Unit -3

Thermal Oxidation for VOC Control

Lesson Goal
 To provide you with an understanding of the basic concepts of waste gas
incineration.

Lesson Objective.

Upon completion of this lesson, you should be able to:

 List three methods used to incinerate gaseous air pollutants.

 Identify the conditions necessary for efficient combustion of organic materials

in direct flame incinerator including the effects of gas conditioning,
Turbulence. temperature and residence time.

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 Unit - 3 Thermal Oxidation for VOC Control

1. Introduction

 Volatile organic compounds (VOCs) generally are fuels that are

easily combustible.

 Combustion similar with thermal oxidation and incineration

 The organic compounds are oxidized to CO2 and water

 Trace elements such as sulfur and chlorine are oxidized to species

such as SO2 and HCl.

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 Introduction….
 combustion requires the three legs of the fire triangle.

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 Introduction….

 Incinerators are equipment's where combustion process is carried out.

 Combustion is often used to control the emissions of organic

compounds from process industries

 At sufficient high temperature and adequate residence time, any

hydrocarbon can be oxidized to carbon dioxide and water by the

combustion process

 Combustion systems are often relatively simple devices accomplished of a

very high removal destruction efficiencies.

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Introduction….
Combustion systems consists of:
• Burners - which is used to ignite the fuel and organic materials
• Chamber- which is used to provides appropriate residence time
(detention time) for the oxidation process
Combustion systems may be designed to:
 Serious gaseous air pollutants destruction, such as the emission of
toxic or hazardous gases.
 Heat recovery
 Incomplete combustion of many organic compounds results in the
formation of aldehydes and organic acids, which may create an
additional pollution problem.
• Oxidizing organic compounds containing sulfur or halogens produce
unwanted pollutants such as sulfur dioxide, hydrochloric acid, and
hydrofluoric acid.
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 Introduction…...

 Many basic combustion systems are use. These devices are physically

similar, the operate conditions may be different.

Choosing the proper combustion device depends on many factors including:

 The type of hazardous contaminants in the waste stream

 Concentration of combustibles in the steam

 Process flow rate

 Control requirements, and

 Economic condition.

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 Introduction…
 Combustion is a chemical process occurring from the rapid combination of
oxygen

 ToThe
achieve
processcomplete combustion
of combustion the to
is also referred following conditions
as oxidation or incineration.
must be required
To achieve complete combustion. The following condition must be provide.

 Temperature high enough to ignite the waste/fuel mixture

 Turbulent mixing of the air and waste/fuel, and

 Sufficient residence time

 These three conditions are referred to as the “three Ts of combustion.” Time,

temperature, and turbulence govern the speed and completeness of
reaction.

 They are dependent variables since changing one can affect the other two.
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 Introduction…...

 Combustion is complete, the gaseous stream is converted to

carbon dioxide and water vapor
 combustion such as a mixture organic compounds
containing carbon, hydrogen and oxygen is described
by the over exothermic reaction
Combustion Stoichiometry
𝑏 𝑐 𝑏
CaHbOc + [ a + - ]O2 aCo2 + H2O……………….......2.1
4 2 2
exothermic reaction

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 Combustion Stoichiometry…

 Balancing any chemical reaction requires equating the number of atoms on

both the reactant and product side.

 In combustion reactions, one of the reactants is air.

 Air is approximately 20.9% 𝑂2 and 79.1% 𝑁2 by volume

 Air also has argon, 𝐶𝑂2 and trace amounts of many other species but we will
ignore these for now).

 This works out to 79.1/20.9 = 3.78 moles of 𝑁2 per mole of O2.

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Applications of the Combustion Equation

 Stoichiometric proportions for finding the correct air supply rate for a fuel
 Composition of the combustion products is useful during the design and
routine maintenance of a furnace installation.
Example 1
Write the balanced combustion equation for a general hydrocarbon (𝐶𝑎 𝐻𝑏)
burned in an oxygen-only atmosphere.
Step 1. Write out the equation.
𝑪𝒂 𝑯𝒃 + 𝑶𝟐 𝑪𝑶𝟐 + 𝑯𝟐 𝐎

Final balanced equation

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Example .2

Write the balanced combustion equation for a general

hydrocarbon (𝐶𝑎 𝐻𝑏 ) burned in air ( 𝑂2 + 3.76𝑁2 ).
Step 1. Write out the equation
𝐶𝑎 𝐻𝑏 +(𝑂2 + 3.78𝑁2 ) 𝐶𝑂2 + 𝐻2 O + 𝑁2
Step 2. Balance the equation.
𝑏 𝑏
𝐶𝑎 𝐻𝑏 +( a + ) (𝑂2 + 3.76𝑁2 ) a𝐶𝑂2 + 𝐻 O + 𝑁2
4 2 2
Final balanced equation
𝑏 𝑏 𝑏
𝐶𝑎 𝐻𝑏 +( a + ) (𝑂2 + 3.76𝑁2 ) a𝐶𝑂2 + 𝐻2 O + ( a+ ) 3.78𝑁2
2 2 2

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 Example 2.

