BIOFUEL AND GREEN BIOTECHNOLOGY

Course Code: BTE2509 Credit Units: 03

Module I: Biomass Sources, Characteristics & Preparation:

 Biomass Sources and Classification-Chemical composition and properties of different biomass materials
 Bio-fuels – Sugar cane molasses for fermentation of ethanol;
 Sources and processing of oils and fats for liquid fuels
 Energy plantations - Preparation of woody biomass
 Drying, Storage and Handling of Biomass.

Module II: Biogas Technology-

 Biodegradable organic matter
 Feedstock for biogas production,
 Operating parameters for biogas production,
 Dry and wet fermentation

Module III: Bio-Ethanol and Bio-Diesel Technology-

 Production of Fuel Ethanol by Fermentation of Sugars.
 Trans-esterification of Oils to Produce Bio-Diesel.

Module IV: Pyrolysis and Gasification of Biomass

 Thermo-chemical conversion of Ligno-cellulose biomass - Pyrolysis of biomass
 Thermo-chemical gasification principles

Module V: Combustion of Biomass and Cogeneration Systems-

 Combustion of Woody Biomass,
 Cogeneration in Biomass Processing Industries.
 Use of biogases for cogeneration.

Examination Scheme:
Components CT Attendance Assignment/ EE
Project/Seminar/Quiz
Weightage (%) 15 5 10 70
Text & References:
 Biotechnology and Alternative Technologies for Utilization of Biomass or Agricultural Wastes, A. Chakravarthy, Oxford & IBH
publishing Co., New Delhi, 1989.
 Biogas Systems: Principles and Applications, K.M. Mital, New Age International Publishers (p) Ltd., 1996.
 Biomass Energy Systems, P. Venkata Ramana and S.N. Srinivas, Tata Energy Research Institute, New Delhi, 1996.
 Fuels from Biomass and Wastes, D.L. Klass and G.M. Emert, Ann Arbor Science publ. Inc. Michigan, 1985.
 Bio-gas Technology, Khandelwal K.C. and Mahdi, Tata McGraw-Hill pub. Co. Ltd., New Delhi
 Advances in bio-gas Technology, O.P. Chawla, I.C.A.R., New Delhi. 1970.
 4 Pyrolysis and Gasification of Biomass
Thermo-chemical conversion of Ligno-cellulose biomass
Thermochemical biomass conversion includes a number of possible roots to produce from the initial bio-renewable
feedstock useful fuels and chemicals. Bio renewable feedstocks can be used as a solid fuel, or converted into liquid or
gaseous forms for the production of electric power, heat, chemicals, or gaseous and liquid fuels. Thermochemical
conversion processes include three subcategories: pyrolysis, gasification, and liquefaction. A variety of biomass
resources can be used to convert to liquid, solid, and gaseous fuels with the help of some physical, thermochemical,
biochemical, and biological conversion processes. Main biomass conversion processes are direct liquefaction, indirect
liquefaction, physical extraction, thermochemical conversion, biochemical conversion, and electrochemical conversion.

The conversion of biomass materials has the precise objective to transform a carbonaceous solid material, which is
originally difficult to handle, bulky and of low energy concentration, into fuels having physico-chemical characteristics
that permit economic storage and transferability through pumping systems.

 Gasification of biomass for use in internal

combustion engines for power generation
provides an important alternate renewable
energy resource. Gasification is partial
combustion of biomass to produce gas and
char at the first stage and subsequent
reduction of the product gases, chiefly CO2
and H2O, by the charcoal into CO and H2.
The process also generates some methane
and other higher hydrocarbons depending on
the design and operating conditions of the
reactor.
 Pyrolysis is the fundamental chemical reaction process that is the precursor of both gasification and combustion
of solid fuels, and is simply defined as the chemical changes occurring when heat is applied to a material in the
absence of oxygen. Flash pyrolysis of biomass is the thermochemical process that converts small dried biomass
particles into a liquid fuel (bio-crude) with a yield of almost 75%, and char and non-condensable gases by heating
the biomass to 775 K in the absence of oxygen. Char in the vapor phase catalyzes secondary cracking.
 Plasma arc and radio frequency (or microwave) heating refer to specific devices providing heat from electricity for
gasification, pyrolysis, or combustion depending on the amount of reactive oxygen, hydrogen, steam, or other
reactant fed to the reactor. Very high temperatures are created in the ionized plasma. Plasma arc processes use
electricity passing through electrodes to produce a discharge converting the surrounding gas to an ionized gas or
plasma. Gases heated in plasmas typically reach temperatures of 377 K and higher.

