1.

Introduction

 Biomass can provide a full range of convenient feedstock for energy,

metallurgical and chemical industries. This feedstock can be in the form of solid,
liquid, or gases.

 Woody, herbaceous aquatic, and municipal solid waste biomass have variable
physical properties and chemical compositions.

These physical properties—such as bulk density, irregular size, and inconsistent

shape—create transportation, storage, handling, and flow challenges that limit
biomass use for large-scale bioenergy production applications.
• Torrefaction is the slow heating of biomass in an inert or oxygen-
deficit environment in the temperature range of 200–300°C.
• Parameters that impact the torrefaction process
heating rate residence time
reaction temperature
reactor environment, residence time, atmospheric pressure,
feedstock flexibility, particle size, and moisture content.
1.1 Torrefaction
 A thermochemical process in an inert or limited oxygen environment where biomass is slowly
heated to within a specified temperature range (200–300°C) and retained there for a stipulated
time such that it results in near complete degradation of its hemicellulose content while
maximizing mass and energy yield of solid product.

 Torrefaction is the slow heating of biomass in an inert or oxygen-deficit environment in the

temperature range of 200–300°C. Often called a pretreatment process as it prepares biomass for

further use instead of direct use in its raw form.

 Parameters that impact the torrefaction process

 Heating rate  Residence time
 Residence time  Particle size
 Reaction temperature  Atmospheric pressure
 Reactor environment  Feedstock flexibility, and moisture content.
During the torrefaction process, moisture is evaporated, and some of the hydrogen- and oxygen-
containing organic components of organic compounds are thermally decomposed, releasing volatile
organic compounds. A solid uniform product with lower moisture and higher energy content is produced
at the end of the torrefaction process.

Mass and energy changes of a feed undergoing torrefaction Schematic of a torrefaction system.
Cont …
 The thermochemical changes in biomass during torrefaction process may be divided into three

main three temperature regimes ; Tumuluru et al. (2011)

1) non-reactive (e.g.,50–150°C); removes the unbound water.

2) reactive (e.g., 150–200°C); removes most of the bound water

3) destructive (e.g.,200–300°C). cause thermal decomposition, devolatilization, and

carbonization reactions.

 Various biomass reactions will takes place on this three regimes, like dehydration,

depolymerization, devolatilization. These reactions bring significant changes in biomass physical

properties, chemical composition, and energy content.

1.2 Mass and Energy Yield


The mass yield from torrefaction usually is less than 1 and the energy yield usually

is greater than one because of the reduced torrefied product mass.


The net thermal process efficiency is defined as the energy yield in the torrefied

products divided by the total energy input (e.g., the energy content of the feedstock

plus energy added to the hea and run the torrefaction process).

1.3 Torrefied Product Properties

 Moisture  Hydrophobicity
 Bulk and energy density  Chemical properties
 Grindability
I, Moisture
Torrefied biomass typically has a moisture content of 1–3% (w.b.).

Tumuluru (2016) Torrefaction of pine biomass indicated that moisture content decreased with increased
torrefaction temperature and residence time. At 270°C torrefaction temperature and 120 min residence
time, the lowest moisture content of about 1.2% (w.b.) (about 69% moisture loss) was observed.

II, Bulk and energy density

 Biomass torrefaction results in the loss of material that evaporates or volatilizes at torrefaction
temperatures. This process results in the increased porosity of the biomass, thereby decreasing the bulk
density.
 Phusunti et al. (2018) reported that torrefied microalgae reached the highest calorific value of about
19 MJ/kg after torrefaction at 200°C for 30 min. Chen et al. (2015) reported a decrease in bulk density
of about 180–350 kg/ m3 based on the conditions of their studies on Eucalyptus grandis.
III, Grindability
 Biomass grinding is an essential preprocessing unit operation. It helps reduce the particle size of the
biomass and makes it a more usable material for pelletizing or other handling unit operations.

 The grinding behavior (especially grinding energy) of raw and torrefied biomass is different.
Torrefaction can increase grindability by making the biomass particles shrink.

A study conducted by Wang et al. (2017) on the torrefaction of woody biomass indicated that the
grinding energy decreased by half, and that the particle size also decreased after torrefaction.

(A) Grinding energy consumption (B) particle size distribution (Ghiasi, 2019).
IV, Chemical properties
 Torrefaction results chemical changes in biomass: lower moisture, hydrogen, sulfur, and volatile
organics content; higher carbon content; and destruction and lower concentrations of organic structures
including hydroxyl and methoxyl groups, cellulose, hemicellulose, and lignin.

 A study on the torrefaction of hemicellulose, lignin, and cellulose at 210–300°C and a 20–60 min
residence time by Zheng et al. (2015) indicated that the thermal stability of the cellulose was the
highest, followed by lignin and hemicellulose.
IV, Hydrophobicity

 During the torrefaction process, the hydroxyl groups in the biomass are partially destroyed by
dehydration, which prevents the formation of hydrogen bonds, thereby causing the torrefied biomass
to become hydrophobic.
 The hydrophobic nature of biomass makes it less susceptible to degradation during storage.
1.4 Torrefaction technologies

 A typical torrefaction plant would include several units like biomass handling, preparation, dryer,
torrefier, and product cooler. Among these, the torrefaction reactor is most important.

