Process Engineering

By: Dr. H.Farzaneh

Chapter One (FossiI FueI Characteristics)
CoaI
Gaseous FueI
Liquid FueI
Process Engineering
By: Dr. H.Farzaneh
FossiI FueI Characteristics
Most chemical fuels are found in nature in the form of crude oil,
natural gas, and coal.
These fuels are called fossil fuels because they are believed to
have been formed by the decay of vegetable and animal matter
over many thousands of years under conditions of high pressure
and temperature and with a deficiency or absence of oxygen.
Other fuels such as gasoline, syngas (synthetic gas), and coke may
be derived from fossil fuels by some form of industrial or chemical
processing. These derived fuels are also called fossil fuels.
Process Engineering
By: Dr. H.Farzaneh
1- CoaI
1-1- Definition and categorization
Coal is an abundant solid fuel found in many locations around the
world in a variety of forms.
The American Society for Testing Materials, ASTM, has
established a ranking system that classifies coals as:
1) Anthracite
2) Bituminous
3) Sub bituminous
4) Lignite
according to their physical characteristics.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Coal is formed over long periods of time, in a progression shown from
left to right in below figure.
Process Engineering
By: Dr. H.Farzaneh
The bars on the ordinate show the division of the combustibles
between fixed carbon and volatile matter in the fuels.
Fixed carbon and volatile matter indicate roughly how much of the
fuel burns as a solid and as a thermally generated gas, respectively.
t is seen that the volatile matter and oxygen contained in the fuels
decrease with increasing age.
Process Engineering
By: Dr. H.Farzaneh
Anthracite Anthracite is the oldest coal from a geological perspective. t is a hard
coal composed mainly of carbon with little volatile content and
practically no moisture.
Peat Peat is a moist fuel, at the geologically young end of the scale, that
has a relatively low heating value.
t is not considered a coal but, nevertheless, follows the patterns of
characteristics shown in the figure.
Peat is regarded as an early stage or precursor of coal.
At the other extreme, anthracite is a geologically old, very hard, shiny
coal with high carbon content and high heating value.
Process Engineering
By: Dr. H.Farzaneh
Bituminous Bituminous is much more abundant than anthracite, has a slightly
lower carbon content, but also has a high heating value.
Subbituminous Subbituminous coal, lignite, and peat have successively poorer
heating values and higher volatile matter than bituminous.
Lignite Lignite is the youngest coal from a geological perspective. t is a soft
coal composed mainly of volatile matter and moisture content with
low fixed carbon.
Coal is a highly inhomogeneous material, of widely varying
composition, found in seams (layers) of varying thickness at varying
depths below the earth's surface.
Process Engineering
By: Dr. H.Farzaneh
1-2- CoaI AnaIyses
t is often difficult to obtain representative samples of coal because of
composition variations from location to location even within a given
seam.
As a result there are limits on the accuracy and adequacy of coal
analyses in assessing coal behavior in a given application.
Before discussing the nature of these analyses, it is important to
establish the basis on which they are conducted.
Process Engineering
By: Dr. H.Farzaneh
Coal contains varying amounts of loosely held moisture and
noncombustible materials or mineral matter (ash), which are of little
or no use.
The coal sample may be freshly taken from the mine, the as-mined
basis. t may have resided in a coal pile for months, and be analyzed
just before burning, the as-fired basis.
Coal ranking and analysis of combustion processes rely on two types
of analysis of coal composition: the proximate analysis and the
ultimate analysis.
Process Engineering
By: Dr. H.Farzaneh
The proximate analysis starts with a representative sample of coal.
A) The sample is first weighed, then raised to a temperature high
enough to drive off water, and then reweighed.
B) The weight loss divided by the initial weight gives the coal
moisture content,
C) The remaining material is then heated at a much higher
temperature, in the absence of oxygen, for a time long enough to
drive off gases. The resulting weight-loss fraction gives the volatile
matter content, VM, of the coal.
D) The remainder of the sample is then burned in air until only
noncombustibles remain. The weight loss gives the fixed carbon, FC,
and the remaining material is identified as non-combustible mineral
matter or ash,
Process Engineering
By: Dr. H.Farzaneh
The proximate analysis may be reported as percentages (or
fractions) of the four quantities:
1) Moisture
2) Ash
3) volatile matter
4) Fixed carbon,
or without ash and moisture and with the FC and VM normalized to
100%.
Sulfur, as a fraction of the coal mass, is sometimes reported with the
proximate analysis.
The proximate analysis, while providing very limited information, can
be performed with limited laboratory resources.
Process Engineering
By: Dr. H.Farzaneh
A more sophisticated and useful analysis is the ultimate analysis, a
chemical analysis that provides the elemental mass fractions of:
1) Carbon
2) Hydrogen
3) Nitrogen
4) Oxygen
5) Sulfur
usually on a dry, ash-free basis.
The ash content of the coal and heating value are sometimes
provided also.
Process Engineering
By: Dr. H.Farzaneh
ReIationship between uItimate anaIysis and proximate anaIysis
Process Engineering
By: Dr. H.Farzaneh
Data from a dry, ash-free analysis can be converted to another basis
as follows.
Dividing through by the total mass m and rearranging, we get the
following as the ratio of the mass of components to the total mass:
Where A is the ash fraction and M is the moisture fraction of the total
coal mass.
| | kg lb m m m m
m moist ash comp
, + + =
M A
m
m
comp
=1
Process Engineering
By: Dr. H.Farzaneh
A component of a coal analysis may be converted from the dry, ash-
free basis to some other basis by forming the product of the
component fraction and the basis adjustment factor.
Thus an equation for the wet and ashy volatile matter fraction in the
proximate analysis may be determined from the dry, ash-free
proximate analysis by using:
Where A and M are, respectively, the ash and moisture fractions for
the as-fired coal.
Here the as-fired (wet, ashy) mass fraction of volatile matter is the
product of the dry, ash-free mass fraction and the basis adjustment
factor.
ashfree drv
ashfree drv fired as
JM M A
JM mass Total es combustibl of Mass JM
,
,
) 1 (
) / (
=
=