Thermochemical conversion is characterized by higher temperatures and conversion rates than most other processes.
Thermochemical conversion includes a continuum of processes ranging from thermal decomposition in a primarily
nonreactive environment (commonly called pyrolysis) to decomposition in a chemically reactive environment (usually
called gasification if the products are primarily fuel gases). Pyrolysis can be considered an incomplete gasification
process, in which a mixture of gaseous, liquid, and solid products is produced, each of which may have some
immediate use to sustain the process. The characteristics of each of these processes can also vary depending on the
oxidizing or reducing media, process temperature, and process pressure.

 The hemicelluloses, which are present in deciduous woods chiefly as pentosans and in coniferous woods
almost entirely as hexosanes, undergo thermal decomposition very readily. It was therefore to be expected
that furan derivatives would readily be found among the decomposition products. The hemicelluloses
decomposed more readily than cellulose during heating. The thermal degradation of hemicelluloses begins
above 475 K.
 Thermal degradation of cellulose proceeds through a gradual degradation, decomposition, and charring on
heating at lower temperatures, and a rapid volatilization accompanied by the formation of laevoglucose on
pyrolysis at higher temperatures. The glucose chains in cellulose are first cleaved to glucose and, in a second
 stage, glucosan is formed by the splitting off of one molecule of water. Initial degradation reactions include
depolymerization, hydrolysis, oxidation, dehydration, and decarboxylation. Cellulose decomposes more readily
than lignin by heating.
 Lignin decomposes over a wider temperature range. As the resistance time increases the quantity of unstable
substances decrease. For example, quantitatively, 1-hydroxy-2-propanone and 1-hydroxy-2-butanone present
high concentrations in the liquid products from fast pyrolysis. These two alcohols are partly esterified by acetic
acid. In conventional slow pyrolysis, these two products are not found in so great a quantity because of their
low stability. Many unstable fragments and radicals form from degradation of lignin. As a result, it is believed
that as the reaction progresses the remaining mass becomes less reactive and forms stable chemical
structures, and consequently the activation energy increases as the conversion level of biomass increases.

Pyrolysis
Pyrolysis is a thermochemical decomposition of biomass into a range of useful products, either in the total absence of
oxidizing agents or with a limited supply that does not permit gasification to an appreciable extent . It is one of several
reaction steps or zones observed in a gasifier. During pyrolysis, large complex hydrocarbon molecules of biomass
break down into relatively smaller and simpler molecules of gas, liquid, and char.

Pyrolysis has similarity to and some overlap with processes like cracking, devolatilization, carbonization, dry distillation,
destructive distillation, and thermolysis, but it has no similarity with the gasification process, which involves chemical
reactions with an external agent known as gasification medium. Pyrolysis of biomass is typically carried out in a
relatively low temperature range of 300 to 650 °C compared to 800 to 1000 °C for gasification.

Pyrolysis involves heating biomass or other feed in the absence of air or oxygen at a specified rate to a maximum
temperature, known as the pyrolysis temperature, and holding it there for a specified time. The nature of its product
depends on several factors, including pyrolysis temperature and heating rate. The initial product of pyrolysis is made of
condensable gases and solid char.

The condensable gas may break down further into non-condensable gases (CO, CO 2, H2, and CH4), liquid, and char.
This decomposition occurs partly through gas-phase homogeneous reactions and partly through gas-solid–phase
heterogeneous thermal reactions. In gas-phase reactions, the condensable vapor is cracked into smaller molecules of
non-condensable permanent gases such as CO and CO2.