 Many different torrefaction reactor designs—such as fixed bed, microwave, rotary drum, fluidized
bed, and augur-driven—have been conceptualized, tested, or operated.

 Common torrefaction reactor designs used at the laboratory- and pilot-scales are;
Reactor Classification by Heat Transfer Mode and FluidSolid
Contacting Mode
 2. Pyrolysis

CONTENT

 Introduction
 Types of Pyrolytic Reactors
 Parameters Influencing Pyrolysis Process
 Mechanism and Products of Biomass Pyrolysis

14
2.1 Overview
 Pyrolysis is defined as irreversible chemical change brought about by heat in the absence of
oxygen.

 During pyrolysis biomass undergoes a sequence of changes and normally yields a mixture of
gases, liquids and solid.

The solid is called charcoal while the condensable liquid is variously referred to as
pyroligneous liquid, pyroligneous liquor, pyroligneous acid or pyrolysis oil. The gas is called
producer gas or wood gas.

In a now obsolete process for production of methanol, acetic acid and acetone, wood is heated
in a retort in absence of air and the liquid vapours are condensed.

 This type of pyrolysis is generally called destructive distillation.

Cont.
• In a relatively recent development it is found that yields of volatiles (gas and liquid) increase with
the rate of heating. At sufficiently high heating rates all biomass can be nearly converted to
volatiles.

 This is known as fast pyrolysis.

• Although pyrolysis (as a process for charcoal making) has been known to man since time
immemorial, the complex pattern of series and parallel reactions involved in the process is not yet
fully understood.

Fig 4. Percentage composition of liquid,

solid and gaseous products
2.2 Pyrolysis Technology Variant
 Pyrolysis processes classified based on heating rates and residence time
Process Residence Heating Temp Products
Time Rate (C)
Carbonization Days Very low 400 Charcoal
Conventional 5 – 30 min Low 600 Oil, Gas, Char
Fast 0.5 – 5 sec Very high 650 Bio-oil
Flash-liquid < 1 sec High <650 Bio-oil
Flash-gas < 1 sec High <650 Chemicals, Gas
Ultra < 0.5 sec Very high 1000 Chemicals, Gas
Vacuum 2- 30 sec Medium 400 Bio-oil
Hydro-pyrolysis < 10 sec High <500 Bio-oil
Methano- < 10 sec High >700 Chemicals
pyrolysis
Cont.
Pyrolysis Technology Variant
 It is important to differentiate pyrolysis from gasification.

 Unlike pyrolysis, gasification of solid biomass is carried out in the presence of

oxygen, where the material is decomposed into producer gas or syngas by carefully
controlling the amount of oxygen present.

 Moreover, gasification aims to produce gaseous products while pyrolysis aims to

produce bio-oils and biochar.

 Liquefaction can also be confused with pyrolysis.

 The two processes differ in operating parameters, requirement of catalyst, and final
products.

 Liquefaction produces mainly liquid.

2.3 Types of pyrolytic reactors
• System Configuration

• A pyrolysis system unit typically consists of the equipment for biomass pre-
processing, the pyrolysis reactor, and equipment for downstream processing.
• Can be classified as units that produce heat and biochar (using slow pyrolysis) or
units that produce biochar and bio-oils (using fast pyrolysis),
Gas
Heat
Condensers

Air
Biomas
Pyrolysis Combustion Combustion
vapors Biomas
s Chamber Gases
s
Pyrolysis
vapors
PYROLYSIS PYROLYSIS
REACTORS Bio-oil
REACTORS
Char Char

(a) Biochar and bio-oil production (b) Biochar and heat production
Types of pyrolytic reactors
• Classification based on solid movement
 Biomass pyrolysis reactor commonly classified
depending on the way the solids move through the
reactor during pyrolysis.
 Type A:
No solid movement through the reactor
during pyrolysis (Batch reactors)
 Type B:
Moving bed (Shaft furnaces)
 Type C:
Movement caused by mechanical forces (e.g.
rotary kiln, rotating screw etc.)
 Type D:
Movement caused by fluid flow (e.g.,
fluidized bed, spouted bed, entrained bed
etc.)
• Classification based on method of heat
supplied
 Pyrolytic reactor can also be classified depending the
way heat is supplied to biomass:
Type 1:
Part of the material burnt inside the reactor to
provide the heat to carbonize the remainder
Type 2:
Direct heat transfer from hot gases produced
by combustion of the pyrolysis products or
any other fuel outside the reactor.
Type 3:
Direct heat transfer from inert hot material
(hot gases or sand introduced into the reactor).
Type 4:
Indirect heat transfer through the reactor walls
(i.e. external heat source due to combustion of
one or more pyrolysis products or any other
fuel).
Types of pyrolytic reactors
• Types of Pyrolysis Reactor Designs

 A number of different pyrolysis reactor designs are available.