Process Engineering
By: Dr. H.Farzaneh
EXAMPLE 1
f the as-fired moisture fraction for Schuylkill, Pa. anthracite culm is
4.5%, determine the as-fired proximate and heating value of the coal.
(Culm is the fine coal refuse remaining from anthracite mining.)
Solution:
Because ash is already present in the analysis, the appropriate
adjustment factor is:
1 - A - M = 1 - 0.0 - 0.045 = 0.955
VM
as-fired
= (0.955)(8.3) = 7.927
FC
as-fired
= (0.955)(32.6) = 31.133
A
as-fired
= (0.955)(59.1) = 56.411
M
as-fired
= 4.500
Check Sum = 99.971
Heating value
as-fired
= (0.955)(4918) = 4697 Btu/lb
m
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
1-3- CoaI Combustion Devices
Coal combustion is a two-phase process and the objective of the
burner is, as always, to achieve complete combustion of the fuel with
maximum energy efficiency.
Three common ways of burning solid fuels are currently in use and
are briefly reviewed below.
1-3-1- PuIverized FueI
The coal is ground to a very fine size (about 0.08mm or more than
70% pass through #200 mesh) when it can be made to behave rather
like a liquid if air is blown upwards through the powder.
The preparation and handling equipment is very expensive and
pulverized fuel installations are generally only economically viable in
very large scale applications, such as thermal power stations.
Process Engineering
By: Dr. H.Farzaneh
The fuel is injected in the form of a conical spray, inside a swirling
conical primary air supply in a fashion analogous to that for an oil
burner.
1-3-2- FIuidized Bed Combustors (FBC)
The basic principle of operation is that the coal is mixed with an inert
material (e.g. sand) and the bed is "fluidized by an upwards flow of
air.
Although the fluidization requires more fan power than the
conventional grate combustions, there are a number of advantages in
FBC:
(1) The bed temperature can be kept cooler than in the case of grate
combustion. Fluidized bed temperatures are generally within the
range 750-950
0c
. This means that ash fashion does not occur and the
low temperatures produce less NOX.
Process Engineering
By: Dr. H.Farzaneh
(2) High rates of heat transfer can be attained between the bed and
heat exchanger tubes immersed in it.
(3) A wide range of fuel types can be burned efficiently.
(4) Additives (such as limestone) can be used which react with oxides
of sulfur retaining the sulfur in the bed with consequent reduction in
SOx emission.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
1-3-3- Grate Combustion
The simplest, and most common, way of burning coal is by igniting a
bed of the fuel on a porous grate which allows air to rise through the
bed, either by buoyancy in smaller equipment or with fan assistance
in the larger, automatic stokers.
The combustion of a coal on a grate commences with heat transfer to
the raw coal from the adjacent incandescent fuel.
The first effect that this has is to drive off the volatile matter from the
coal.
The volatiles will then rise through the bed, partly reacting with the
hot carbonaceous material above it, to burn as a yellow flame above
the bed.
Process Engineering
By: Dr. H.Farzaneh
As the combustion process proceeds, the volatile matter decreases
until there is only the carbonaceous residue left, which burns with the
intense emission of radiation.
As the air enters the fuel bed from below, the initial reaction is the
combustion of the carbon to carbon dioxide.
n the hot upper region of the gas this is reduced to carbon monoxide:
CO2 + C 2CO
Which burns in the secondary air above the bed.
The effect of this is to decrease the concentration of oxygen from
21% at entry, to zero at about 100 mm above the grate.
Process Engineering
By: Dr. H.Farzaneh
At this point, there is a peak in the carbon dioxide concentration
which falls away as the reduction to carbon monoxide proceeds
Process Engineering
By: Dr. H.Farzaneh
1-3-4- Underfeed Stoker
Coal is fed into the retort by the action of a screw.
When combustion is completed at the top of the bed, a residue of ash
and clinker remains which falls to the sides of the retort.
The de-ashing of underfeed stokers is generally a manual process,
although some manufacturers offer automatic ash-handling facilities
Bituminous singles with an ash fashion temperature of around
1,200
0c
are an appropriate fuel for this type of device.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
1-3-5- Chain Grate Stoker
The coal is supplied by the traveling grate and the thickness of the
bed controlled by the guillotine door.
The speed of the grate and an air damper setting control the firing
rate.
The fuel for such boilers is usually smalls (about 13-25 mm) with a
high ash fashion temperature.
The ash falls from the end of the grate into a pit, from where it can be
removed by a conveyor belt or screw.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
1-4- Storage and handIing of coaI
Uncertainty in the availability and transportation of fuel necessitates
storage and subsequent handling.
Storing coal has its own disadvantages like build-up of inventory,
space constraints, deterioration in quality and potential fire hazards .
Other minor losses associated with the storage of coal include
oxidation, wind and carpet loss .
A 1% oxidation of coal has the same effect as 1% ash in coal. Wind
losses may account for nearly 0.5 1.0 % of the total loss.
Process Engineering
By: Dr. H.Farzaneh
The main goal of good coal storage is to minimize carpet loss and the
loss due to spontaneous combustion.
Formation of a soft carpet, comprising of coal dust and soil, causes
carpet loss.
On the other hand, if the temperature gradually rises in a coal heap,
then oxidation may lead to spontaneous combustion of coal stored.
Carpet losses can be reduced by:
1) Preparing a hard solid surface for coal to be stored
2) Preparing standard storage bays of concrete and brick
Process Engineering
By: Dr. H.Farzaneh
n industry, coal handling methods range from manual and conveyor
systems.
t would be advisable to minimize the handling of coal so that further
generation of fines and segregation effects are reduced .
The preparation of coal prior to feeding into the boiler is an important
step for achieving good combustion.
Large and irregular lumps of coal may cause the following problems:
1) Poor combustion conditions and inadequate furnace temperature
2) Higher excess air resulting in higher stack loss
3) ncrease of unburned in the ash
4) Low thermal efficiency
Process Engineering
By: Dr. H.Farzaneh
2- Gaseous FueI
Gas fuels are the most convenient because they require the least
amount of handling and are used in the simplest and most
maintenance-free burner systems.
Gas is delivered "on tap" via a distribution network and so is
suited for areas with a high population or industrial density.
However, large individual consumers do have gasholders and
some produce their own gas.
Gaseous fuels in common use are liquefied petroleum gases
(LPG), Natural gas, producer gas, blast furnace gas, coke oven
gas etc.
The calorific value of gaseous fuel is expressed in Kilocalories per
normal cubic meter (kCal/Nm
3
) i.e. at normal temperature (20
0C
)
and pressure (760 mm Hg).
Process Engineering
By: Dr. H.Farzaneh
2-1- Types of gaseous fueI
The following is a list of the types of gaseous fuel:
1) Fuels naturally found in nature:
- Natural gas
- Methane from coal mines
2) Fuel gases made from solid fuel
- Gases derived from coal
- Gases derived from waste and biomass
- From other industrial processes (blast furnace gas)
3) Gases made from petroleum
- Liquefied Petroleum gas (LPG)
- Refinery gases
- Gases from oil gasification
4) Gases from some fermentation process
Process Engineering
By: Dr. H.Farzaneh
2-2- Properties of gaseous fueIs
Since most gas combustion appliances cannot utilize the heat
content of the water vapor, gross calorific value is of little interest.
Fuel should be compared based on the net calorific value.
This is especially true for natural gas, since increased hydrogen
content results in high water formation during combustion.
Process Engineering
By: Dr. H.Farzaneh
LPG vapor is denser than air: butane is about twice as heavy as
air and propane about one and a half times as heavy as air.
Consequently, the vapor may flow along the ground and into
drains sinking to the lowest level of the surroundings and be
ignited at a considerable distance from the source of leakage.
n still air vapor will disperse slowly. Escape of even small
quantities of the liquefied gas can give rise to large volumes of
vapor / air mixture and thus cause considerable hazard.
To aid in the detection of atmospheric leaks, all LPG's are required
to be odorized.
There should be adequate ground level ventilation where LPG is
stored. For this very reason LPG cylinders should not be stored in
cellars or basements, which have no ventilation at ground level.
Process Engineering
By: Dr. H.Farzaneh
2-3- LPG
LPG is a predominant mixture of propane and Butane with a small
percentage of unsaturated (Propylene and Butylenes) and some
lighter C
2
as well as heavier C
5
fractions.
ncluded in the LPG range are propane (C
3
H
8
), Propylene(C
3
H
6
),
normal and iso-butane (C
4
H
10
)and Butylene(C
4
H
8
).
LPG may be defined as those hydrocarbons, which are gaseous
at normal atmospheric pressure, but may be condensed to the
liquid state at normal temperature, by the application of moderate
pressures.
Although they are normally used as gases, they are stored and
transported as liquids under pressure for convenience and ease of
handling.
Process Engineering
By: Dr. H.Farzaneh
2-4- NaturaI gas
Methane is the main constituent of natural gas and accounting for
about 95% of the total volume.
Other components are: Ethane, Propane, Butane, Pentane,
Nitrogen, Carbon Dioxide, and traces of other gases.
Very small amounts of sulphur compounds are also present.
Since methane is the largest component of natural gas, generally
properties of methane are used when comparing the properties of
natural gas to other fuels.
Natural gas is a high calorific value fuel requiring no storage
facilities.
t mixes with air readily and does not produce smoke or soot. t
contains no sulphur.
Process Engineering
By: Dr. H.Farzaneh
t is lighter than air and disperses into air easily in case of leak.
Comparison of chemicaI composition of various fueIs
Process Engineering
By: Dr. H.Farzaneh
3- Liquid FueIs
Liquid fuels like furnace oil and LSHS are predominantly used in
industrial application.
Liquid fuels are primarily derived from crude oil through cracking
and fractional distillation .
Cracking is a process by which long-chain hydrocarbons are
broken up into smaller molecules.
Fractional distillation separates high-boiling-point hydrocarbons
from those with lower boiling points.
Liquid fuels satisfy a wide range of combustion requirements and
are particularly attractive for transportation applications because of
their compactness and fluidity.
Process Engineering
By: Dr. H.Farzaneh
The various properties of liquid fuels are given below.
3-1-Density
This is defined as the ratio of the mass of the fuel to the volume of
the fuel at a reference temperature of 15C.
Density is measured by an instrument called hydrometer.
The knowledge of density is useful for quantity calculations and
assessing ignition quality. The unit of density is kg/m3.
Process Engineering
By: Dr. H.Farzaneh
3-2- Specific gravity
This is defined as the ratio of the weight of a given volume of oil to
the weight of the same volume of water at a given temperature.
The density of fuel, relative to water, is called specific gravity. The
specific gravity of water is defined as 1.
Since specific gravity is a ratio, it has no units. The measurement
of specific gravity is generally made by a hydrometer.
Specific gravity is used in calculations involving weights and
volumes.
Process Engineering
By: Dr. H.Farzaneh
3-3- Viscosity
The viscosity of a fluid is a measure of its internal resistance to
flow. Viscosity depends on temperature and decreases as the
temperature increases.
Any numerical value for viscosity has no meaning unless the
temperature is also specified. Viscosity is measured in Stokes /
Centistokes. Sometimes viscosity is also quoted in Engler, Saybolt
or Redwood.
Each type of oil has its own temperature - viscosity relationship.
The measurement of viscosity is made with an instrument called
Viscometer.
Viscosity is the most important characteristic in the storage and
use of fuel oil. t influences the degree of pre-heat required for
handling, storage and satisfactory atomization.
Process Engineering
By: Dr. H.Farzaneh
f the oil is too viscous, it may become difficult to pump, hard to
light the burner, and tough to operate.
Poor atomization may result in the formation of carbon deposits on
the burner tips or on the walls. Therefore pre-heating is necessary
for proper atomization.
3-4- FIash Point
The flash point of a fuel is the lowest temperature at which the fuel
can be heated so that the vapour gives off flashes momentarily
when an open flame is passed over it. Flash point for furnace oil is
66
o
C.
3-5- Pour Point
The pour point of a fuel is the lowest temperature at which it will
pour or flow when cooled under prescribed conditions. t is a very
rough indication of the lowest temperature at which fuel oil is
readily pumpable
Process Engineering
By: Dr. H.Farzaneh
3-6- Specific Heat
Specific heat is the amount of kcal needed to raise the
temperature of 1 kg of oil by 1
oC
.
The unit of specific heat is kcal/kg
oC
. t varies from 0.22to 0.28
depending on the oil specific gravity.
The specific heat determines how much steam or electrical energy
it takes to heat oil to a desired temperature. Light oils have a low
specific heat, whereas heavier oils have a higher specific heat.
3-7- CaIorific VaIue
The calorific value is the measurement of heat or energy
produced, and is measured either as gross calorific value or net
calorific value. The difference being the latent heat of
condensation of the water vapour produced during the combustion
process. Gross calorific value (GCV) assumes all vapour
produced during the combustion process is fully condensed.
Process Engineering
By: Dr. H.Farzaneh
Net calorific value (NCV) assumes the water leaves with the
combustion products without fully being condensed. Fuels should
be compared based on the net calorific value.
The calorific value of coal varies considerably depending on the
ash, moisture content and the type of coal while calorific value of
fuel oils are much more consistent. The typical Gross Calorific
Values of some of the commonly used liquid fuels are given
below:
Fuel Oil Gross Calorific Value (kCal/kg)
Kerosene - 11,100
Diesel Oil - 10,800
L.D.O - 10,700
Furnace Oil - 10,500
LSHS - 10,600
Process Engineering
By: Dr. H.Farzaneh
3-8- SuIphur
The amount of sulphur in the fuel oil depends mainly on the
source of the crude oil and to a lesser extent on the refining
process.
The normal sulfur content for the residual fuel oil (furnace oil) is in
the order of 2-4 %.
Fuel oil Percentage of Sulphur
Kerosene 0.05- 0.2
Diesel Oil 0.05 - 0.25
L.D.O 0.5 - 1.8
Furnace Oil 2.0 - 4.0
LSHS < 0.5
The main disadvantage of sulphur is the risk of corrosion by
sulphuric acid formed during and after combustion, and
condensing in cool parts of the chimney or stack, air pre heater
and economiser .
Process Engineering
By: Dr. H.Farzaneh
3-9- Ash Content
The ash value is related to the inorganic material in the fuel oil.
The ash levels of distillate fuels are negligible.
Residual fuels have more of the ash-forming constituents. These
salts may be compounds of sodium, vanadium, calcium,
magnesium, silicon, iron, aluminum, nickel, etc.
Typically, the ash value is in the range 0.03- 0.07%.
Excessive ash in liquid fuels can cause fouling deposits in the
combustion equipment.
Ash has erosive effect on the burner tips, causes damage to the
refractories at high temperatures and gives rise to high
temperature corrosion and fouling of equipments.
Process Engineering
By: Dr. H.Farzaneh
3-10- Carbon Residue
Carbon residue indicates the tendency of oil to deposit a
carbonaceous solid residue on a hot surface, such as a burner or
injection nozzle, when its vaporizable constituents evaporate.
Residual oil contains carbon residue ranging from 1 percent or
more.
3-11- Water Content
Water content of furnace oil when supplied is normally very low as
the product at refinery site is handled hot and maximum limit of
1% is specified in the standard.
Water may be present in free or emulsified form and can cause
damage to the inside furnace surfaces during combustion
especially if it contains dissolved salts.
t can also cause spluttering of the flame at the burner tip, possibly
extinguishing the flame and reducing the flame temperature or
lengthening the flame.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
3-12- Storage of FueI oiI
t can be potentially hazardous to store furnace oil in barrels.
A better practice is to store it in cylindrical tanks, either above or
below the ground.
Furnace oil, that is delivered, may contain dust, water and other
contaminants.
The sizing of storage tank facility is very important.
A recommended storage estimate is to provide for at least 10 days
of normal consumption.
ndustrial heating fuel storage tanks are generally vertical mild
steel tanks mounted above ground.
Process Engineering
By: Dr. H.Farzaneh
t is prudent for safety and environmental reasons to build bund
walls around tanks to contain accidental spillages.
As a certain amount of settlement of solids and sludge will occur
in tanks over time, cleaning should be carried out at regular
intervals-annually for heavy fuels and every two years for light
fuels.
A little care should be taken when oil is decanted from the tanker
to storage tank. All leaks from joints, flanges and pipelines must
be attended at the earliest.
Fuel oil should be free from possible contaminants such as dirt,
sludge and water before it is fed to the combustion system.
LOSS OF EVEN ONE DROP OF OIL EVERY SECOND CAN
COST YOU OVER 4000 LITRES A YEAR
Process Engineering
By: Dr. H.Farzaneh
3-13- RemovaI of Contaminants
Furnace oil arrives at the factory site either in tank lorries by road
or by rail.
Oil is then decanted into the main storage tank.
To prevent contaminants such as rags, cotton waste, loose nuts or
bolts or screws entering the system and damaging the pump,
coarse strainer of 10 mesh size (not more than 3 holes per linear
inch) is positioned on the entry pipe to the storage tanks.
Progressively finer strainers should be provided at various points
in the oil supply system to filter away finer contaminants such as
external dust and dirt, sludge or free carbon.
t is advisable to provide these filters in duplicate to enable one
filter to be cleaned while oil supply is maintained through the
other.
Process Engineering
By: Dr. H.Farzaneh
DupIex Arrangement of Strainers in a PipeIine
gives sizing of strainers at various Iocations.
Process Engineering
By: Dr. H.Farzaneh
3-14- Pumping
Heavy fuel oils are best pumped using positive displacement
pumps, as they are able to get fuel moving when it is cold.
A circulation gear pump running on LDO should give between
7000-10000 hours of service.
Diaphragm pumps have a shorter service life, but are easier and
less expensive to repair.
A centrifugal pump is not recommended, because as the oil
viscosity increases, the efficiency of the pump drops sharply and
the horsepower required increases.
Light fuels are best pumped with centrifugal or turbine pumps.
When higher pressures are required, piston or diaphragm pumps
should be used.
Process Engineering
By: Dr. H.Farzaneh
3-15- Storage Temperature and Pumping Temperature
The viscosity of furnace oil and LSHS increases with decrease in
temperature, which makes it difficult to pump the oil.
At low ambient temperatures (below 25
oC
), furnace oil is not easily
pumpable.
To circumvent this, preheating of oil is accomplished in two ways:
a) the entire tank may be preheated. n this form of bulk heating,
steam coils are placed at the bottom of the tank, which is fully
insulated;
b) the oil can be heated as it flows out with an outflow heater. To
reduce steam requirements, it is advisable to insulate tanks where
bulk heating is used.
Bulk heating may be necessary if flow rates are high enough to
make outflow heaters of adequate capacity impractical, or when a
fuel such as Low Sulphur Heavy Stock (LSHS) is used.
Process Engineering
By: Dr. H.Farzaneh
3-16- Temperature ControI
Thermostatic temperature control of the oil is necessary to prevent
overheating, especially when oil flow is reduced or stopped.
This is particularly important for electric heaters, since oil may get
carbonized when there is no flow and the heater is on.
Thermostats should be provided at a region where the oil flows
freely into the suction pipe.
The temperature at which oil can readily be pumped depends on
the grade of oil being handled.
Oil should never be stored at a temperature above that necessary
for pumping as this leads to higher energy consumption.
Process Engineering
By: Dr. H.Farzaneh
References
Combustion Engineering and Fuel Technology, Oxford & BH Publishing
Company - A.K.Shaha
Department of Coal, Government of ndia. Coal and Cement ndustry
Efficient utilization. 1985
Bureau of Energy Efficiency. Energy Efficiency in Thermal Utilities.
Chapter 1. 2004
Shaha, A.K. Combustion Engineering and Fuel Technology. Oxford &
BH Publishing Company
Process Engineering
By: Dr. H.Farzaneh
Chapter Two (FueI Conversion TechnoIogy)
Gassification Process
CIassification of gasifiers
FIuidized bed reactor (Gasifier)
Integrated Gasification Combined CycIe (IGCC)
Liquefaction
PetroIeum oiI distiIIation
Cracking Process
Reforming Process
ThermaI Power pIants
Process Engineering
By: Dr. H.Farzaneh
1- Gasification Process
Gasification is a process that converts carbonaceous materials,
such as coal, petroleum, or biomass, into carbon monoxide and
hydrogen by reacting the raw material at high temperatures with a
controlled amount of oxygen and/or steam.
The resulting gas mixture is called synthesis gas or syngas and is
itself a fuel.
Gasification is a very efficient method for extracting energy from
many different types of organic materials, and also has
applications as a clean waste disposal technique.
The advantage of gasification is that using the syngas is more
efficient than direct combustion of the original fuel, more of the
energy contained in the fuel is extracted.
Gasification of fossil fuels is currently widely used on industrial
scales to generate electricity
Process Engineering
By: Dr. H.Farzaneh
n a gasifier, the carbonaceous material undergoes several
different processes:
1) The pyrolysis (or devolatilization) process occurs as the
carbonaceous particle heats up. Volatiles are released and char is
produced, resulting in up to 70% weight loss for coal. The process
is dependent on the properties of the carbonaceous material and
determines the structure and composition of the char, which will
then undergo gasification reactions.
2) The combustion process occurs as the volatile products and some
of the char reacts with oxygen to form carbon dioxide and carbon
monoxide, which provides heat for the subsequent gasification
reactions.
3) The gasification process occurs as the char reacts with carbon
dioxide and steam to produce carbon monoxide and hydrogen
Process Engineering
By: Dr. H.Farzaneh
4) n addition, the reversible gas phase water gas shift reaction
reaches equilibrium very fast at the temperatures in a gasifier.
This balances the concentrations of carbon monoxide, steam,
carbon dioxide and hydrogen.
The principle reactions taking place are:
GJ H CO O H CO
GJ H CO O H C
GJ H CO O H C
GJ CO O C
GJ CO CO C
GJ CO O C
9 . 41
4 . 82 2 2
121
240 2 2
165 2
8 . 404
2 2 2
2 2 2
2 2
2
2
2 2
+ + +
+ +
+ +
+ +
+
+ +
Process Engineering
By: Dr. H.Farzaneh
2- CIassification of gasifiers
Operating temperature for the different gasifiers is to a large
extent dictated by the ash properties of the coal.
Depending on the gasifier, it is desirable either to remove the ash
dry at lower temperatures (non-slagging gasifiers) or as a low
viscosity liquid at high temperatures (slagging gasifiers). For all
gasifiers it is essential to avoid that soft ash particles stick to
process equipment and terminate operation.
Process Engineering
By: Dr. H.Farzaneh
Fixed bed gasifiers and fluidized bed gasifiers have low (425-650
C
) and moderate (900-1050
C
) outlet gas temperatures,
respectively.
Entrained flow gasifiers have high outlet temperatures (1250-1600
C
) and operate in the slagging range (the ash is fully liquid with low
viscosity).
Benefits of entrained flow gasifiers include:
1) Ability to handle practically any coal as feed
2) Syngas is free of oils and tars
3) High carbon conversion
4) Low methane production, suitable for synthesis gas products
5) High throughput because of high reaction rates at elevated
temperature
Process Engineering
By: Dr. H.Farzaneh
Fixed-Bed
FIuidized-Bed
Entrained-FIow
Process Engineering
By: Dr. H.Farzaneh
3- FIuidized bed reactor (Gasifier)
A fluidized bed reactor (FBR) is a type of reactor device that can
be used to carry out a variety of multiphase chemical reactions.
n this type of reactor, a fluid (gas or liquid) is passed through a
granular solid material (usually a catalyst possibly shaped as tiny
spheres) at high enough velocities to suspend the solid and cause
it to behave as though it were a fluid.
This process, known as fluidization, imparts many important
advantages to the FBR. As a result, the fluidized bed reactor is
now used in many industrial applications
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
3-1- Basic principIes
The solid substrate (the catalytic material upon which chemical
species react) material in the fluidized bed reactor is typically
supported by a porous plate, known as a distributor
The fluid is then forced through the distributor up through the solid
material.
At lower fluid velocities, the solids remain in place as the fluid
passes through the voids in the material. The pressure drop may
be calculated from Ergun formula:
75 . 1
/
) 1 ( 150
1
0
3
2
0
+

