a fertilizer is a zero cost &
the most advisable one to apply not only for the industries but also the farmer also can easily
apply it.

42
Bio-oil plant design

Chapter 5
5.1 Material & energy balance
5.2. Material balance
Capacity of the plant
We desire to design a bio-oil producing plant, whose capacity of producing is
75000m3/year bio-oil from bagasse. The design base of the process is based on the
desire of getting 65% bio-oil, 20% non-condensable gas, and 15% char from bagasse.
The capacity of of the plant take it based on consideration of bagasse availability in our
country i.e. Capacity of sugar factorys in our country.

Take of bio-oil= 1.2 Kg/L

= 75000m3/year* 1.2kg/L
= 90000ton/year

For the material balance all necessary data are given below.
Feed stock (bagasse)
Elemental composition of bagasse and some other basic property are given
below. The bagasse property is based on the following data are taken
bagasse
parameter
Value(dry
base)
C
47%
H2
5.5%
N2
1.7%
S
0.1%
O(by )
45.7%
Calorific value
18950 kJ/kg
Moisture content wt 40-45%
%
Solid-(dry) bagasse
57%
wt%
For the material balance calculation we take the average value. Based on the
above data
i.e. bagasse (elemental composition )
C -------------47%
H2-------------5.5%
O--------------45.7%

43
Bio-oil plant design
Moisture content wt%---------43%
Solid-(dry) bagasse wt%-------57%
Product bio-oil
As we know the elemental composition of bio-oil is different, if it is comes from
different bio mass source .for bio-oil produce from bagasse has given below, both the
elemental composition and basic compositions.
Bio-oil (from bagasse)
basic property
H2O (in bio-oil) ------------------15-30
PH--------------------------2.8-4
C (wt% dry base) ---------------56-64
(kg/L)-------------------1.1-1.25
H2-----------------------------------5-8
HHV (MJ/kg)
-------------16-20
N2-----------------------------------0.05-1
viscosity@315k (Cp)
---25-1000
S-------------------------------------0-0.05
O2-----------------------------------balance
Based on the above data all the calculation we perform on material and energy
balance is by taking average and optimum value.
Bio-oil
C (wt % dry base) -----------58%
(kg/L)
----------------------------------1.2
H2-----------------------------65%
H 2O (in bio-oil)
-------------------------20.8
O2------------------------------36%
PH------------------------------------------3
For the feedstock and bio-oil the element N2, S, and ash content are very small
compare to C, H2, and O2, therefore we neglect them and we consider only the
element that can result a significant change on material balance.
Char
The char that from during conversion of bagasse in the reactor as the following
composition
C------------------------------81.5 - 85.6
we take it as
C-------------------------85%
H2----------------------------2.9-3.1
H2------------------------3%
N2---------------------------<0.1
O2------------------------12%
O2+ (ash) -----------------10.214.6
NON-Condensable gas(pyro-gas)
The gas that is not able to condense in a condenser (quencher) has
compositions given blow.
H2-----------------------------------12.8%
CO----------------------------------17%
CO2--------------------------------2.5%

44
Bio-oil plant design
CH4--------------------------------19.2%
C2H4-------------------------------20.8%
C2H6-------------------------------7.2%
C3H6-------------------------------9.4%
C4 (+) -----------------------------10.1%
NH3--------------------------------0.8%

(data refer from DR.R.K.singh, 2005)

Feedstock conversion
Most of the time the biomass (bagasse) during fast pyrolysis is convert into there
components Bio-oil, char and non condensable gas. The range of conversion of this
component, if the row material is bagasse is given below.

For 100Kg dry bagasse mostly we get 6070%bio-oil, (60-70Kg)

1218% char, (12-18Kg)
1325% non condensable gas (1325kg)
Based on the above data our design-base for conversion of bagasse is just to get
around
65%------ bio-oil
20%------ non-condensable gas
15% -----char

Target overall bagasse conversion

(Design Basis)

AIR
The air that we used for the process is normal air by sucking from the atmosphere.
We consider its composition as
N2-----------------------79%
O2-----------------------21%
Basic assumption and consideration for material balance.
- Methods of our calculation on material balance is up stream i.e. based on our capacity
of desire production came to determine the amount of row material bagassse need for
the production process.
-Since the bio-oil and non condensable gas that produce during the process are by
itself are the composition of many various chemical and its difficult to do mass balance
for each elemental composition so we do based on the general product during
conversion as:
Non-condensable gas
Condensable gas (bio-oil)
Char
-Although we dont have exact conversion of bagasse in to bio- oil, char, and
condensable gas, we take 65% bio-oil, 20% non condensable gas and 15% chare

45
Bio-oil plant design
conversion as a design base (desire) value just for the use as a reference data for
calculation.
-Assume the plant operate 24 hour/day,& 300 days/year.