 These include Fluidized bed, Re-circulating fluidized bed, Ablative, Rotating cone,
Auger (or screw), Vacuum, Transported bed, and Entrained flow.

Fluidized bed

Rotating cone
Types of pyrolytic reactors
 Types of Pyrolysis Reactor Designs

Vacuum Re-circulating fluidized bed

Types of pyrolytic reactors
• Types of Pyrolysis Reactor Designs
• As pyrolysis is a precursor to gasification and combustion, the same reactors used for
gasification can be used for pyrolysis.

• Bubbling fluidized bed reactors are simpler to design and construct than other reactor
designs, and have good gas to solids contact, good heat transfer, good temperature control,
and a large heat storage capacity.

• Circulating fluidized bed pyrolysis reactors are similar to bubbling fluidized bed reactors
but have shorter residence times for chars and vapors which results in higher gas
velocities, faster vapor and char escape, and higher char content in the bio-oil.

• They have higher processing capacity, better gas-solid contact, and improved ability to
handle solids that are difficult to fluidize.
Types of pyrolytic reactors
• Heat Transfer Modes and features of various reactors:
Reactor Mode of heat Typical features
type transfer
Fluidized 90% conduction; High heat transfer rates; Heat supply to fluidizing gas or to bed
bed 9% convection; directly; Limited char abrasion; Very good solids mixing; Particle size
1% radiation limit < 2 mm in smallest dimension; Simple reactor configuration

Circulating 80% conduction; High heat transfer rates; High char abrasion from biomass and char
fluidized 19% convection; erosion; Leading to high char in product; Char/solid heat carrier
bed 1% radiation separation required; Solids recycle required; Increased complexity of
system; Maximum particle sizes up to 6 mm; Possible liquids
cracking by hot solids; Possible catalytic activity from hot char;
Greater reactor wear possible
Entrained 4% conduction; Low heat transfer rates; Particle size limit < 2 mm; Limited gas/solid
flow 95% convection; mixing
1% radiation
Ablative 95% conduction; Accepts large size feedstocks; Very high mechanical char abrasion
4% convection; from biomass; Compact design; Heat supply problematical; Heat
1% radiation transfer gas not required; Particulate transport gas not always required
2.4 Parameters influencing pyrolysis process
• The basic phenomena that take place during pyrolysis:
• Heat transfer from a heat source, leading to an increase in temperature inside
the fuel;
• Initiation of pyrolysis reactions due to this increased temperature, leading to
the release of volatiles and the formation of char;
• Outflow of volatiles, resulting in heat transfer between the hot volatiles and
cooler unpyrolysed fuel;
• Condensation of some of the volatiles in the cooler parts of the fuel to produce
tar; and
• Autocatalytic secondary pyrolysis reactions due to these interactions.
Parameters influencing pyrolysis process
• Pyrolysis process control parameters:
• Important pyrolysis process control parameters include:
 Heat rate (length of heating and intensity),
 Prevailing temperature and pressure
 The presence of ambient atmosphere
 The chemical composition of the fuel (e.g., the biomass resource),
 Physical properties of the fuel (e.g. particle size, density),
 Residence time and the existence of catalysts.
• These parameters can be regulated by selection among different reactor types and heat
transfer modes, such as gas–solid convective heat transfer and solid–solid conductive
heat transfer.
2.5 Mechanism and products of biomass pyrolysis
• Overall Mechanism

• On heating, the constituents of biomass materials decompose following

different pathways and yielding a variety of products, each of which has its own
kinetic characteristics.

• In addition, secondary reaction products result from cross-reactions of primary

pyrolysis products and between pyrolysis products and the original feedstock
molecules.
Mechanism and products of biomass pyrolysis
• Biomass Figure
Pyrolysis
4.51 illustrate the main stages and products of the reactions of biomass pyrolysis [82].
High
VAPOUR PHASE Temperature CARBON BLACK
DERIVED TAR Slow (SOLID)
(VAPOUR OR H 2, CO, CH 4,
LIQUID) High Pressure
CO2, H 2O
High High High
Temperature Temperature Temperature
Slow Slow Slow
Low Pressure High Pressure High Pressure
Low High High High
Temperature Temperature Temperature Temperature
Fast TRANSIENT Fast CO
PRIMARY Fast PRIMARY
BIOMASS OXYGENATED CH4
TAR TAR FRAGMENTS H2 OLEFINS
(SOLID) (VAPOUR)
(LIQUID)
Low Pressure Low Pressure (VAPOUR) Low Pressure CO2

High Medium
Temperature Temperature
Slow Slow
Low Pressure Medium Pressure

SECONDARY WATER SOLUBLE

TAR OXYGENATED
(LIQUID) COMPUNDS
 Temperature: (VAPOUR)
Low T < 400 C < High T Low
Temperature
 Pressure: Slow
High Pressure
Low P < 75 kPa < High P
 Residence Time: CHARCOAL
(SOLID)
Fast < 0.1 second < Slow CO2, H 2O

Figure 4.51: Pyrolysis reactions