A

c
c
c

J D
J
D
L
Pg
p s
p s
c
Process Engineering
By: Dr. H.Farzaneh
Where:
c
g
: Newton's law proportionality factor, 32.174 ft-lb/lb
f
-s
2
L : Height of packed or fluidized bed
s

: Sphericity
p
v
: Volume of single particle
p p
p
s
D s
v 6
=
p
s
: Surface are of single particle
p
D : Diameter of spherical particle
0
J
: Volumetric average velocity in empty tower or superficial speed
c : Porosity or volume fraction of voids in bed of solid
Process Engineering
By: Dr. H.Farzaneh
3-1-1- Condition of fIuidization
Consider a vertical tube partly filled with a fine granular material
such as catalytic cracking catalyst.
The tube is open at the top and has a porous plate at the bottom
to support the bed of catalyst and to distribute the flow uniformly
over the entire cross section
Fixed-bed
Fluidized-bed
A
B
C
OM
J
P A
P
r
e
s
s
u
r
e

D
r
o
p

a
n
d

B
e
d

H
e
i
g
h
t
Superficial Velocity
L
P A
Process Engineering
By: Dr. H.Farzaneh
As the velocity is gradually increased, the pressure drop
increases, but the particle do not move and the bed height
remains the same.
Point A : At a certain velocity, the pressure drop across the bed
counterbalances the force of gravity on the particles to move.
Sometimes the bed expands slightly with the grains still in contact,
since just a slight increase in can offset an increase of several
percent in and keep constant.
Point B : With a further increase in velocity, the particles become
separated enough to move about in the bed and true fluidization
begins.
n this point the pressure drop across the bed stays constant and
the bed height continues to increase.
c
0
J P A
Process Engineering
By: Dr. H.Farzaneh
f the flow rate to fluidized bed is gradually reduced, the pressure
drop remains constant and the bed height decreases, following
the line BC which was observed for increasing velocity.
3-1-2- Minimum fIuidization veIocity
An equation for the minimum fluidization velocity can be obtained
by setting the pressure drop across the bed equal to the weight of
the bed per unit area of cross section, allowing for the buoyant
force of the displaced fluid :
At incipient fluidization, is the minimum porosity
c
M
c
) )( 1 ( c =
A
p M
c
g
g
L
P
Process Engineering
By: Dr. H.Farzaneh
2 2
3
1 150
) (
P s
M
M
p
OM
D
g
J
c
c

~
Thus by rearrangement of Ergun equation and take it equal to the
pressure drop across the bed we will have:
For very small particle, only laminar flow term of the Ergun equation
is significant. With Re<1000, the equation for minimum fluidization
velocity becomes:
For Re >1000
3
2
0
3 2 2
0
75 . 1 ) 1 ( 150
) (
M P s
M
M p s
M
p
D
J
D
J
g
c

c
c
+

=
2 / 1
3
75 . 1
) (
(
(

c
M p P s
OM
g D
J
Process Engineering
By: Dr. H.Farzaneh
ExampIe 2
A bed of pulverized coal, 8 ft deep, is to be gasified with hot air. The
particle have a density of 1.25g /cm
3
and an average size of 1.5 mm
What is the minimum fluidization velocity using hot air at 600 K
.
Solution:
The quantities needed are:
From the Ergun equation we will have:
54 . 0
1
/ 25 . 1 ) ( 00058 . 0 25 . 1
) ( 0003 . 0
3
=
=
~ = A
=
M
cm g densitv air
poise P
c

41 . 28506 96 . 135
) 54 . 0 )( 15 . 0 )( 1 (
) 00058 . 0 ( 75 . 1
) 54 . 0 ( ) 15 . 0 )( 1 (
) 54 . 0 1 ( ) 0003 . 0 ( 150
) 25 . 1 ( 980
2
0 0
3
2
0
3 2
0
= +
+