The pyrolysis process may be represented by a

generic reaction such as

Pyrolysis is an essential pre-step in a gasifier. This step is

relatively fast, especially in reactors with rapid mixing.
Biomass is fed into a pyrolysis chamber containing hot
solids (fluidized bed) that heat the biomass to the
pyrolysis temperature, at which decomposition starts. The
condensable and non-condensable vapors released from
the biomass leave the chamber, while the solid char
produced remains partly in the chamber and partly in the
gas. The gas is separated from the char and cooled
downstream of the reactor. The condensable vapor
condenses as bio-oil or pyrolysis oil; the non-
condensable gases leave the chamber as product gas.
These gases may be fired in a burner to heat the
pyrolysis chamber, or released for other purposes.
Similarly, the solid char may be collected as a
commercial product or burned in a separate chamber to produce heat that is necessary for pyrolysis. As this gas is free
from oxygen, part of it may be recycled into the pyrolysis chamber as a heat carrier or fluidizing medium.
Pyrolysis Products

Pyrolysis involves a breakdown of large complex molecules into several smaller molecules. Its product is classified into
three principal types:
 Solid (mostly char or carbon)
 Liquid (tars, heavier hydrocarbons, and water)
 Gas (CO2, H2O, CO, C2H2, C2H4, C2H6, C6H6, etc.)
The relative amounts of these products depend on several factors including the heating rate and the final temperature
reached by the biomass. The pyrolysis product should not be confused with the “volatile matter” of a fuel as determined
by its proximate analysis. In proximate analysis, the liquid and gas yields are often lumped together as “volatile matter,”
and the char yield as “fixed carbon.” Since the relative fraction of the pyrolysis yields depends on many operating
factors, determination of the volatile matter of a fuel requires the use of standard conditions as specified in test codes
such as ASTM D-3172 and D-3175. The procedure laid out in D-3175, for example, involves heating a specified
sample of the fuel in a furnace at 950 °C for seven minutes to measure its volatile matter.

1. Solid
Char is the solid yield of pyrolysis. It is primarily carbon (~85%), but it can also contain some oxygen and
hydrogen. Unlike fossil fuels, biomass contains very little inorganic ash. The lower heating value (LHV) of biomass
char is about 32 MJ/kg, which is substantially higher than that of the parent biomass or its liquid product.
2. Liquid
The liquid yield, known as tar, bio-oil, or bio-crude, is a black tarry fluid containing up to 20% water. It consists
mainly of homologous phenolic compounds. Bio-oil is a mixture of complex hydrocarbons with large amounts of
oxygen and water. While the parent biomass has an LHV in the range of 19.5 to 21 MJ/kg dry basis, its liquid yield
has a lower LHV, in the range of 13 to 18 MJ/kg wet basis.
Bio-oil is produced by rapidly and simultaneously depolymerizing and fragmenting the cellulose, hemicellulose, and
lignin components of biomass. In a typical operation, the biomass is subjected to a rapid increase in temperature
followed by an immediate quenching to “freeze” the intermediate pyrolysis products. Rapid quenching is important,
as it prevents further degradation, cleavage, or reaction with other molecules. Bio-oil is a micro emulsion, in which
the continuous phase is an aqueous solution of the products of cellulose and hemicellose decomposition, and
small molecules from lignin decomposition. The discontinuous phase is largely composed of pyrolytic lignin
macromolecules. Bio-oil typically contains molecular fragments of cellulose, hemicellulose, and lignin polymers that
escaped the pyrolysis environment. The molecular weight of the condensed bio-oil may exceed 500 Daltons.
Compounds found in bio-oil fall into the following five broad categories:
 Hydroxy-aldehydes
 Hydroxy-ketones
 Sugars and dehydrosugars
 Carboxylic acids
 Phenolic compounds
3. Gas
Primary decomposition of biomass produces both condensable gases (vapor) and non-condensable gases
(primary gas). The vapors, which are made of heavier molecules, condense upon cooling, adding to the liquid yield
of pyrolysis. The non-condensable gas mixture contains lower-molecular-weight gases like carbon dioxide, carbon
monoxide, methane, ethane, and ethylene. These do not condense on cooling. Additional non-condensable gases
produced through secondary cracking of the vapor are called secondary gases. The final non-condensable gas
product is thus a mixture of both primary and secondary gases. The LHV of primary gases is typically 11 MJ/Nm 3,
but that of pyrolysis gases formed after severe secondary cracking of the vapor is much higher: 20 MJ/Nm 3.