1. Material balance on product recovery and strong unit

Assumption
The product bio-oil contains 100% pure bio-oil.
Assume we recycle 85% of bio-oil from the total bio-oil produce formed in a day
in to the scrubber in order to cool the pyrolyzed gas.
No mass loss in the pipe during splitting of bio-oil
The plant that we design has a capacity of producing 300ton/day (250m 3/day) bio-oil
as a final product for every day. As we observe from the flow sheet this product is
15% from the total bio-oil out from the scrubber. The remains 85% bio-oil is recover
back to the scrubber for cooling the next coming pyrolysis gas.

B (ton/day) =?
Recovered bio-oil

Bio oil splitting

(ton/day)
=

A=300ton/day
Product Bio-oil

Total mass balance

Mass in =mass out
description we have

based on the above process

C=A+B
300ton/day=15%*C----------------------------2
C=300+B-------------------------1

300ton/day=0.15C

Substituting C=2000ton/day
2000=300+B

B=2700ton/day bio-oil recovery back

C=2000ton/day bio-oil

46
Bio-oil plant design
Therefore 1700ton/day bio-oil is recycling back to the scrubber to cool the coming
gas and to remove any aerosols in a vapor.

2. Material balance on product-mixer

Assumption
-from the total produced bio-oil in a day the ESP can save around 0.5% of the total
The bio-oil from scrubber and ESP (electro static precipitator) is mix (bland) before
.they goes to storage. But from the total bio-oil produce most of the product are
comes from the scrubber only around 0.5% from total bio-oil produce is comes from
ESP with in a day.

D (ton/day) =?
Bio-oil from
ESP

E
(ton/day) =?
Bio-oil from
scrubber

Mixer

C=2000ton/day
bio-oil

Total mass balance

Mass in=mass out
description we have

D+E=C
D+E=2000ton/day
Substitute D=10ton/day
10+E=2000
out from ESP

from the above process

D=0.5 % of(C)
D=0.005*C
D=0.005*2000ton/day

D=10ton/day bio-oil

E=1900ton/day bio-oil out from scrubber.

Thus we save around 10ton/day bio-oil by using ESP, and 1990ton/day bio-oil is coming
out from scrubber in everyday production process.

47
Bio-oil plant design
3. Material balance

on product (bio-oil) cleaning process

Assumption
-Assume the percentage of produced bio-oil is equal to our desire value 65% of the
total biomass feed.
-The gas composition in to the scrubber is calculated based on the above assumption.

When we take the scrubber, ESP and product storage as one system boundary
and make it a total material balance for the system boundary. The composition of gas
into the scrubber is first, we have to calculate based on the process description data
and our design base consideration.

H (ton/day) =?

100% non-condgas

ESP

F
(ton/day) =?
X% BIOOIL
Y% noncond -gas

Scrubb
er
Mixer

Bio-oil
splitting

A=300ton/day
100% Biooil

First, we have to calculate the composition of gas that comes from pyrolysis
reactor .based on our design base consideration and the pyrolysis reactor feed to gas
ratio.

Our design base, is to get 65%bio-oil, 20%non-condesable gas and 15%char

from 100Kg (base) bagasse.
Assume: On pyrolysis reactor the bagasse (feed) to gas is 1.08 by mass.
Based on the above two point consideration the composition of pyrolysis gas
that comes from reactor become:
33.85%----------bio-oil
7.8%-------------char
58.3%--------------non-condensable gas

48
Bio-oil plant design
This composition is before the char is removed, but we need the composition of
gas without char for point. (F) .so to convert the bio-oil and non- condensable gas only
into 100% we based on the ratio of the two gas.