=
M M
M M
J J
J J
s m J
OM
/ 14 . 1 =
Process Engineering
By: Dr. H.Farzaneh
3-1-3- Heat transfer in fIuidized bed
The mechanism is not yet fully understood, and back up tests are
needed to correlate properly. But the following guidelines apply:
1) Radiation occurs from the bed to tubes set in. The Boltzman
equation applies roughly. About 40 to 50 percent of heat transfer
is by radiation.
2) Due to rapid movement of particles, there is much higher heat
transfer than by normal convection due to:
a) Particles touching surfaces, with transfer by conduction
b) Breakdown of the boundary layer particles
c) Greater turbulence due to particles constantly "falling through the
gas
d) Particle to particle transfer
e) The effective density is much higher than for a gas
Process Engineering
By: Dr. H.Farzaneh
3) The effects of radiation and convection are not strictly additive
4) Particle size is important.
5) Heat transfer varies about 10% in range 0.3 to 1.2 ms
-1
with
fluidizing velocity. Above this level the coefficient falls off rapidly,
due to large bubbles forming in the bed.
6) The effect of pressure variation is small.
dp Transfer heat Convective
Process Engineering
By: Dr. H.Farzaneh
4- INTEGRATED GASIFICATION COMBINED CYCLE (IGCC)
The integrated gasification combined cycle (GCC) produces
electricity from a solid or liquid fuel.
First, the fuel is converted to syngas which is a mixture of
hydrogen and carbon monoxide.
Second, the syngas is converted to electricity in a combined cycle
power block consisting of a gas turbine process and a steam
turbine process which includes a heat recovery steam generator
(HRSG).
The combined cycle technology is similar to the technology used
in modern natural gas fired power plants.
Process Engineering
By: Dr. H.Farzaneh
4-1- IGCC process description
The coal is supplied to the gasifier where it is partially oxidized
under pressure (30-80 bar). The plant uses oxygen as oxidant and
therefore has an air separation unit (ASU).
n the gasifier, which is of the entrained flow slagging type, the
temperature may exceed 1500
C
.
The high temperature ensures that the ash is converted to a liquid
slag with low viscosity, so that it may easily flow out of the gasifier.
n addition to its chemical energy (heating value), the hot raw
syngas contains sensible heat which may be recovered in heat
exchangers to produce steam for the steam turbine.
The use of syngas coolers for this purpose increases efficiency,
but adds capital costs.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
n the gas clean up process, particles, sulfur and other impurities
are removed. At this point, CO
2
may also be captured.
Because of the high partial pressures of the species and the low
volume flow of syngas, the gas clean up process is very efficient
and low cost compared to traditional flue gas cleaning.
The clean syngas is then fed to the gas turbine for production of
electricity. Gas turbines for syngas operation are commercially
available. Compared to natural gas operation, some minor
modifications in combustors and operating conditions are
required.
Most of the sensible heat in the hot gas turbine exhaust gas is
recovered in the heat recovery steam generator (HRSG) which
supplies the steam to a turbine for additional electricity production.
Process Engineering
By: Dr. H.Farzaneh
4-2- Factors infIuence the efficiency:
1) Coal type: Coals of high rank can be gasified more efficiently than
coals of low rank. The higher moisture and ash content of low rank
coals require a higher degree of oxidation (more oxygen) to
achieve slagging temperatures because of the energy needed to
vaporize the moisture and melt the ash. Most recent studies have
focused on high rank coals.
2) Gasification technology: Gasifiers with a dry feed are more
efficient than gasifiers with a slurry feed because less water must
be vaporized. Gasifier technologies which include syngas coolers
for heat recovery of the sensible heat of the hot gas, are more
efficient than those with a water quench.
3) Degree of ASU integration: ntegration of the air separation unit
with the gas turbine increases the electrical efficiency. By
supplying part or all of the ASU air from the GT compressor outlet,
less efficient compression in a separate compressor is reduced or
avoided.
Process Engineering
By: Dr. H.Farzaneh
4) Technology level: Gas turbine technology and turbine inlet
temperature will together with the choice of steam cycle have a
significant impact on electrical efficiency.
While the three first bullets addresses the efficiency gap between
an GCC and an NGCC, the last bullet points to the fact that
improvements in combined cycle technology will also benefit the
GCC.
A review of recent studies of GCC plants indicates efficiencies in
the range 38.0- 47.4% (LHV). The wide range is explained by the
above factors.
Process Engineering
By: Dr. H.Farzaneh
Schematic of Air Separation Unit
N
2
52%
78 K
1 atm
99 K
5 atm
468 K
9 atm
N
2
98%
82 K
1 atm
N
2
99%
78 K
1 atm
O
2
99%
78 K
1 atm
Process Engineering
By: Dr. H.Farzaneh
5- LIQUEFACTION
Coal liquefaction offers the following benefits:
Largely proven technology for the manufacture of useful liquid
products.
Ability to manufacture transportation fuels from abundant coal.
nsurance against depleting oil stocks and oil supply problems.
Coal is a solid with a high carbon content but a hydrogen content
of typically 5% and never more than 6%.
n comparison with liquid fuels it is inconvenient to handle and
unsuited to some applications.
Process Engineering
By: Dr. H.Farzaneh
Most notably, it cannot be used directly to fuel the internal
combustion (C) engines and turbines that dominate transportation
infrastructure worldwide.
Transportation fuels for these are derived overwhelmingly from
crude oil, which has about twice the hydrogen content of coal.
They account for over 50% of total oil consumption.
The hydrogen content of these fuels varies from ~12.5% in some
gasoline to 14.5% in aviation turbine fuels.
For coal to replace them, it must be converted to liquids with
similar hydrogen content.
This can be achieved either by removing carbon or by adding
hydrogen, either directly or indirectly.
Process Engineering
By: Dr. H.Farzaneh
The first approach is known as carbonization or pyrolysis and the
second as liquefaction.
1-1- Carbonization
High-temperature carbonization is the oldest route for the
production of liquids from coal, wherein hydrocarbon liquid is
predominantly a byproduct of coke-making.
The low yields (<~5%) of liquid product and relatively high
upgrading costs mean that traditional high-temperature
carbonization is not an option for the production of liquid fuels on a
commercial basis.
Mild pyrolysis is also a carbonization technology but with less severe
operating conditions.
Process Engineering
By: Dr. H.Farzaneh
Mild pyrolysis consists of heating the coal to a temperature in the
range ~450-650C (compared with ~950C in high temperature
carbonization), driving off volatile matter from the original coal and
generating other volatile organic compounds formed by thermal
decomposition during the treatment.
Liquid yields are higher than for high-temperature carbonization,
but are still no more than 15-20% at most.
The main product is a char with a reduced hydrogen and
heteroatom content.
A higher yield of liquids can be obtained by rapid pyrolysis.
These processes operate at temperatures up to 1200C, but the
residence time of the coal is significantly reduced, to a few
seconds at most.
Process Engineering
By: Dr. H.Farzaneh
Rapid pyrolysis is aimed at producing chemical feedstock rather
than liquid fuels and process economics are likely to be highly
unfavorable for production of liquid fuels. There also appear to be
unresolved engineering difficulties.
The disadvantage of all pyrolysis and carbonization processes is
that, if the hydrogen content of the feedstock coal is to be
increased to the point at which it becomes a distillable liquid, the
hydrogen content of the remaining solid must be reduced.
n any case, the liquids produced are still of low quality and
require, at least, additional treatment to remove solid
contaminants and water.
The LFC process (is a mild pyrolysis method which has two
saleable products:
1) low-sulphur, high heating-value solid known as 'process-derived
fuel' (PDF) and 2) hydrocarbon liquid known as 'coal-derived
liquid' (CDL).
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
1) The coal is crushed and screened and then heated by a hot gas
stream on a rotary grate dryer.
2) The dried coal is then fed into the main rotary grate pyrolyser
where it is heated to ~540C by a hot recycled gas stream.
3) On discharge from the pyrolyser the solids are cooled and pass to
a deactivation step, consisting of treatment in a vibrating fluidized
bed with a gas stream of controlled oxygen content.
4) The gas stream leaving the pyrolyser is cooled in a quench tower,
condensing CDL but leaving water in the gas phase.
5) Most of the residual gas is recycled to the pyrolyser, some being
burned in the pyrolyser combustor to provide the necessary heat.
6) The remaining gas is burned in the dryer combustor and passes
into the dryer gas recycle loop.
Process Engineering
By: Dr. H.Farzaneh
7) The purge from this loop is wet-scrubbed to remove particulates
and sulphur oxides.
8) Purge liquor from the scrubbers is discharged to ponds for
evaporation.
9) After being stabilized by mild oxidation, the PDF, a low-sulphur
reactive fuel suitable for pulverized coal-fired boilers, is shipped by
rail to power plant.
Process Engineering
By: Dr. H.Farzaneh
1-2- Direct Liquefaction
Direct liquefaction processes aim to add hydrogen to the organic
structure of the coal, breaking it down only as far as is necessary
to produce distillable liquids.
The liquid products from direct liquefaction processes are of much
higher quality than those from pyrolysis processes and can be
used unblended for most stationary fuel applications.
Direct liquefaction processes can conveniently be divided into two
main groups:
1) A single-stage direct liquefaction process gives distillates via one
primary reactor or a train of reactors in series.
2) A two-stage direct liquefaction process is designed to give distillate
products via two reactors or reactor trains in series.
Process Engineering
By: Dr. H.Farzaneh
1-2-1- SingIe Liquefaction
The major method of this group is named as Kohleoel process
Process Engineering
By: Dr. H.Farzaneh
Coal is slurried with a process-derived recycle solvent and a 'red
mud' disposable iron catalyst, pressurized and preheated .
H
2
is added and the mixture passed to an up-flow tubular reactor,
operating typically at 300 bar and 470
C
.
The specific coal feed rate to this reactor is in the range 0.5- 0.65
tones/hour
Products from the top of the reactor pass to a hot separator.
The overheads from this separator remain in the gas phase and
are hydro treated at a temperature of 350-420C in a fixed-bed
reactor at the same pressure as the main reactor.
The hydro treated products are depressurized and cooled in two
stages.
Process Engineering
By: Dr. H.Farzaneh
The liquid product from the first of these stages is recycled to the
slurring step as part of the solvent.
The liquid product from the second stage is routed to an
atmospheric distillation column, yielding a light oil (C5 - 200
C
bp)
and a medium oil (200-325
C
bp) product.
The bottoms from the original hot separator pass to a vacuum
distillation column to recover distillable liquids.
These are added to the hydro treating reactor feed, and are
subsequently largely recycled as solvent.
The vacuum column bottoms consist of pitch, mineral matter,
unreacted coal and catalyst, and in commercial operation would
be used as a gasified feedstock for H
2
production.
Process Engineering
By: Dr. H.Farzaneh
1-2-2- CataIytic Two-Stage Liquefaction
The CTSL process is a development of the H-Coal single-stage
process.
Process Engineering
By: Dr. H.Farzaneh
Coal is slurried with a process-derived recycle solvent, preheated,
mixed with H
2
and fed to the bottom of an reactor.
This reactor contains a supported catalyst, generally nickel-
molybdenum on alumina, which is fluidized by an internal recycle
in the reactor.
The reactor, therefore, has the characteristics of a uniform-
temperature continuous-stirred tank reactor.
The solvent acts as a hydrogen donor and solubilises the coal by
breaking down its structure to a substantial extent in the first
reactor.
This first reactor substantially rehydrogenates the solvent.
Typically, operating conditions of 170 bar and a temperature of
400-410
C
are used when processing bituminous coals.
Process Engineering
By: Dr. H.Farzaneh
The reactor products pass directly into the base of a second,
reactor stage, operating at the same pressure as the first stage
but at a higher temperature (~430-440
C
).
This reactor also contains a supported catalyst, generally but not
necessarily the same as that in the first reactor.
After separation and depressurization steps, the products from the
second reactor enter an atmospheric distillation column, where
distillate products boiling up to 400C are removed.
The bottom stream from this column contains solvent, unreacted
coal and mineral matter. These solids are removed by one of
several possible techniques and the solvent is recycled to the
slurring step.
Process Engineering
By: Dr. H.Farzaneh
6- PetroIeum oiI distiIIation
Distillation is a method of separating mixtures based on differences
in their volatilities in a boiling liquid mixture.
Distillation is a unit operation, or a physical separation process, and
not a chemical reaction
The most widely used industrial applications of distillation are in
petroleum refineries.
ndustrial distillation is typically performed in large, vertical cylindrical
columns known as distillation towers or distillation columns with
diameters ranging from about 65 centimeters to 16 meters and
heights ranging from about 6 meters to 90 meters or more.
Process Engineering
By: Dr. H.Farzaneh
When the process feed has a diverse composition, as in distilling
crude oil, liquid outlets at intervals up the column allow for the
withdrawal of different fractions or products having different boiling
points or boiling ranges.
The "lightest" products (those with the lowest boiling point) exit from
the top of the columns and the "heaviest" products (those with the
highest boiling point) exit from the bottom of the column and are
often called the bottoms.
Process Engineering
By: Dr. H.Farzaneh
6-1- Crude oiI distiIIation process steps:
1) Preheat the crude feed utilizing recovered heat from the product
streams
2) Desalt and dehydrate the crude using electrostatic enhanced
liquid/liquid separation (Desalter)
3) Heat the crude to the desired temperature using fired heaters
4) Flash the crude in the atmospheric distillation column
5) Utilize pump around cooling loops to create internal liquid reflux
6) Product draws are on the top, sides, and bottom
Process Engineering
By: Dr. H.Farzaneh
Crude oiI distiIIation products
Process Engineering
By: Dr. H.Farzaneh
Large-scale industrial towers use reflux to achieve a more complete
separation of products.
Reflux refers to the portion of the condensed overhead liquid product
from a distillation or fractionation tower that is returned to the upper
part of the tower as shown in the schematic diagram of a typical,
large-scale industrial distillation tower.
.
nside the tower, the down flowing
reflux liquid provides cooling and
condensation of the up flowing
vapors thereby increasing the
efficacy of the distillation tower
Process Engineering
By: Dr. H.Farzaneh
6-2- CaIcuIation of number of stages required
The internal reflux ratio at any tray is the ratio:
J
O
entering vapor mole
leaving liquid moles
=
For any given vapor/liquid
equilibrium, a minimum
reflux ratio is necessary for
separation.
At minimum reflux ratio, an
infinite number of trays is
necessary.
The optimum reflux ratio is
obtained by balancing the
number of trays in a column
against capital costs.
Process Engineering
By: Dr. H.Farzaneh
At a given tray n in the upper, rectifying part of the column, the
vapor (Y
n-1
) entering from the tray below is dispersed the edges of
the bubble caps as a stream of bubbles in the liquid (x
n+1
) entering
from the tray above, and leaving as composition x
n
.
n theoretical tray, the vapor is in equilibrium with the liquid.
Y
n
=Kx
n
The relationship between the liquid and vapor streams passing in
the column, e.g. V, Y
n-1
and O, x
n+1
is calculated from heat and
material balances.
Assuming constant overflow, and constant vaporization, on each
tray:
D n n
x
J
D
x
J
O
Y + =
1
Process Engineering
By: Dr. H.Farzaneh
Where, D is the amount of distillate obtained in unit time. And x
D
is the molecular fraction of the more volatile component in D.
x
n
is obtained by equilibrium calculation and also:
Y
n-1
=Kx
n-1
The complete analysis for multi component systems is laborious,
but may be simplified by use of McCabe-Thiele graphical
method.
This is based on a binary mixture, making the following assumption:
1) Sensible heat changes are negligible compared with latent heat
changes.
2) The molar latent heats of all components are equal.
3) The heat of mixing is negligible.
4) The heat losses from the column are negligible.
Process Engineering
By: Dr. H.Farzaneh
6-2-1- The rectifying section. We shall write
the mass balances as one total balance and
one component balance. For the top section
these equations are:
The constant molar overflow assumption yields
L
0
= L
1
= . . . = L
n~1
= L.
Furthermore, it is customary to define the
external reflux ratio of the column as R L/D
1
1
1
1
0
1
1 0

+
+
+
= + =
i
i
i
i i
i
i
i
i
L D
L
x
L D
D
x
J
L
x
J
D
x v
| | n i
R
R
x
R
x v
i i
, 1
1 1
1
1 0
e
+
+
+
=

Process Engineering
By: Dr. H.Farzaneh
This is the so-called operating line representing the combined mass
and energy balances in the rectifying section of the column.
The equation is valid for all of the internal stages i = 1 , 2, . . . , n and in
particular for i = 1 which yields y
1
= x
0
= x
D
.
6-2-2- The stripping section
The constant molar overflow assumption yields:
V
n+1
= V
n+2
= . . . = V
N+1
= V.
Furthermore, we may characterize the heat duty of the reboiler as
S V/(V + B )
and write
| | 1 , 1
1 1
1
+ + e +

=

N n i
S
x
S
S
x v
i B i
Process Engineering
By: Dr. H.Farzaneh
Where S is the fraction of the downcoming liquid which is being
evaporated. Alternatively we can define S as the heat duty of the
reboiler divided by the heat which is needed to evaporate all the
downcoming liquid.
The operating line is valid for all the internal stages i = n + 1, n + 2, . .
. , N and also for the reboiler i = N + 1.
The stripping section has therefore one external equilibrium stage in
addition to the internal stages of the column (the situation is similar to
that of a partial condenser in the rectifying section).
The cross-over between the operating line and the main diagonal is
given by y
N+2
= x
N+1
= x
B
.
The index i = N + 2 is strictly speaking outside the control volume but
it does still serve as an easy-to remember construction point of the
diagram.
Process Engineering
By: Dr. H.Farzaneh
At this point it is possible to count the number of theoretical stages
from the specifications of the top and bottom products together with
the condenser and reboiler duties.
t is more common, however, to specify the feed stream rather than
the reboiler duty.
6-2-3- The feed tray
the feed quality may be represented by:
and:
J L
L
q
A A
A