Types of Pyrolysis
Based on heating rate, pyrolysis may be broadly classified as slow and fast. It is considered slow if the time, theating,
required to heat the fuel to the pyrolysis temperature is much longer than the characteristic pyrolysis reaction time, tr,
and vice versa. That is:
  Slow pyrolysis: theating >> tr
 Fast pyrolysis: theating << tr

These criteria may be expressed in terms of heating rate as well, assuming a simple linear heating rate (Tpyr/theating, K/s).
The characteristic reaction time, tr, for a single reaction is taken as the reciprocal of the rate constant, k, evaluated at
the pyrolysis temperature.
There are a few other variants depending on the medium in and pressure at which the pyrolysis is carried out. Given
specific operating conditions, each process has its characteristic products and applications. In the following list, the first
two types are based on the heating rate while the third is based on the environment or medium in which the pyrolysis is
carried out:
 Slow pyrolysis,
 Fast pyrolysis, and
 Hydro pyrolysis.

Slow and fast pyrolysis are carried out generally in the absence of a medium. Two other types are conducted in a
specific medium:
 Hydrous pyrolysis (in H2O) and
 Hydro pyrolysis (in H2).

These types are used mainly for the production of chemicals. In slow pyrolysis, the residence time of vapor in the
pyrolysis zone (vapor residence time) is on the order of minutes or longer. This process is used primarily for char
production and is broken down into two types:
 Carbonization
 Conventional.

In fast pyrolysis, the vapor residence time is on the order of seconds or milliseconds. This type of pyrolysis, used
primarily for the production of bio-oil and gas, is of two main types:
 Flash
 Ultra-rapid.

1. Slow Pyrolysis: Carbonization is a slow pyrolysis process, in which the production of charcoal or char is the
primary goal. It is the oldest form of pyrolysis, in use for thousands of years. The biomass is heated slowly in the
absence of oxygen to a relatively low temperature (~400 °C) over an extended period of time, which in ancient
times ran for several days to maximize the char formation. A small fire at the bottom provided the required heat,
which essentially stayed in the well-insulated closed chamber. Carbonization allows adequate time for the
condensable vapor to be converted into char and non-condensable gases. Conventional pyrolysis involves all
three types of pyrolysis product (gas, liquid, and char). As such, it heats the biomass at a moderate rate to a
moderate temperature (~600 °C). The product residence time is on the order of minutes.
2. Fast Pyrolysis: The primary goal of fast pyrolysis is to maximize the production of liquid or bio-oil. The biomass is
heated so rapidly that it reaches the peak (pyrolysis) temperature before it decomposes. The heating rate can be
as high as 1000 to 10,000 °C/s, but the peak temperature should be below 650 °C if bio-oil is the product of
interest. However, the peak temperature can be up to 1000 °C if the production of gas is of primary interest. Four
important features of the fast pyrolysis process that help increase the liquid yield are:
 Very high heating rate,
 Reaction temperature within the range of 425 to 600 °C,
 Short residence time (< 3 s) of vapor in the reactor,
 Rapid quenching of the product gas.
3. Flash Pyrolysis: In flash pyrolysis biomass is heated rapidly in the absence of oxygen to a relatively modest
temperature range of 450 to 600 °C. The product, containing condensable and non-condensable gas, leaves the
pyrolyzer within a short residence time of 30 to 1500 ms. upon cooling, the condensable vapor is then condensed
into a liquid fuel known as bio-oil. Such an operation increases the liquid yield while reducing the char production.
A typical yield of bio-oil in flash pyrolysis is 70 to 75% of the total pyrolysis product.
4. Ultra-Rapid Pyrolysis: Ultra-rapid pyrolysis involves extremely fast mixing of biomass with a heat carrier solid,
resulting in a very high heat-transfer and hence heating rate. A rapid quenching of the primary product follows the
 pyrolysis, occurring in its reactor. A gas–solid separator separates the hot
heat-carrier solids from the non- condensable gases and primary product
vapors, and returns them to the mixer. They are then heated in a separate
combustor. Then a non-oxidizing gas transports the hot solids to the mixer. A
precisely controlled short uniform residence time is an important feature of
ultra-rapid pyrolysis. To maximize the product yield of gas, the pyrolysis
temperature is around 1000 °C for gas and around 650 °C for liquid.
5. Pyrolysis in the Presence of a Medium: Normal pyrolysis is carried out in
the absence of a medium such as air, but a special type is conducted in a
medium such as water or hydrogen.
 In Hydro pyrolysis, thermal decomposition of biomass takes place in an
atmosphere of high-pressure hydrogen. Hydro pyrolysis can increase the
volatile yield and the proportion of lower-molar-mass hydrocarbons. This process is different from the
hydrogasification of char. Its higher volatile yield is attributed to hydrogenation of free-radical fragments
sufficient to stabilize them before they repolymerize and form char.
 Hydrous pyrolysis is the thermal cracking of the biomass in high-temperature water. It is used by a
commercial company, Changing World Technology to convert turkey offal into light hydrocarbon that can be
used for production of fuel, fertilizer, or chemicals. In a two-stage process, the first stage takes place in water
at 200 to 300 °C under pressure; in the second stage the produced hydrocarbon is cracked into lighter
hydrocarbon at a temperature of around 500 °C. High oxygen content is an important shortcoming of bio-oil.
Hydro pyrolysis can produce bio-oil with reduced oxygen.

