Chapter Four

Gasification

1
Introduction

2
 Cont…
The main gasifying
agents used for
gasification are Gasifying agents
Gasifying +solid carbon and
Mediums heavier
Oxygen hydrocarbons

Steam Low-molecular
weight gases like
CO and H2
Air
3
C-H-O diagram of the gasification process
Heating Values for Product Gas Based on
Gasifying Medium

If oxygen is used as the gasifying

agent, the conversion path moves
toward the oxygen corner

If steam is used as the

gasification agent, the path
is upward toward the
hydrogen corner

4
 The Gasification Process

Potential paths for

gasification

5
Typical Gasification reactions at 25oC

6
 Gasification Processes…
Preheating and drying

Pyrolysis

Char gasification and

Char combustion

=> The steps modeled in series but no sharp

boundary between them
7
 Char Gasification Reactions
The char produced through pyrolysis of biomass
is not necessarily pure carbon. It contains a
certain amount of hydrocarbon comprising
hydrogen and oxygen.
Biomass char is more porous and reactive than
coke. Its porosity is in the range of 40 to 50%
while that of coal char is 2 to 18%.
The reaction behavior of biomass char is
different from that of chars derived from coal,
lignite, or peat.
8
The reactivity of peat char decreases with conversion or time, while the
reactivity of biomass char increases with conversion . This reverse trend can
be attributed to the increasing catalytic activity of the biomass char’s alkali
metal constituents
9
 Char Gasification Reactions (Cont…)

• Gasification of biomass char involves

several reactions between the char
and the gasifying mediums.
✓Char +O2 → CO2 and CO
✓Char + CO2 → CO
✓Char + H2O→ CH4and CO
✓Char+ H2 →CH4

10
 Speed of Char Reactions
• The rate of gasification of char (comprising of
mainly carbon) depends primarily on its
reactivity and the reaction potential of the
gasifying medium.
• Oxygen is the most active, followed by steam
and carbon dioxide.
• The relative rates, R,
RC+O2 >> RC+H2O > RC+CO2 >> RC+H2

11
 Boudouard Reaction Model (Gasification of Char in CO2)
𝑘𝐽
R1 (Boudouard) 𝐶 + 𝐶𝑂2 ↔ 2𝐶𝑂 + 172
𝑚𝑜𝑙
The reaction proceeds according to the
following steps.
C(O)= carbon oxygen
complex

The rate of gasification in CO2 is insignificant

below 1000K (727oC)

12
• Water–Gas Reaction Model (Gasification of char in steam)

𝑘𝐽
R2 (water gas or steam) 𝐶 + 𝐻2𝑂 ↔ 𝐶𝑂 + 𝐻2 + 131
𝑚𝑜𝑙

• The presence of hydrogen has a strong inhibiting effect on

the char gasification by reacting with Cfas to form C(H)2 and
C(H) complexes.
• 30% H2 in the gasification=> reduced the gasification rate by
a factor of more than 15.
Continuous removal H2 is necessary to increase the reaction
13
Shift Reaction Model
R9 CO+H2O↔CO2+H2-41.2KJ/mol
• It increases the hydrogen content of the
gasification product at the expense of carbon
monoxide.
• It is a pre-step in syngas production when the
ratio of hydrogen and carbon monoxide in the
product gas is critical
• Above 1000 °C the shift reaction (R9) rapidly
reaches equilibrium, but at a lower
temperature it needs heterogeneous catalysts.
14
 Hydrogasification Reaction Model
• The gasification of char in hydrogen
environment C+2H2→CH4
• The reaction is much slower than the other
reactions

15
 Char Combustion Reactions
• Most gasification reactions are endothermic.
• To provide the required heat of reaction as well as
that required for heating, drying, and pyrolysis, a
certain amount of exothermic combustion
reaction is allowed in a gasifier.
• R5 (C + O2 → CO2) amount of heat (394 kJ) per
mol of carbon consumed.
• R4 (C + 1/2O2 → CO) produces 111 kJ/mol of
carbon
• When carbon comes in contact with oxygen both
R4 & R5 can take place.
16
 Char Combustion Reactions (cont.…)

• A partition coefficient, β, may be defined to

determine how oxygen will partition itself
between the two.
• The value of the partition coefficient β lies
between 1 and 2 and depends on temperature.
• 𝛽𝐶+𝑂2→2(𝛽−1)𝐶𝑂+(2−𝛽)𝐶𝑂2
6234
𝐶𝑂 −( )
• 𝛽= = 2400𝑒 𝑇
𝐶𝑂2
• Where T is surface temperature of the char
17
 Example
In an updraft gasifier, the water–gas
gasification reaction (C + H2O → CO + H2 +
131 kJ/mol) is to be carried out. Assume that
drying and other losses in the system need
50% additional heat. Find a means to adjust
the extent of the combustion reaction by
controlling the supply of oxygen and carbon
such that this need is met.