Therefore by the same ratio difference we can calculate the composition of biooil and non-condensable gas out of 100% at point (F).
Therefore at point (F) we have
37%----------------bio-oil
i.e. X=37%
63%---------------- non-condensable gas
Y=63%

Total mass-balance- the above system boundary

Mass in

F
F

= mass out

= H+A

= H+300--------------1
Balance on bio-oil
X*F=A
(37%) *F=300
0.37F=300
F=810.8ton/day
By substituting F=810.8ton/day in to --------------eq 1
F=H + 300ton/day
H= 810.8-300
H=510.8ton/day non-condensable gas recycled back in to the combustor &
pyrolysis reactor.

3. Material- balance on Quencher

Assumption
-No mass in loss, generate and consume
-Mass in = mass out by the composition.
On this part of the process (we have two consider 1 and 2) and we have no mass
transfer or loss in this part. (Mass in=mass out) no addition mass inter into the
process. We have only heat transfer to cool the process gas only his position.

I
(ton/day)
=?

Condenser
1

Condenser
2

Total mass balance

Mass-in = mass-out

I= F =810.8ton/day with the same composition.

F=810.8ton/day
37% bio-oil
57% noncondensable gas

49
Bio-oil plant design

4. Material-balance on Cyclone
Assumption
-The cyclone removes at the bottom all the char.
-The solid (char) found in bio-oil very small and can neglect it.

The cyclone is used to separate the char from the process gas that come
from pyrolysis reactor. To calculate material balance on this unit .we have already
calculate the composition of process gas (pyrolysis) that comes out from the reactor.
(Based on our design base consideration and pyrolysis reactor)

K (ton/day) =?
33.85% bio-oil
7.5%char
58.3% noncondensable gas

Total mass balance

Cyclone

I=810.8ton/day
37% bio-oil
63% non
condensable gas

J (ton/day) =?
100% char

balance on bio-

oil
Mass in = mass out
0.37*(810.8)

0.3383*K =

K=J+I

K= J + 810.3 ton/day
Substitute K=886.3 ton/day

ton/day

K = 866.3

50
Bio-oil plant design
866.3 = J + 810.8

J = 75.5 ton/day char

4. Material balance on pyrolysis

Assumption
-The dry bagasse moisture content is 7%.
- The dry bagasse to fluidize gas ratio is 1.08 by mass.
- The sand circulate (in & out) by the same amount, we can neglect it in the calculation
- assume no mass accumulation, generation,& loss in the reactor.
In pyrolysis reactor we have two feed to the reactor the first one is a relatively
dry bagasse about 7% moisture content and the second one is a hot recycle pyro-gas
(non-condensable gas) in order to fluidize the chips .the bagasse (feed) to gas ratio is
0.92:1 is mostly advisable for a good production of bio-oil. All the incoming bagasse is
converted in to gas (e.g . CO, H2..) H 2O, ash, etc. as a general the conversion of
bagasse yield the following three products based on our design base composition.

Bio-oil-------------------------------65%
Char----------------------------------15%
Non-condensable gas-----------20%
For material balance on the reaction, we neglect the sand because it is recycled
by the same amount between the reactor and combustor.

Dry
bagasse
L

Pyrolys
is
reactor

K=886.3ton/day
33.85% bio-oil
58.3% non
condensable gas
7.5%char

(ton/day) =?

M (ton/day) =?
100% noncondensable gas

51
Bio-oil plant design

Based on the above, assumption in the disciption of the process

Gas-to-bagasse feed ratio is 0.92 :1

Therefore: M= 0.92*L---------------1

Total mass balance on pyrolysis reactor

Mass in = mass out

L+M=K

since M=0.92*L

L + M = 886.3ton/day
L + 0.92*L= 866.3
1.92*L = 866.3ton/day

Therefore L = 461.6 ton/day

dry-bagasse is need to feed to the
reactor in order to produce 300ton/day bio-oil. The total amount of non-condensable
gas needs in to day to fluidize 461.6 ton/ day bagasse is
M = 0.92*L
= 0.92 * 461 .6ton/day

M= 424.6 ton/day. Non-condensable gas is needed to fluidize

the dry bagasse.