1
1
1

=
q
x
q
q
x v
F
Process Engineering
By: Dr. H.Farzaneh
ExampIe 3
Consider the binary mixture of following compositions:
C
6
H
6
45%
C
7
H
8
55%
A continues fractionating column is to be design to separate 30000
lb/h of above mixture. The bottom product should be contained 88
weight percent toluene. The overhead product containing 87 percent
benzene. A reflux ratio of 3.5 to 1 mol of product is to be used.
Determine the number of ideal plates.
Solution:
The molecular weight of benzene is 78 and that of toluene is 92.
Therefore:
14 . 0
92
88
78
12
78
12
89 . 0
92
13
78
87
78
87
5 . 0
92
55
78
45
78
45
=
+
=
=
+
= =
+
=
B
D F
x
x x
Process Engineering
By: Dr. H.Farzaneh
First Step is to plot the equilibrium diagram of vapor/liquid
i) Calculate the vapor pressure of pure C
6
H
6
and C
7
H
8
from the
following equation:
Where A and B are constants and may be found from anthimuan
standard table and T is the absolute temperature.
T
B
A P log
0.25 265.1 0.55 482 C
7
H
8
1 1061.6 1 Total
0.75 796.5 0.45 1770 C
6
H
6
Mass Fraction
vapor
Partial Pressure Mass Fraction
Liquid
V.P of pure
Process Engineering
By: Dr. H.Farzaneh
ii) Plot the equilibrium curve y/x from the obtained data.
Second step is to plot y=x curve.
Third step is to plot rectifying operation curve:
Calculate curve slop form
Find the value of x
D
on line of y=x
Plot the line with slope of from this point and connect it to
y-axis
Forth step is to plot stripping operation curve.
i) Calculate curve slop form
The average molecular weigh of the feed is
77 . 0
1
=
+ R
R
1 + R
R
s / 1
12 . 85
92
55
78
45
100
=
+
Process Engineering
By: Dr. H.Farzaneh
Therefore F is 30000/85.12=352 lbmole/h
We know and
ii) Find the value of x
B
on line of y=x
iii) Plot the line with slope of from this point and cross the
rectifying operation curve
B D F
Bx Dx Fx + =
h lbmol D / 169
14 . 0 89 . 0
14 . 0 5 . 0
352 =

=
B D F + =
h lbmol B / 183 169 352 = =
h lbmole R D RD D L D J / 5 . 760 ) 5 . 4 ( 169 ) 1 ( = = + = + = + =
81 . 0 ) 183 5 . 760 /( 5 . 760 ) /( = + = + = B J J S
s / 1
Process Engineering
By: Dr. H.Farzaneh
The cross point of the rectifying operation curve and the stripping
operation curve represent the theoretical feed plate composition.
The combined line which is obtained from connecting the rectifying
operation curve and the stripping operation curve named total
operation line.
Forth step is calculate theoretical steps by drawing horizontal line
from start point x
D
on total operation line to equilibrium curve and
drawing vertical line from this point to total operation line again and
it will be finished when the last line connect equilibrium curve to
point of x
B
Process Engineering
By: Dr. H.Farzaneh
) 1 /( + = R R Slope
S Slope / 1 =
D
x
F
x
B
x
Process Engineering
By: Dr. H.Farzaneh
7- Cracking Process
cracking is the process whereby complex organic molecules such as
kerogens or heavy hydrocarbons are broken down into simpler
molecules (e.g. light hydrocarbons) by the breaking of carbon-
carbon bonds in the precursors.
The rate of cracking and the end products are strongly dependent on
the temperature and presence of any catalysts.
Oil refinery cracking processes allow the production of "light" products
such as LPG and gasoline from heavier crude oil distillation
fractions such as gas oils and residues .
Fluid Catalytic Cracking (FCC) produces a high yield of gasoline and
LPG while hydrocracking is a major source of jet fuel, diesel,
naphtha and LPG .
Process Engineering
By: Dr. H.Farzaneh
Thermal cracking is currently used to "upgrade" very heavy fractions
("upgrading", "visbreaking"), or to produce light fractions or
distillates, burner fuel and/or petroleum coke.
Two extremes of the thermal cracking in terms of product range are
represented by the high-temperature process called "steam
cracking" or pyrolysis (ca. 750 to 900
C
or more) which produces
valuable ethylene and other feedstocks for the petrochemical
industry, and the milder-temperature delayed coking (ca. 500 C)
which can produce, under the right conditions, valuable needle
coke, a highly crystalline petroleum coke used in the production of
electrodes for the steel and aluminum industries.
Process Engineering
By: Dr. H.Farzaneh
7-1- FCC Process
1) Gas oil feed is dispersed into the bottom of the riser using steam
2) Thermal cracking occurs on the surface of the catalyst
3) Disengaging drum separates spent catalyst from product vapors
4) Steam strips residue hydrocarbons from spent catalyst
5) Air burns away the carbon film from the catalyst in either a "partial-
burnor "full-burnmode of operation
6) Regenerated catalyst enters bottom of riser-reactor
.
Process Engineering
By: Dr. H.Farzaneh
Fluidic Catalytic Cracking (FCC) Process Schematic
Process Engineering
By: Dr. H.Farzaneh
7-2- Hydrocracking
Hydrocracking is a catalytic cracking process assisted by the
presence of an elevated partial pressure of hydrogen gas. Similar
to the hydrotreater, the function of hydrogen is the purification of
the carbon stream from sulfur and nitrogen hetero -atoms.
The products of this process are saturated hydrocarbons; depending
on the reaction conditions (temperature, pressure, catalyst activity)
these products range from ethane, LPG to heavier hydrocarbons
comprising mostly of isoparaffins.
Hydrocracking is normally facilitated by a bi functional catalyst that is
capable of rearranging and breaking hydrocarbon chains as well
as adding hydrogen to aromatics and olefins to produce
naphthenes and alkanes .
Process Engineering
By: Dr. H.Farzaneh
HCC Process steps:
1) Preheated feed is mixed with hot hydrogen and passes through a
multi-bed reactor with interstage hydrogen quenches for
hydrotreating
2) Hydrotreated feed is mixed with additional hot hydrogen and
passes through a multi-bed reactor with quenches for first pass
hydrocracking
3) Reactor effluents are combined and pass through high and low
pressure separators and are fed to the fractionator where valuable
products are drawn from the top, sides, and bottom
4) Fractionator bottoms may be recycled to a second pass hydro
cracker for additional conversion all the way up to full conversion
.
Process Engineering
By: Dr. H.Farzaneh
HCC Process Schematic
Process Engineering
By: Dr. H.Farzaneh
7-3- ThermaI cracking
William Merriam Burton developed one of the earliest thermal
cracking processes in 1912 which operated at 700 -750 F (370-400
C) and an absolute pressure of 90 psia (620 kPa) and was known
as the Burton process.
Shortly thereafter, in 1921, , an employee of the Universal Oil
Products Company, developed a somewhat more advanced
thermal cracking process in 1921 which operated at 750-860 F
(400-460 C) and was known as the Dubbs process .
Modern high-pressure thermal cracking operates at absolute
pressures of about 7,000 kPa. An overall process of
disproportionate can be observed, where "light", hydrogen-rich
products are formed at the expense of heavier molecules which
condense and are depleted of hydrogen. The actual reaction is
known as homolytic fission and produces alkenes, which are the
basis for the economically important production of polymers .
Process Engineering
By: Dr. H.Farzaneh
8- Reforming process
8-1- CataIytic reforming
Catalytic reforming is a chemical process used to convert
petroleum refinery naphthas, typically having low octane ratings,
into high-octane liquid products called reformates which are
components of high-octane gasoline (also known as petrol).
Basically, the process re-arranges or re-structures the hydrocarbon
molecules in the naphtha feedstocks as well as breaking some of
the molecules into smaller molecules.
The overall effect is that the product reformate contains
hydrocarbons with more complex molecular shapes having higher
octane values than the hydrocarbons in the naphtha feedstock. n
so doing, the process separates hydrogen atoms from the
hydrocarbon molecules and produces very significant amounts of
byproduct hydrogen gas for use in a number of the other processes
involved in a modern petroleum refinery. Other byproducts are
small amounts of methane, ethane, propane and butanes .
Process Engineering
By: Dr. H.Farzaneh
The liquid feed (at the bottom left in the diagram) is pumped up to the
reaction pressure (5 to 45 atm) and is joined by a stream of
hydrogen-rich recycle gas. The resulting liquid-gas mixture is
preheated by flowing through a heat exchanger.
The preheated feed mixture is then totally vaporized and heated to
the reaction temperature (495 to 520 C) before the vaporized
reactants enter the first reactor.
As the vaporized reactants flow through the fixed bed of catalyst in
the reactor, the major reaction is the dehydrogenation of naphthenes
to aromatics (as described earlier herein) which is highly endothermic
and results in a large temperature decrease between the inlet and
outlet of the reactor.
To maintain the required reaction temperature and the rate of
reaction, the vaporized stream is reheated in the second fired heater
before it flows through the second reactor.
Process Engineering
By: Dr. H.Farzaneh
Temperature again decreases across the second reactor and the
vaporized stream must again be reheated in the third fired heater
before it flows through the third reactor.
As the vaporized stream proceeds through the three reactors, the
reaction rates decrease and the reactors therefore become larger. At
the same time, the amount of reheat required between the reactors
becomes smaller. Usually, three reactors are all that is required to
provide the desired performance of the catalytic reforming unit.
The hot reaction products from the third reactor are partially cooled
by flowing through the heat exchanger where the feed to the first
reactor is preheated and then flow through a water-cooled heat
exchanger before flowing through the pressure controller (PC) into
the gas separator.
Process Engineering
By: Dr. H.Farzaneh
Most of the hydrogen-rich gas from the gas separator vessel returns
to the suction of the recycle hydrogen gas compressor and the net
production of hydrogen-rich gas from the reforming reactions is
exported for use in other the other refinery processes that consume
hydrogen (such as hydrodesulfurization units and/or a hydrocracker
unit).
The liquid from the gas separator vessel is routed into a fractionating
column commonly called a stabilizer.
The overhead offgas product from the stabilizer contains the
byproduct methane, ethane, propane and butane gases produced by
the hydrocracking reactions as explained in the above discussion of
the reaction chemistry of a catalytic reformer, and it may also contain
some small amount of hydrogen.
That offgas is routed to the refinery's central gas processing plant for
removal and recovery of propane and butane.
Process Engineering
By: Dr. H.Farzaneh
The residual gas after such processing becomes part of the refinery's
fuel gas system.
The bottoms product from the stabilizer is the high-octane liquid
reformate that will become a component of the refinery's product
gasoline.
Process Engineering
By: Dr. H.Farzaneh
8-2- Steam reforming
Steam reforming, hydrogen reforming or catalytic oxidation, is a
method of producing hydrogen from hydrocarbons.
On an industrial scale, it is the dominant method for producing
hydrogen. Small-scale steam reforming units are currently subject to
scientific research, as way to provide hydrogen to fuel cells.
Steam reforming of natural gas, sometimes referred to as steam
methane reforming (SMR) is the most common method of
producing commercial bulk hydrogen as well as the hydrogen used in
the industrial synthesis of ammonia. t is also the least expensive
method.
At high temperatures (700 1100 C) and in the presence of a metal-
based catalyst (nickel), steam reacts with methane to yield carbon
monoxide and hydrogen
Process Engineering
By: Dr. H.Farzaneh
2 2 4
3H CO O H CH + +
Additional hydrogen can be recovered by a lower-temperature gas-shift
reaction with the carbon monoxide produced.
The reaction is summarized by:
2 2 2
H CO O H CO + +
The produced carbon monoxide can combine with more steam to
produce further hydrogen via the water gas shift reaction. Other
reactions (some undesirable, like coke formation) can take place if local
conditions are favorable.
The first reaction is endothermic (consumes heat), the second reaction
is exothermic (produces heat).
Process Engineering
By: Dr. H.Farzaneh
9- ThermaI Power pIants
9-1- Brayton CycIe
Brayton cycle is a constant pressure cycle for a perfect gas. t also
called Joule cycle.
Process Engineering
By: Dr. H.Farzaneh
Schematic of an industriaI Gas turbine
Process Engineering
By: Dr. H.Farzaneh
CIosed cycIe Gas Turbine
Process Engineering
By: Dr. H.Farzaneh
Open cycIe Gas Turbine
Process Engineering
By: Dr. H.Farzaneh
JouIe- Brayton CycIe
P
V
1
2 3
4
Process Engineering
By: Dr. H.Farzaneh
Operation 1-2: The air is compressed isentropically from lower
pressure to upper pressure.
Operation 2-3: Heat flows into the system increasing the volume
and temperature while the pressure remains constant.
Operation 3-4: The air is expanded isentropically.
Operation 4-1: Heat is rejected from the system as the volume and
temperature decreases while the pressure remains constant.
Process Engineering
By: Dr. H.Farzaneh
9-1-2- ThermaI efficiency

q
q
q
1
1
4 3
1
1
2
4
3
1
1 2
1
1
2
1
2
2 3
1 4
2 3
1 4 2 3
) (
1
1
) (
) (
1
) (
) ( ) (