1. How much 𝐶𝑂2 is produced when 200 gm of methane (𝐶𝐻4 ) is

combusted in pure oxygen.

2. When ethanol (𝐶2 𝐻5 OH) is completely combusted, the products are

carbon dioxide and water in an oxygen-only atmosphere

a. Write the balanced reaction equation.

b. If 150 mol/hr of water is produced, at what rate (molar) is the ethanol

combusted?

c. If 2000 kg of the ethanol is combusted, what mass of oxygen is

required?

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 Air-fuel rations

• One factor that influences combustion is the ratio of air to fuel in the feed.
• The air-fuel (AF) ratio can be expressed in terms of mass or moles

Example 4
C. Calculate the stoichiometric fuel/air mass ratio and product
gas composition for the combustion of heptane (C7H16) in
air.
𝐶7 𝐻16 + 11 (𝑂2 + 3.78 𝑁2 ) ===> 7𝐶𝑂2 + 8𝐻2 O + 11 x 3.78𝑁2

Molar mass of air 11 x (32 + 3.78*28) = 1516.24 gm/mole

The molar mass of heptane is 7 x 12 + 16 x 1 = 100gm/mole
Therefore, the air/ fuel mass ratio is

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 Air-fuel rations ……..

𝑀𝑎𝑖𝑟 11(32+3.78 ∗28) 1,516

𝑀𝑓𝑢𝑒𝑙
= 100
=
100
= 15.16
The total number of moles of combustion products is
7 + 8 + 11 x 3.78 = 7 + 8 + 41.5 = 56.58
The product gas composition, on a mole fraction basis, is
7
x𝐶𝑂2 = = 0.124
56.58
8
x𝐻2 o = = 0.141
56.58
41.5
x𝑁2 = = 0.711
56.58

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 Stoichiometric air

• The theoretical air required to complete combustion of fuel results from

the equation of stoichiometry of oxygen/fuel reaction.

• Stoichiometric air means the minimum air in stoichiometric mixture.

• The stoichiometric air/fuel ratio (AFR) can be calculated from the

reaction equation (g/g).

• For gas AFR is usually determined in 𝑚3 /𝑚3 .

The actual combustion air depends also on the assumed

air excess (equivalence ratio or stoichiometric ratio).

𝑎𝑐𝑡𝑢𝑎𝑙 𝑎𝑖𝑟
Sthiocimeteric ratio =
𝑠𝑡ℎ𝑖𝑜𝑐𝑖𝑚𝑒𝑡𝑒𝑟𝑖𝑐 𝑎𝑖𝑟

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 Excess air

• Insufficient air Combustion causes:-

A reduction in fuel efficiency
Creates highly toxic carbon monoxide gas
Produces soot
• To ensure there is enough oxygen to completely react with the fuel, extra
combustion air is usually supplied
• This extra air, called “Excess Air,” is expressed as the percent air above the
amount theoretically needed for complete combustion
• In real-world combustion, the excess air required for gaseous fuels is
typically about 15%
• Significantly more may be needed for liquid and solid fuels.
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Excess air….

To much excess air is also a source of waste as

 Loss of an excessive amount of heat
 Cause of the formation of carbon monoxide.

𝑎𝑐𝑡𝑢𝑎𝑙 𝑎𝑖𝑟 −𝑠𝑡ℎ𝑖𝑜𝑐𝑖𝑚𝑒𝑡𝑟𝑖𝑐 𝑎𝑖𝑟

Excess air = *100
𝑠𝑡ℎ𝑖𝑜𝑐𝑖𝑚𝑒𝑡𝑒𝑟𝑖𝑐 𝑎𝑖𝑟

Excess air = (sthiocimetric ratio – 1)*100

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 Excess air….

Example
Calculate the percentage excess air for methane burning. The flow
rate of methane and air are 20 and 290 𝑚3 /h respectively.
Stoichiometric air for methane burning is 10 𝑚3 /𝑚3
Assuming the flow rate of methane = 20𝑚3 /h
The flow rate of air = 290 𝑚3 /h
Air required = 20𝑚3 /h *10𝑚3 /𝑚3 =200 𝑚3 /h
𝑎𝑐𝑡𝑢𝑎𝑙 𝑎𝑖𝑟 290
Sthiocimeteric ratio = , = 1.45
𝑠𝑡ℎ𝑖𝑜𝑐𝑖𝑚𝑒𝑟𝑡𝑟𝑖𝑐 𝑎𝑖𝑟 200
Excess air = (1.45 – 1)*100 = 45%

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 Combustion process types

 Three combustion processes that control vapor emissions by

destroying collected vapors to prevent release to the environment.

(a) Thermal oxidation — flares,

(b) Thermal oxidation/ incineration, and

(c) Catalytic oxidation.

 Each of these processes has unique advantages and

disadvantages that require consideration for proper application.