Thermo-chemical Gasification

Thermochemical gasification is a partial oxidation process whereby a carbon-rich material such as biomass (or coal) is
broken down into a gas consisting of carbon monoxide (CO) and hydrogen (H 2) plus carbon dioxide (CO2), methane
(CH4) and other gaseous hydrocarbons along with contaminants, such as tars, char, ash etc. This mix of gases is
known as ‘producer gas’ or ‘syngas’ (synthesis gas) and the precise characteristics of the gas will depend on the
feedstock properties, gasification parameters – such as temperature – and the oxidizer used. Gasification using air
results in relatively low operating temperatures, higher amount of tar and about 50% nitrogen in the gas – this gas can
be burned directly for heat or used for running engines after removing the tar. When oxygen and steam are used to
produce a gas consisting of CO and H2, it is called syngas.

Gasification is the conversion of solid or liquid feedstock into useful and convenient gaseous fuel or chemical feedstock
that can be burned to release energy or used for production of value-added chemicals. Gasification and combustion
are two closely related thermochemical processes, but there is an important difference between them. Gasification
packs energy into chemical bonds in the product gas; combustion breaks those bonds to release the energy. The
gasification process adds hydrogen to and strips carbon away from the feedstock to produce gases with a higher
hydrogen-to carbon (H/C) ratio, while combustion oxidizes the hydrogen and carbon into water and carbon dioxide,
respectively.
A typical biomass gasification process may include the following steps:
 Drying
 Thermal decomposition or pyrolysis
 Partial combustion of some gases, vapors, and char
 Gasification of decomposition products
Pyrolysis is a thermal decomposition process that partially removes carbon from the feed but does not add hydrogen.
Gasification, on the other hand, requires a gasifying medium like steam, air, or oxygen to rearrange the molecular
structure of the feedstock in order to convert the solid feedstock into gases or liquids; it can also add hydrogen to the
product. The use of a medium is essential for the gasification process.

Gasifying Mediums
Gasifying agents react with solid carbon and heavier hydrocarbons to convert them into low-molecular-weight gases
like CO and H2. The main gasifying agents used for gasification are
 Oxygen
  Steam
 Air
Oxygen is a popular gasifying agent, though it is primarily used for the combustion step. It may be supplied to a gasifier
either in pure form or through air. The heating value and the composition of the gas produced in a gasifier are strong
functions of the nature and amount of the gasifying agent used. If oxygen is used as the gasifying agent, the
conversion path moves toward the oxygen corner. Its products include CO for low oxygen and CO 2 for high oxygen.
When the amount of oxygen exceeds a certain (stoichiometric) amount, the process moves from gasification to
combustion, and the product is “flue gas” instead of “fuel gas.” Neither flue gas nor the combustion product contains
residual heating value when cooled. A move toward the oxygen corner leads to a lowering of hydrogen content and an
increase in carbon-based compounds such as CO and CO 2 in the product gas.
If steam is used as the gasification agent, the path is upward toward the hydrogen corner. Then the product gas
contains more hydrogen per unit of carbon, resulting in a higher H/C ratio. Some of the intermediate reaction products
like CO and H2 also help to gasify the solid carbon.
The choice of gasifying agent affects the heating value of the product gas. If air is used instead of oxygen, the nitrogen
in it greatly dilutes the product.