=
=
|
|
.
|

\
|
=
=
|
|
.
|

\
|
=

= =
p
p
p
p
p p
r
r T T
P
P
T
T
r T T
P
P
T
T
T T
T T
T T mc
T T mc T T mc
received Heat
refected Heat recevied Heat
received Heat
done Work
Process Engineering
By: Dr. H.Farzaneh
Performance map of simpIe Brayton cycIe
Process Engineering
By: Dr. H.Farzaneh
ExampIe 4 Air enters the compressor of a gas turbine plant operating
on Brayton cycle at 101.325 kPa, 27 C. The pressure ratio in the
cycle is 6.
Calculate the maximum temperature in the cycle and the cycle
efficiency.
Assume W
T
=2.5 W
C
. Where W
T
and W
C
are the turbine and the
compressor work respectively.
SoIution:
668 . 1
668 . 1 ) (
4 . 500 300 668 . 1 668 . 1
668 . 1 ) 6 ( ) (
3
4
1
4
3
1 2
4 . 1
1 4 . 1
1
1
2
T
T
r
T
T
K T T
r
T
T
p
p
=
= =
= = =
= = =

Process Engineering
By: Dr. H.Farzaneh
4 . 0
) 6 (
1
1
) (
1
1
750
1251
501 ) 300 4 . 500 ( 5 . 2
668 . 1
) ( 5 . 2 ) (
4 . 1
1 4 . 1 1
4
3
3
3
1 2 4 3
= = =
=
=
= =
=

q
p
p p
r
K T
K T
T
T
T T mc T T mc
Process Engineering
By: Dr. H.Farzaneh
ExampIe 5 n a gas turbine plant working on Brayton cycle, the air at
inlet in 27 C and 0.1 MPa. The pressure ratio is 6.25and the
maximum temperature is 800 C. The turbine and compressor
efficiencies are each 80% .
Find compressor work, turbine work, heat supplied, cycle efficiency
and turbine exhaust temperature.
Mass of air may be considered as 1 kg.
T
S
1
2
2
/
3
4
4
/
Process Engineering
By: Dr. H.Farzaneh
For the compression process 1-2 :
kg kJ T T cp W
K T
T T T
T T
K T
P
P
T
T
comp
comp
/ 3 . 259 ) 300 558 ( 005 . 1 1 ) ( 1
558
300
300 4 . 506
8 . 0
4 . 506 688 . 1 300
668 . 1 ) 25 . 6 (
1 2
2
2 1 2
1 2
2
4 . 1
1 4 . 1
1
1
2
1
2
= =
'
=
=
'

'

=

'

=
= =
= =
|
|
.
|

\
|
=

Process Engineering
By: Dr. H.Farzaneh
For the expansion process 3-4:
kg kJ T T cp W
K T
T
T T
T T
K T
P
P
T
T
turb
turb
/ 6 . 351 ) 1 . 723 1073 ( 005 . 1 1 ) ( 1
1 . 723
6 . 635 1073
1073
8 . 0
6 . 635
688 . 1
1073
668 . 1 ) 25 . 6 (
4 3
4
4
4 3
4 3
4
4 . 1
1 4 . 1
1
4
3
4
3
= =
'
=
=
'

'

'

=
= =
= =
|
|
.
|

\
|
=

Net work output:

kg kJ W W W
comp turb net
/ 31 . 92 = =
Process Engineering
By: Dr. H.Farzaneh
Heat Supplied:
6 . 517 ) 558 1073 ( 005 . 1 1 = = Q
Cycle Efficiency:
38 . 17 = =
Q
W
net
cvcle
q
Process Engineering
By: Dr. H.Farzaneh
9-2- Rankine cycIe
The Rankine vapor cycle is the basis for a widely used combustion
cycle that uses coal, fuel oil, or other fuels to compress and heat water
to vapor, and then expand the vapor through a turbine in order to
convert heat to mechanical energy.
The following stages occur between states in the cycle:
1) Compression of the fluid using a pump
2) Heating of the compressed fluid to the inlet temperature of turbine,
including increasing temperature to boiling point, and phase
change from liquid to vapor
3) Expansion of the vapor in the turbine
4) Condensation of the vapor in a condenser
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
T-S Diagram of Rankine cycIe
Process Engineering
By: Dr. H.Farzaneh
ExampIe 6 The cycle is represented in the accompanying
temperature-entropy (T-s) diagram. At the beginning of the analysis, it
is useful to present all enthalpy and entropy values that can be read
directly from steam tables, as follows:
Pump work: The change in pressure is 4 0.1 = 3.9 MPa. The specific
volume of water at 100 kPa is 0.104 m3/kg. Therefore, the pump work
is
kg kJ w
pump
/ 4 9 . 3 00104 . 0 = =
Process Engineering
By: Dr. H.Farzaneh
t follows that
kg kJ w h h
pump
/ 5 . 421
1 2
= + =
Turbine output: n order to solve for the work output from the turbine, we
need to evaluate h
4
. First, evaluate the quality of the steam leaving the
turbine, that is, the percent of the mixture that is vapor.
Use the entropy values for liquid water and saturated steam at 100 kPa:
Process Engineering
By: Dr. H.Farzaneh
The quality x is then
7 . 78
3028 . 1 3589 . 7
3028 . 1 0696 . 6
4
=

=
f g
f
s s
s s
x
Using the enthalpy values from the tables for liquid water and
saturated steam at 100 kPa, h
f
= 417.5 and h
g
= 2675.0 kJ/kg, h
4
is
calculated by rearranging:
kg kJ h
h h
h h
x
f g
f
/ 5 . 2194 5 . 417 ) 5 . 417 2675 ( 787 . 0
4
4
= + =