5. Material balance on Dryer

The bagasse that we used from sugar factory in our country has moisture content of
43% , but we need to drop this moisture into 7% ,
Assumption

52
Bio-oil plant design
- Assume The bagasse we use has 43% moisture content & the dry bagasse out from
dryer has 7% moisture content.
-Assume the hot air that are used for drying in exhausted with the steam that
evaporate by the same amount with that of mass in and can ignore it in calculation.
-Assume no consumption an generation
Mass in= Mout + Mloss
The bagasse that we used from sugar factory in our country has moisture content
of 43%, but we need to drop this moisture into 7%,
Hot air

Dryer

Wet bagasse
O
(ton/day) = ?
43% H2O
(moisture)
57% solid
bagasse

Cold Air & steam

N (ton/day) =
100%H2O (steam

Total mass balance on dryer

(H2O)
Mass in = mass out

Dry bagasse
L =461.6ton/day
93% solid
bagasse
7% H2O
(Moisture)

balance on moisture
(0.43) O + N = 0.07

(L)
O=N+L
(461.6)
O-N = 461.6---------------1
32.3--------------2

0.43 O + = 0.07
0.43 O + N =

Balance on dryer solid bagasse

0.57* O = 0.93 * 461.6

O = 753.1 ton/day wet bagasse is need to produce 300ton/day bio-oil based

on our design base consideration. The amount of moisture evaporated from bagasse is
calculated is by substituting O = 753.1 ton/day into eq.1or 2
N = O-461.6
=753.1-461.6

N=291.5 ton/day amount of H2O is evaporated from the bagasse to drop

its moisture content to the design value of 7% from 43%.

53
Bio-oil plant design

6.

Material-balance on combustor

Assumption
-Complete combustion of chare
-The air (O2) is 20% excess from the stiocheometrey value just to make it share the
complete combustion process
-The recovered non condensable gas to total air in to the air is 6% (value based on our
non condensable gas remain after using in the reactor.)
-The mass of sand that come in to the combustor and out from it are equal.
Since, we assume the char combustion is complete combustion there fore the amount
of air for combustion is depend on O2 (Air) into the combustor.
The reaction takes place in the combustor.
C +1/2 O2
CO
CO = O2
CO2
_____________________________________
C + O2
CO2
Taking 1Kg of char as bases
1Kg
x
C
+
O2
CO2
12g/mol
32g/mol
Therefore, the amount of air required for the complete combustion of char.

X= 2.66Kg of O2 is required for 1Kg of char to combust completely. Since O 2 in air is

21% of air, therefore
2.66=0.21 Mass of air
Mass of air= 12.7 Kg of air

54
Bio-oil plant design
For the reaction to be quite sure complete combustion, the amount of air must excess
i.e. around 20% excess O2 (air) is needed.
Therefore total mass of air need is= 12.7 + 12.7(0.2)
=15.24 Kg air
Hence for 1Kg C (char) we need 15.24 Kg of air for complete combustion of the char. in
the same manner for our big plant in order to fire completely 75.5 tan/day char.

1Kg (char)

15.24Kg air need

75.5tan/day

Assume the non-condensable gas into the combustor is 6% of the total air need
for complete combustion of char. since this gas is need to reach the char into the
ignite- temperature in order to start combustion by itself in a combustor. Therefore the
combusted air and non-condensable gas should combine and heated to around 500 0c
prior to the combustor.
Mass of non-condensable gas = 6% of Air
=0.06*1150.6
=69ton/day
Therefore total mass of gas in at the bottom of the combustor is :
= 69ton/day +1150.6ton/day
=1219.6 ton/day

Flue
gas
Char &
sand
75.5 ton/day
sand

Combusto
r

55
Bio-oil plant design

S
and
Combustion air & non
condensable gas
1219.6 ton/day
Assume
The sand in to the combustor is circulating (in and out) with out loss therefore we dont
concern its mass.
Mass in =Mass out

Mchar +M air+ non-condensable gas =

75.5 ton/day

MFlue gas

+ 1219.6 ton/day=

MFlue gas =1295.1 ton/day

From the combustor 1295.1ton/day hot flue gas is out from the combustor
for heating some process part & in order to produce steam for electric
generation.