18
 Cont…
196.5𝑘𝐽
• 𝐶 + 𝐻2𝑂 → 𝐶𝑂 + 𝐻2 + ……1
𝑚𝑜𝑙
• The total amount of energy needed = (131+50%131)kJ/mol=196.5kJ/mol
(i.e 131 kJ of heat for gasification reaction and 50% for drying and other
losses)
• In oxygen-deficient or sub-stoichiometric conditions like that present in a
gasifier, the exothermic combustion reaction (C + 1/2O2 CO - 111 kJ/mol)
will be held instead of the complete combustion. Assume we need to burn d
amount of carbon to get 196.5kJ/mol of energy.
111𝑘𝐽
• 𝐶 + 0.5𝑂2 → 𝐶𝑂 – ∗ 𝑑…...2
𝑚𝑜𝑙
• We need to get the same energy output from equation 1 and 2.
• 196.5=d*111
• d= 1.77 mol of carbon should be combusted to get the required amount of
energy
• So equation 2 becomes 1.77𝐶 + 0.885𝑂2 → 1.77𝐶𝑂 − 196.5𝑘𝐽/𝑚𝑜𝑙 19
 Class activity
• In an updraft gasifier the gasification reaction
(C+CO2=>2CO+172KJ/mol) is to be carried
out. Assume that drying and other losses in
the system need 35% of additional heat. Find
a means to adjust the extent of combustion
reactions by controlling the supply of oxygen
and carbon such that this need is met.

20
 Catalytic gasification
• Reading Assignment

21
 Gasification Processes in the Reactors

Stages of gasification in an updraft gasifier Updraft gasifier 22

 Gasification reactions in a downdraft gasifier

Results in tar-free
but low-energy-content gases
Combustion of pyrolysis gas supplied the heat required for drying, pyrolysis and gasification
23
Bubbling fluidized-bed gasifier

• The fuel fed from

either the top or the
sides mixes relatively
fast over the whole
body of the fluid bed
• The gasifying medium
(air, oxygen, steam, or
their mixture) also
serves as the
fluidizing gas and so is
sent through the
bottom of the reactor.
24
 Draw backs of bubbling fluidized bed

• Cannot achieve complete char conversion

because of the back mixing of solid
• High degree of solid mixing helps to get uniform
temperature but owing to the intimate mixing of
fully gasified and partially gasified char
• Char particles entrained from a bubbling bed can
also contribute to the loss in the gasifier
• Low diffusion of oxygen from the bubbles to the
emulsion phase=>encourages combustion in this
phase=> gasification efficiency ↓
25
 Individual Assignment
Circulating fluidized bed reactors and Entrained
flow gasifires
• For what types of fuel are they suitable?
• What are the advantages and disadvantages
of these gasifiers?
(Due date: Monday 29/04/24)

26
 Kinetics of Gasification
• Stoichiometric calculations can help determine the
products of reaction.
• Not all reactions are instantaneous and
completely convert reactants into products.
Chemical Equilibrium
• To what extent a reaction progresses is
determined by its equilibrium state.
• Its kinetic rates, on the other hand, determine
how fast the reaction products are formed and
whether the reaction completes within the gasifier
chamber.

27
 Chemical Equilibrium (Con…)
Let us consider the reaction
when the two rates are equal
to each other (r1 = r2). This is
the equilibrium state.
At equilibrium,
• There is no further
change in the
concentration of the
reactants and the
products.
• The forward reaction
rate is equal to the
reverse reaction rate.
• The Gibbs free energy
of the system is at
minimum
• The entropy of the
system is at maximum .
28
 Cont…

• Under equilibrium state, we have

The ratio of rate constants for the

forward and reverse reactions is the
equilibrium constant, Ke.

29
 Reaction Rate Constant
• A rate constant, ki, is independent of the
concentration of reactants but is dependent on
the reaction temperature, T.
• The temperature dependency of the reaction rate
constant is expressed in Arrhenius form as:

Where A0 is a pre-exponential constant, R is the

universal gas constant, and E is the activation
energy for the reaction.

30
Gibbs Free Energy
∆G = ∆H − T∆S
• The change in enthalpy or entropy for a
reaction system is computed by finding the
enthalpy or entropy changes of individual
gases in the system.
• An alternative approach uses the empirical
equations

31
32
• The equilibrium constant of a reaction
occurring at a temperature T may be known
using the value of Gibbs free energy.

➢Here, ΔG is the standard Gibbs function of

reaction or free energy change for the
reaction, R is the universal gas constant, and T
is the gas temperature.

33
 Example
Find the equilibrium constant at 2000 K for the
reaction

34
Cont..
Take the values h and s
from table

35
Types of Gasifier

36
Range of applicability for biomass gasifier types

37
 Entrained-flow gasifiers for Biomass

1300-
1500oC

800oC

400-500oC
Limited supply of air

Choren process. The biomass is gasified in an entrained-flow gasifier 38

 Plasma Gasifiers
• Plasma Gasifiers
• Plasma, referred to as the "fourth
state of matter," is a very high
temperature, highly ionized
(electrically charged) gas capable
of conducting electrical current
• Mainly suitable for Municipal
solid waste
• Also called “plasma pyrolysis”
because it essentially involves
thermal disintegration of
carbonaceous material into
fragments of compounds in an
oxygen-starved environment
• Temp. Arc 13000oC
• When contact with sold waste the
T lowers 2700-4500oC
• Life of the reactor liner is an issue Picture of plasma torch 39
Comparison of Gasifier types

40