=
Overall efficiency is then
3 . 25
5 . 421 8 . 2800
4 ) 5 . 2194 8 . 2800 (
=

=
Q
w w
in out
th
q
Process Engineering
By: Dr. H.Farzaneh
9-2- SupercriticaI cycIe
One way to increase the efficiency of the Rankine cycle is to increase
the pressure at which heat is added to the vapor in the boiler.
n a conventional Rankine cycle such as that of Example 5, the water in
the boiler is heated until it reaches the saturation temperature for water
at the given pressure, and then heated at a constant temperature in the
liquid-vapor region until it becomes saturated steam.
However, if sufficiently compressed, the fluid exceeds the critical
pressure for water and does not enter the liquid-vapor region. n this
case, the process is called a supercritical cycle, and the boiler achieves
a temperature that is in the supercritical region for water,
Process Engineering
By: Dr. H.Farzaneh
SupercriticaI T-S diagram
Process Engineering
By: Dr. H.Farzaneh
9-4- combined CycIe
t was mentioned that the remaining energy in the exhaust from the
gas turbine can be put to some other use in order to increase overall
system output.
f the exhaust gas temperature is sufficiently high, one innovative
application is to boil water for use in a Rankine cycle, thus effectively
powering two cycles with the energy in the gas that is initially
combusted.
This process is called a combined gas-vapor cycle, or simply a
combined cycle.
Process Engineering
By: Dr. H.Farzaneh
Schematic of Combined CycIe
Process Engineering
By: Dr. H.Farzaneh
T-S Diagram of Combined CycIe
Process Engineering
By: Dr. H.Farzaneh
9-5- Cogeneration and combined heat and power
n a cogeneration system, a single source of energy, such as a fossil
fuel, is used for more than one application.
One of the most prominent types of cogeneration system is combined
heat and power (CHP), in which a working fluid is used to generate
electricity, and then the exhaust from the generating process is used for
some other purpose, such as a district heating system for residential or
commercial buildings located near the CHP power plant, or for process
heat in an industrial process.
n addition to the pumps, boiler, turbine, and condenser seen
previously, several new components are introduced:
A process heater: This component extracts heat from incoming vapor
flow and transfers it to an outside application, such as district heating.
Process Engineering
By: Dr. H.Farzaneh
An expansion valve: This valve permits the reduction in steam
pressure so that the steam can pass directly from the boiler exit at
higher pressure to the process heater at lower pressure, without
expansion in the turbine. n an ideal expansion valve, the enthalpy of the
steam is not changed, but the entropy is changed, due to the reduction
in pressure and hence quality of the steam.
A mixing chamber: This unit permits mixing of water from two different
pumps before transfer to the boiler. Enthalpy of the exiting water is
determined using a mass balance and energy balance across the mixing
chamber
Process Engineering
By: Dr. H.Farzaneh
Schematic of Cogeneration
Process Engineering
By: Dr. H.Farzaneh
T-S Diagram of Cogeneration
Process Engineering
By: Dr. H.Farzaneh
References
W.Fransis, M.C.Peters, Fuels and Fuel Technology, Pergamon Press
1980
W.Mc Cabe,J.C.Smith, Unit Operation of Chemical Engineering, McGraw-
Hill. 1985
J.Harker, J.R.Backhurst, Fuel and Energy, Academic Press. 1977
D. F. Othmer Distillation - Some Steps in its Development, in W. F. Furter
(ed) A Century of Chemical Engineering.1999
Perry, Robert H. and Green, Don W. Perry's Chemical Engineers'
Handbook, 6th Edition, McGraw-Hill. 1984
Francis M. Vanek, Louis D. Alberight, Energy systems engineering, MC
Graw Hill 2008
Process Engineering
By: Dr. H.Farzaneh
Chapter Three (Performance EvaIuation of FueIs)
PrincipIes of Combustion
Concept of Excess Air
Draft System
Energy Efficiency Opportunities
Mechanism of Combustion
Process Engineering
By: Dr. H.Farzaneh
1- PrincipIes of Combustion
Combustion Combustion is the conversion of a substance called a fuel into
chemical compounds known as products of combustion by
combination with an oxidizer.
The combustion process is an exothermic chemical reaction, i.e.,
a reaction that releases energy as it occurs. Thus combustion may
be represented symbolically by:
Fuel + Oxidizer Products of combustion + En Fuel + Oxidizer Products of combustion + Energy ergy
Here the fuel and the oxidizer are reactants, i.e., the substances
present before the reaction takes place. This relation indicates that
the reactants produce combustion products and energy.
Process Engineering
By: Dr. H.Farzaneh
Fuels are evaluated, in part, based on the amount of energy or
heat that they release per unit mass or per mole during
combustion of the fuel. Such a quantity is known as the fuel's heat heat
of reaction of reaction or heating value heating value. .
n combustion processes the oxidizer is usually air but could be
pure oxygen, an oxygen mixture, or a substance involving some
other oxidizing element such as fluorine. Here we will limit our
attention to combustion of a fuel with air or pure oxygen.
Most of the 79% of air (that is not oxygen) is nitrogen, with traces
of other elements.
Nitrogen reduces combustion efficiency by absorbing heat from
the combustion of fuels and diluting the flue gases. This reduces
the heat available for transfer through the heat exchange surfaces.
Process Engineering
By: Dr. H.Farzaneh
Nitrogen also can combine with oxygen (particularly at high flame
temperatures) to produce oxides of nitrogen (NOx), which are
toxic pollutants.
Carbon, hydrogen and sulphur in the fuel combine with oxygen in
the air to form carbon dioxide, water vapour and sulphur dioxide,
releasing 8,084 kcals, 28,922 kcals and 2,224 kcals of heat
respectively.
Under certain conditions, carbon may also combine with oxygen to
form carbon monoxide, which results in the release of a smaller
quantity of heat (2,430 kcals/kg of carbon). Carbon burned to CO2
will produce more heat per unit of fuel than when CO or smoke are
produced.
Process Engineering
By: Dr. H.Farzaneh
1-1- Three T's of combustion
The objective of good combustion is to release all of the heat in
the fuel.
This is accomplished by controlling the "three T's" of combustion
which are:
1) Temperature high enough to ignite and maintain ignition of
the fuel
2) Turbulence or intimate mixing of the fuel and oxygen
3) Time, sufficient for complete combustion.
Commonly used fuels like natural gas and propane generally
consist of carbon and hydrogen.
Water vapor is a by-product of burning hydrogen. This removes
heat from the flue gases, which would otherwise be available for
more heat transfer.
Process Engineering
By: Dr. H.Farzaneh
Natural gas contains more hydrogen and less carbon per kg than
fuel oils and as such produces more water vapor. Consequently,
more heat will be carried away by exhaust while firing natural gas.
Process Engineering
By: Dr. H.Farzaneh
1-2- Characterizing Air for Combustion CaIcuIations
Air is a mixture of about 21% oxygen, 78% nitrogen, and 1% other
constituents by volume.
For combustion calculations it is usually satisfactory to represent
air as a 21% oxygen, 79% nitrogen mixture, by volume.
Thus for every 21 moles of oxygen that react when air oxidizes a
fuel, there are also 79 moles of nitrogen involved.
Therefore, 79/21 = 3.76 moles of nitrogen are present for every
mole of oxygen in the air.
Process Engineering
By: Dr. H.Farzaneh
ExampIe 7
Stochiometric calculation of air for furnace oil combustion
Solution:
The first step is to determine the composition of the furnace oil.
Typical specifications of furnace oil from lab analysis is given
below:
Process Engineering
By: Dr. H.Farzaneh
f we take these analysis data, and considering a sample of 100
kg of furnace oil, then the chemical reactions are as follows:
Element Molecular Weight (kg / kg mole)
C 12
O
2
32
H
2
2
S 32
N
2
28
CO
2
44
SO
2
64
H
2
O 18
C + O
2
CO
2
H
2
+ 1/2O
2
H
2
O
S + O
2
SO
2
Process Engineering
By: Dr. H.Farzaneh
Constituents of fuel
C + O2 CO2
12 + 32 44
12 kg of carbon requires 32 kg of oxygen to form 44 kg of carbon
dioxide therefore 1 kg of carbon requires 32/12 kg i.e 2.67 kg of
oxygen
(85.9) C + (85.9 x 2.67) O
2
315.25 CO
2
2H
2
+ O
2
2H
2
O
4 + 32 36
4 kg of hydrogen requires 32 kg of oxygen to form 36 kg of water,
therefore 1 kg of hydrogen requires 32/4 kg i.e. 8 kg of oxygen.
Process Engineering
By: Dr. H.Farzaneh
(12) H2 + (12 x 8) O2 (12 x 9 ) H2O
S + O2 SO2
32 + 32 64
32 kg of sulphur requires 32 kg of oxygen to form 64 kg of sulphur
dioxide, therefore 1 kg of sulphur requires 32/32 kg i.e. 1 kg of
oxygen.
(0.5) S + (0.5 x 1) O2 1.0 SO2
Total oxygen required = 325.57 kg
(229.07+96+0.5)
Oxygen already present in
100 kg fuel (given) = 0.7 kg
Process Engineering
By: Dr. H.Farzaneh
Additional oxygen required = 325.57 0.7
= 3 24.87 kg
Therefore quantity of dry air needed = (324.87) / 0.23
(air contains 23% oxygen by weight)
= 1412.45 kg of air
Theoretical air required = (1412.45) / 100
= 14.12 kg of air / kg of fuel
Therefore, in this example, for each kg of furnace oil burnt, 14.12 14.12 kg
of air is required.
Process Engineering
By: Dr. H.Farzaneh
ExampIe 8
Calculation of theoretical CO
2
content in the flue gases
t is necessary to also calculate the CO2 content in the flue gases,
which then can be used to calculate the excess air in the flue
gases. A certain amount of excess air is needed for complete
combustion of furnace oils. However, too much excess air points
to heat losses and too little excess air points to incomplete
combustion.
Solution:
Nitrogen in flue gas = 1412.45 324.87
= 1087.58 kg
Theoretical CO2% in dry fIue gas dry fIue gas by volume is calculated as below:
Moles of CO2 in flue gas = (315.25) / 44 = 7.16
Moles of N2 in flue gas = (1087.58) / 28 = 38.84
Moles of SO2 in flue gas = 1/64= 0.016
Theoretical CO2 % by Volume = (Moles of CO2 x 100) / Total Moles
(Dry)= (7.16 x 100) / (7.16 + 38.84 + 0.016) = 15.5% 15.5%
Process Engineering
By: Dr. H.Farzaneh
ExampIe 9
Calculation of constituents of flue gas with excess air
Now we know the theoretical air requirements and the theoretical
CO
2
content of flue gases. The next step is to measure the actual
CO
2
percentage in the flue gases. n the calculation below it is
assumed that the measured %CO
2
in the flue gas is 10%.
Solution:
% Excess air = [(Theoretical CO
2
% /Actual CO
2
) 1 ] x 100
= [(15.5/10 1)] x 100 = 55%
Theoretical air required for 100kg of fuel burnt = 1412.45 kg
Total quantity of air supply required with 55% excess air =
1412.45 x 1.55= 2189.30 kg
Process Engineering
By: Dr. H.Farzaneh
Excess air quantity (actual theoretical excess air) = 2189.30
1412.45 = 776.85
O
2
(23%) = 776.85 x 0.23= 178.68 kg
N
2
(77%) = 776.85 178.68 = 598.17 kg
The final constituents of flue gas with 55% excess air for every 100
kg fuel is as follows:
CO
2
= 315.25 kg
H
2
O = 108.00 kg
SO
2
= 1 kg
O
2
= 178.68 kg
N
2
= 1685.75 kg (= 1087.58 in air + 598.17 in excess air)
Process Engineering
By: Dr. H.Farzaneh
ExampIe 10
Calculation of theoretical CO
2
% in dry flue gas by volume
Solution:
Now that we have the constituents by weight, we can calculate the
constituents on a volume basis as follows:
Moles of CO
2
in flue gas = 315.25 / 44 = 7.16
Moles of SO
2
in flue gas = 1/64= 0.016
Moles of O
2
in flue gas = 178.68 / 32 = 5.58
Moles of N
2
in flue gas = 1685.75 / 28 = 60.20
Theoretical CO
2
% by volume = (Moles of CO
2
x 100) / Total moles
(dry)= ( 7.16x 100) / (7.16+ 0.016 + 5.58+ 60.20) = 10%
Theoretical O2% by volume = (5.58x 100) / 72.956 = 7.5% 7.5%
Process Engineering
By: Dr. H.Farzaneh
2- Concept of Excess Air
For optimum combustion, the real amount of combustion air must be
greater than that required theoretically.
Part of the stack gas consists of pure air, i.e. air that is simply heated
to stack gas temperature and leaves the boiler through the stack.
Chemical analysis of the gases is an objective method that helps to
achieve finer air control.
By measuring CO
2
or O
2
in flue gases (by continuous recording
instruments or Orsat apparatus or some cheaper portable
instruments) the excess air level and stack losses can be estimated.
The excess air to be supplied depends on the type of fuel and the
firing system.
Process Engineering
By: Dr. H.Farzaneh
ReIation between CO2 & Excess Air
Process Engineering
By: Dr. H.Farzaneh
ReIationship between residuaI oxygen and excess air
Process Engineering
By: Dr. H.Farzaneh
The air/fuel parameters just discussed emphasize the amount of air
supplied to burn a given amount of fuel relative to the theoretical
requirement.
An alternate approach considers a given amount of air and indicates
the mass of fuel supplied , the fuel-air ratio, F/A, which is the inverse
of the air-fuel ratio.
A measure of how much fuel is actually supplied, called the
equivalence ratio, is the ratio of the actual fuel-air ratio to the
theoretical fuel-air ratio:
l theoretica
actual
A F
A F
) / (
) / (
= |
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
3- Draft System
The function of draft in a combustion system is to exhaust the
products of combustion, i.e. flue gases, into the atmosphere.
The draft can be classified into two types namely natural draft and
mechanical draft.
3-1- NaturaI draft
Natural draft is the draft produced by a chimney alone. t is caused
by the difference in weight between the column of hot gas inside the
chimney and column of outside air of the same height and cross
section.
Being much lighter than outside air, chimney flue gas tends to rise,
and the heavier outside air flows in through the ash pit to take its
place.
Process Engineering
By: Dr. H.Farzaneh
Draft is usually controlled by hand-operated dampers in the chimney
and breeching connecting the boiler to the chimney.
Here no fans or blowers are used. The products of combustion are
discharged at such a height that it will not be a nuisance to the
surrounding community.
3-2- MechanicaI draft
t is draft artificially produced by fans. Three basic types of drafts that
are applied are:
1) Balanced draft: Forced-draft (F-D) fan (blower) pushes air into
the furnace and an induced draft (-D ) fan draws gases into the
chimney thereby providing draft to remove the gases from the boiler.
Here the pressure is maintained between 0.05to 0.10in . of water
gauge below atmospheric pressure in the case of boilers and slightly
positive for reheating and heat treatment furnaces.
Process Engineering
By: Dr. H.Farzaneh
2) Induced draft: An induced-draft fan draws enough draft for flow
into the furnace, causing the products of combustion to discharge to
atmosphere. Here the furnace is kept at a slight negative pressure
below the atmospheric pressure so that combustion air flows through
the system.
3) Forced draft: The Forced draft system uses a fan to deliver the
air to the furnace, forcing combustion products to flow through the
unit and up the stack.
Process Engineering
By: Dr. H.Farzaneh
4-4- Combustion ControIs
Combustion controls assist the burner in regulation of fuel supply,
air supply, (fuel to air ratio), and removal of gases of combustion
to achieve optimum boiler efficiency.
The amount of fuel supplied to the burner must be in proportion to
the steam pressure and the quantity of steam required.
The combustion controls are also necessary as safety device to
ensure that the boiler operates safely.
Process Engineering
By: Dr. H.Farzaneh
Various types of combustion controls in use are:
1) On/Off control: The simplest control, ON/OFF control means that
either the burner is firing at full rate or it is OFF. This type of
control is limited to small boilers.
2) High/low/off control: Slightly more complex is HGH/LOW/OFF
system where the burner has two firing rates. The burner operates
at slower firing rate and then switches to full firing as needed.
Burners can also revert to the low firing position at reduced load.
This control is fitted to medium sized boilers.
3) Modulating control: The modulating control operates on the
principle of matching the steam pressure demand by altering the
firing rate over the entire operating range of the boiler. Modulating
motors use conventional mechanical linkage or electric valves to
regulate the primary air, secondary air, and fuel supplied to the
burner. Full modulation means that boiler keeps firing, and fuel
and air are carefully matched over the whole firing range to
maximize thermal efficiency.
Process Engineering
By: Dr. H.Farzaneh
5- Mechanism of Combustion
Details of the mechanics of combustion depend to a great extent
on the fuel and the nature of the combustion system.
The chemical reaction equations presented here do not portray
the actual mechanism of combustion; they merely indicate the
initial and final chemical compositions of a reaction.
n most cases the reactions involve a sequence of steps, leading
from the reactants to the products, the nature of which depends on
the temperature, pressure, and other conditions of combustion.
Fuel molecules, for instance, may undergo thermal cracking,
producing more numerous and smaller fuel molecules and
perhaps breaking the molecules down completely into carbon and
hydrogen atoms before oxidation is completed.
Process Engineering
By: Dr. H.Farzaneh
n the case of solid fuels, combustion may be governed by the rate
at which oxidizer diffuses from the surrounding gases to the
surface and by the release of combustible gases near the surface.
Combustion of solids may be enhanced by increasing the fuel
surface area exposed to the oxidizer by reducing fuel particle size.
ExampIe 11
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Example 11 is, of course, an idealized example. n reality, the
reacting surface area of solid fuels is usually much larger than the
spherical surface area implied by their size.
We have seen that, for combustion to occur, molecules of oxidizer
must affiliate with fuel molecules, an action enhanced by the three
T's of combustion: turbulence, time, and temperature.
Chemical reactions take place more rapidly at high temperatures
but nevertheless require finite time for completion.
t is therefore important that burners be long enough to retain the
fuel-air mixture for a sufficiently long time so that combustion is
completed before the mixture leaves.
Turbulence, or mixing, enhances the opportunities for contact of
oxidizer and fuel molecules and removal of products of
combustion.
Process Engineering
By: Dr. H.Farzaneh
A flame propagates at a given speed through a flammable
mixture.
t will propagate upstream in a flow of a combustible mixture if its
flame speed exceeds the flow velocity.
f a fixed flame front is to exist at a fixed location in a duct flow in
which the velocity of the combustion gas stream exceeds the
propagation speed, some form of flame stabilization is required.
Otherwise the flame front is swept downstream and flameout
occurs.
Stabilization may be achieved by using fixed flameholders (partial
flow obstructions that create local regions of separated flow in
their bases where the flame speed is greater than the local flow
velocity) or by directing a portion of the flow upstream to provide a
low-speed region where stable combustion may occur.
Process Engineering
By: Dr. H.Farzaneh
Each combination of oxidizer and fuel has been seen to have a
particular stoichiometric oxidizer-fuel ratio for which the fuel is
completely burned with a minimum of oxidizer.
t has also been pointed out that it is usually desirable to operate
burners at greater than the theoretical air-fuel ratio to assure
complete combustion of the fuel and that this is sometimes
referred to as a lean mixture.
Occasionally it may be desirable to have incomplete combustion,
perhaps to produce a stream of products in which carbon
monoxide exists or to assure that all the oxidizer in the mixture is
consumed.
n that case a burner is operated at less than the stoichiometric
air-fuel ratio with what is called a rich mixture.
Process Engineering
By: Dr. H.Farzaneh
There are limits to the range of air-fuel ratios for which combustion
will occur called limits of flammability.
Here the density of the mixture is important.
The limits of flammability around the stoichiometric A/F are
reduced at low densities. f combustion is to occur reliably in
mixtures at low densities, it is necessary to closely control the air-
fuel ratio.
Process Engineering
By: Dr. H.Farzaneh
FIammabiIity:
Flammability is the ease with which a substance will ignite, causing
fire or combustion.
Flammability limits, also called flammable limits, or explosive limits
give the proportion of combustible gases in a mixture, between
which limits this mixture is flammable.
Gas mixtures consisting of combustible, oxidizing, and inert gases
are only flammable under certain conditions.
The lower flammable limit (LFL) (lower explosive limit) describes the
leanest mixture that is still flammable, i.e. the mixture with the
smallest fraction of combustible gas, while the upper flammable
limit (UFL) (upper explosive limit) gives the richest flammable
mixture.
ncreasing the fraction of inert gases in a mixture raises the LFL and
decreases UFL.
Process Engineering
By: Dr. H.Farzaneh
Deflagration is a propagation of a combustion zone at a velocity less
than the speed of sound in the unreacted medium.
Detonation is a propagation of a combustion zone at a velocity
greater than the speed of sound in the unreacted medium.
Explosion is the bursting or rupture of an enclosure or container due
to the development of internal pressure from a deflagration or
detonation
Flammability limits of mixtures of several combustible gases can be
calculated using Le Chatelier's mixing rule for combustible volume
fractions x
i
:
and similar for UFL
mix