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 Combustion process types…

(a) Thermal oxidation — flares

 Flaring is a combustion process in which VOCs are piped to a remote location
and burned in either an open or an enclosed flame.

 Flares can be used to control a wide variety of flammable VOC streams, and
can handle large fluctuations in VOC concentration, flow rate, and heating
value.

 The primary advantage of flares is that they have a very high turndown ratio
and rapid turndown response.

 Flares cannot be used for dilute VOC streams, less than about 7.5*10-4 J/m3 ,
without supplemental fuel because the open flame cannot be sustained. Adding

 supplemental fuel, such as natural gas or propane, increases operating cost.

Flammable gas sensors can be used to regulate supplemental fuel.
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 Combustion process types…
Table:1 Relative Destructability of VOC Pollutants by Combustion

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Types of flares

Flares divide in two categories

1. Elevated, open flare

2. Ground flare

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 Combustion process types…..

1. Elevated, open flare

 The commonly known flare is the elevated, open type.

 Elevated open flares prevent potentially dangerous Condition at

ground level

 elevating the open flame above working areas to reduce the effects of
noise, heat, smoke, and objectionable odors.

 The elevated flame burns freely in open air.

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 Elevated, open flare

Fig. elevated, open flare

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 Combustion processtypes …..

 Elevated, open flare system consists of a header to collect waste

gases, some form of assist to promote mixing (frequently steam is
used)

 an elevated burner tip with a pilot light, and

 Atmospheric combustion air is added by turbulence at the burner tip.

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 Elevated, open flare

• .

Fig 3.2 Steam-assisted flare: (a) steam off, (b) steam on

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 Thermal oxidation/incineration
 In thermal oxidation, the combustible waste gases pass over
and/or around a burner flame into a residence chamber where
oxidation of the waste gases is completed.

Fig. Schematic of a thermal incinerator.

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Thermal oxidation…..

Fig. Schematic of a thermal oxidation

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 Thermal oxidation….

The volume of thermal oxidation chamber calculated using eq. (2.1)

𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟 = (𝑇𝑅 )(𝐹𝑎𝑐𝑡𝑢𝑎𝑙 )……………………………….(2.1)Stop.
𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟 = volume of combustion chamber (𝑚3 )
𝑇𝑅 = residence time(sec)
𝑚3
𝐹𝑎𝑐𝑡𝑢𝑎𝑙 = actual volumetric flow rate of waste gas ( )
𝑠

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 Catalytic incinerator….

• Catalytic oxidation is very similar to thermal oxidation.

• The main difference is that after passing through the flame
area, the gases pass over a catalyst bed that promotes
oxidation at a lower temperature than does thermal
oxidation

Fig. Schematic of a catalytic incinerator

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Catalytic incinerator…..

Fig. Schematic of a catalytic incinerator

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 Catalytic incinerator….

𝑇𝑅 , empty = V/𝐹𝑎𝑐𝑡𝑢𝑎𝑙 ………………………………………..(3)

𝑉𝑣𝑜𝑖𝑑
𝑇𝑅 , actual = ………………………………................(4)
𝐹𝑎𝑐𝑡𝑢𝑎𝑙
Where, 𝑇𝑅 , empty = empty-bed residence time (sec)
𝑇𝑅 , actual = actual residence time (sec)
V= volume of empty catalytic chamber (𝑚3 )
𝑉𝑣𝑜𝑖𝑑 = void volume of catalytic chamber (𝑚3 )
𝑚3
𝐹𝑎𝑐𝑡𝑢𝑎𝑙 = actual volumetric flow rate of the waste gas ( )
𝑆

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 Catalytic incinerator….

Advantages of catalytic incinerator

• Lower operating Temperature
• Lower auxiliary fuel need
• Lower construction material cost

Disadvantages of catalytic incinerator

 Particulate fouling
 Catalyst poisoning

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 Operation and performance of incinerator

Operation
 The most important parameters in the design and operation
of an incineration system are what are called the 'three T's '
Temperature, Turbulence, and residence Time.
Temperature
 The reaction kinetics are very sensitive to temperature
 The higher the temperature, the faster the reaction
Timing
 A certain time has to be provided for the reaction to proceed
Turbulence
 Turbulence promotes mixing between the waste gas and
oxygen
 Proper mixing helps the reaction to proceed to completion
in the given time.

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 Performance of incinerator

 complete combustion results of 99 % control of VOC

 Turbulence, residence time and incinerator temperature are the primary incinerator parameters
affecting incinerator performance, other important parameters are the heat content and water
content of the gas stream, and the amount of excess combustion air.

Applicability

• It can be used to any organic material, their application is limited to a range of gas vapor
concentration

• to prevent explosions, the vapor concentration must be substantially below the gas lower
flammable level (lower explosive limit).

• Processes with the potential for excessive fluctuations in flow rate (i.e., process upsets) may
not be suitable for incinerator use, since control efficiency could decrease outside the
acceptable range

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