=
i
i
mix
LFL
x
LFL
1
Process Engineering
By: Dr. H.Farzaneh
Temperature and pressure also influences flammability limits.
Higher temperature results in lower LFL and higher UFL, while
greater pressure increases both values.
The effect of pressure is very small at pressures below 10 millibar
and difficult to predict, since it has hardly been studied.
Controlling gas and vapor concentrations outside the explosive limits
is a major consideration in occupational safety and health.
Methods used to control the concentration of a potentially explosive
gas or vapor include use of sweep gas, an unreactive gas such as
nitrogen or argon to dilute the explosive gas before coming in
contact with air.
Use of scrubbers or adsorption resins to remove explosive gases
before release are also common.
Process Engineering
By: Dr. H.Farzaneh
Gases can also be maintained safely at concentrations above the
UFL, although a breach in the storage container can lead to
explosive conditions or intense fires.
Dusts also have upper and lower explosion limits, though the upper
limits are hard to measure and of little practical importance.
Lower explosive limits for many organic materials are in the range of
1050 g/m, which is much higher than the limits set for health
reasons, as is the case for the LFL of many gases and vapours.
Dust clouds of this concentration are hard to see through for more
than a short distance, and normally only exist inside process
equipment.
Explosion limits also depend on the particle size of the dust involved,
and are not intrinsic properties of the material.
Process Engineering
By: Dr. H.Farzaneh
n addition, a concentration above the LFL can be created suddenly
from settled dust accumulations, so management by routine
monitoring, as is done with gases and vapours, is of no value.
The preferred method of managing combustible dust is by preventing
accumulations of settled dust through process enclosure,
ventilation, and surface cleaning.
However, lower explosion limits may be relevant to plant design
Process Engineering
By: Dr. H.Farzaneh
The explosive limits of some gases and vapors are given below.
Concentrations are given in percent by volume of air.
Process Engineering
By: Dr. H.Farzaneh
ExampIe 12
A coal with a dry, ash-free composition of 0.87C , 0.09H
2
, 0.02S ,
and 0.02O
2
is burned with 25% excess air. The as-fired ash and
moisture contents are 6% and 4%, respectively.
(a) What are the stoichiometric and actual air-fuel ratios?
(b) What is the flue gas composition?
Solution:
(a) Before performing combustion calculations, it is necessary to
convert coal composition data to an as-fired basis. The ratio of as-
fired to dry, ash-free masses is:
9 . 0 04 . 0 06 . 0 1 1 = = M A
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
(b) The ratio of the masses of the flue gas components j per unit mass
of fuel are individually determined from the mass fraction of each
component of the coal.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
ExampIe 13
The Orstat analyzer of the stack gases for the fuel burned is 13%
CO
2
, 0.5% CO, and 3.2% O
2
. What is the actual fuel-air ratio and
the percentage of excess air?
Solution:
The mass of nitrogen supplied by the combustion air is the total
mass of nitrogen minus the mass of nitrogen from the fuel.
f f
CO CO
N
N C
x x
x
or
fuel of Mass
fuel in N Mass
fuel of Mass
C Mass
gas flue in C Moles
gas flue in N Moles
) ( ) )(
12
28
(
) )( )(
12
28
(
2
2
2
2
2

Process Engineering
By: Dr. H.Farzaneh
Where the mass fraction of carbon and nitrogen in the fuel are given
by C
f
and (N
2
)
f
The mole fraction of nitrogen in the flue gas is :
1-0.13- 0.005-0.032=0.833
The nitrogen-carbon mole ratio is then 0.833/(0.13+0.005)=6.17
Using C
f
= 0.783 and (N
2
)
f
=0
From the example 9, we know the theoretical air-fuel ratio is 11.79
( )| |
766 . 0
) ( ) /( 12 / 28
/
2
2 2
f f CO CO N
N C x x x
F A
+
=
( )
( )
7 . 14
766 . 0
0 ) 783 . 0 )( 17 . 6 ( 12 / 28
/ =

=
actual
F A
8 . 24 )
79 . 11
79 . 11 7 . 14
)( 100 ( =

= air excess
Process Engineering
By: Dr. H.Farzaneh
ExampIe 14
A) Determine the carbon component of the ultimate analysis, the
theoretical mass and mole air-fuel ratio and the molecular weight
of Oklahoma natural gas.
B) Determine the true air-fuel ratio and the percentage of excess air if
the flue gas Orstat analysis is 9% CO
2
, 3% O
2
, and 0.5% CO.
C) Determine also the mass of wet combustion products per unit
mass of natural gas.
Solution:
Calculations are presented in the spreadsheet table.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Carbon component of the uItimate anaIysis
M
i
=MW
i
.x
i
=16X0.841=13.456
M
T
= Sum of M
i
= 18.17
X
mi
=M
i
/M
T
=13.456/18.17=0.7406
Process Engineering
By: Dr. H.Farzaneh
Carbon component of the uItimate anaIysis
CF=MW
C
/MW
i
=12/16=0.75
MCF=x
mi
CF
=0.7406X0.75=0.555421
MCF
T
= Sum of MCF
= 0.6492
Process Engineering
By: Dr. H.Farzaneh
Air-Fuel Ratio
O H CO O H C
2 2 2 6 2
6 4 7 2 + +
733 . 3
) 6 24 )( 2 (
) 32 )( 7 (
=
+
= OF
Mass O
2i
=OF
i
x
mi
=3.733X0.1106=0.412988
TMO
2
=Sum Mass O
2i
=3.375234
Theory AFR=TMO
2
/0.2325=14.55
MoIe AFR= AFR(MW
f
/MW
A
)=9.15
Process Engineering
By: Dr. H.Farzaneh
Air-Fuel Ratio
M
i
=MW
i
.x
i
=0.09X44=3.96
M
T
= Sum of M
i
= 29.56
X
mi
=M
i
/M
T
=3.96/29.56=0.134
CF=MW
C
/MW
i
=12/44=0.27273
MCF=x
mi
CF
=0.27273X0.134=0.0365
MCF
T
= Sum of MCF
= 0.038566
Process Engineering
By: Dr. H.Farzaneh
Air-Fuel Ratio
N
2
to C Ratio
=0.875/0.03856=21.49 | |
766 . 0
) ( ) /(
/
2
2 2
f f CO CO N
N C x x x
F A
+
=
| |
06 . 18
766 . 0
) 1294 . 0 ( ) 6492 . 0 )( 49 . 21 (
/ =

= F A
Process Engineering
By: Dr. H.Farzaneh
Wet combustion products
Process Engineering
By: Dr. H.Farzaneh
The mole composition of the fuel is tabulated in the first tier of the
computations and converted to mass fraction by multiplying by
component molecular masses.
The sum of the masses of components per mole of fuel is the
average molecular mass of the fuel.
The mass fraction of the methane, for example is
mf
i
=13.456/18.17= 0.7405.
The carbon factor for each of the components are obtained by
dividing the mass of atoms of carbon of each compound by its
molecular mass.
For example for methane and ethane the carbon factors are
12/16=0.75and 24/30=0.8.
Process Engineering
By: Dr. H.Farzaneh
Respectively, the masses of carbon per mass of fuel are then the
products of the carbon factor and the mass fraction of the
compound in the fuel.
For methane this is (0.75)( 0.7405)=0.5554.
The carbon mass fractions of each of the components are then
summed to obtain the carbon component of the ultimate analysis
of the fuel, the mass fraction of the carbon in the fuel is 0.6492 .
The oxygen requirement for complete combustion of the fuel is
obtained by summing the oxygen requirements of each of
components. For example, for ethane:
Gives the mass of oxygen per unit mass of ethane
O H CO O H C
2 2 2 6 2
6 4 7 2 + +
733 . 3
) 6 24 )( 2 (
) 32 )( 7 (
=
+
Process Engineering
By: Dr. H.Farzaneh
The oxygen required for combustion of ethane per unit mass of
fuel is then the product of oxygen factor and the ethane mass
fraction:
The total oxygen requirement per unit mass of fuel is obtained by
summing the contributions of each of components, which in this
case is 3.375.
The stoichiometric air-fuel ratio is then 3.375/0.2325
The mole A/F is obtained using the molecular masses of air and
fuel:
4129 . 0 ) 1106 . 0 )( 733 . 3 ( =
15 . 9
9 . 28
) 17 . 18 )( 5 . 14 (
=
Process Engineering
By: Dr. H.Farzaneh
n the second tier of the computations in the table, the Orstat
analysis is given and the mole fraction are converted to mass
fraction.
The mass fraction of the carbon in the flue gas is calculated from
Orstat mass fractions in the same way as the earlier fuel carbon
computation.
The nitrogen-to-carbon mass ratio may then be determined as
0.8288/0.03857=21.49.
So the air-fuel ratio is:
The total flue gas products per mass of fuel consumed, including
water vapor, may then be determined from the mass of air and
fuel by applying the conversion of mass to products and reactants
to obtain 1+A/F=1+18.1=19.06
06 . 18
766 . 0
1294 . 0 ) 6492 . 0 )( 49 . 21 (
=

Process Engineering
By: Dr. H.Farzaneh
ExampIe 15
Raw coal has the following dry mass composition: 61.6% C, 4.2%
H
2
, 9.7% O
2
, 1.3% N
2
, 4.6% S, and 18.5% ash.
Determine the higher and lower heating values, in kJ / kg, of the
as-fired coal with 10% moisture.
Solution:
To adjust the composition for 10% moisture, the factor 1-A-M
becomes 1 0- 0.1 = 0.9.
The heat of reaction of hydrogen in its standard state is the heat of
formation of its product of combustion:
H
2
+ 0.5 O
2
H
2
O
Shows that one mole of hydrogen produces one mole of water.
The heat of formation of steam, - 241,826 kJ per kg-mole of water
formed or per kgmole of hydrogen burned, is also the heat of
combustion of hydrogen in the standard state.
Process Engineering
By: Dr. H.Farzaneh
Thus the hydrogen contributes 241,826/2 kJ per kg of hydrogen in
the coal.
The total energy released by the hydrogen in the coal is then
241,826/2 times the mass fraction of hydrogen in the coal.
Similar arguments may be made for hydrogen with product water
in the liquid phase and the carbon and sulfur components of the
coal.
Thus the lower and higher heating values of the coal are 23,135.2
and 23,966.9kJ /kg, respectively.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
References
Singer, Joseph G. (Ed.), Combustion / Fossil Power Systems. Windsor,
Conn Combustion Engineering nc., 1981.
Culp, Archie W., Principles of Energy Conversion. New York: McGraw-
Hill, 1979.
Sorenson, Harry A., Energy Conversion Systems. New York: Wiley,
1983.
Moeckel, W. E., and Weston, Kenneth C., .Composition and
Thermodynamic Properties of Air in Chemical Equilibrium,. NACA TN
4265, April 1958.
Process Engineering
By: Dr. H.Farzaneh
Chapter Four (PrincipIes of Process SimuIation )
Why we use process simuIation
Required competency
Impact of simuIation on process industry
Strategy for simuIation of compIex chemicaI processes
MathematicaI modeI
o RuIe of thumb for mass baIance
o Component Mass BaIance
o MuItipIe Components in MuItipIe Processes
AnaIyze a RecycIe System
Energy baIance
o OveraII steady - state energy baIance
o Unsteady-state Energy BaIance
Process Engineering
By: Dr. H.Farzaneh
1- Why we use process simuIation
Process simulation successful tool for design, optimization and
control of chemical processes.
Use of simulation expanded due to availability of high-speed
computers and software packages
2- Required competency
- Sound understanding of engineering fundamentals (physical
system & mechanisms). Process cannot be viewed as a black
box!
- Modeling skills (sound mathematical relations).
- Computational skills (proper solution technique, software
package, computer, etc.)
Process Engineering
By: Dr. H.Farzaneh
3- Impact of simuIation on process industry
A) Economic: cheaper to use simulation than to build numerous
different-size pilot-plants
B) Operation: Easier to develop alternative operating approaches via
a mathematical model than by experimental methods
C) Scale up: First-principles simulations can predict system
performance in new and different operating conditions
Process Engineering
By: Dr. H.Farzaneh
4- Strategy for simuIation of compIex chemicaI processes
A model (M) for a system (S) and and experiment (E) is anything
to which (E) can be applied in order to answer questions about
(S).
A system (S) can be regarded as an operator mapping its inputs,
u, to its outputs, y
x: states mass,
energy,
momentum,.
Process Engineering
By: Dr. H.Farzaneh
Strategy for simulation of complex chemical processes
Process Engineering
By: Dr. H.Farzaneh
5- MathematicaI modeI
1) Total mass balance:
Rate of Accumulation of total mass= (Rate of total mass in) (Rate
of total mass out)
2) Species mass balance:
Rate of accumulation of i = (Rate of i in) (Rate of i out) + (Rate of
generation i)
3) Energy balance:
Rate of accumulation of energy = (Rate of energy in) (Rate of
energy out) + (Rate of generation of energy)
4) Momentum balance:
Rate of accumulation of momentum = (Rate of momentum in)
(Rate of momentum out) + (Rate of generation of momentum)
Process Engineering
By: Dr. H.Farzaneh
5-1- RuIe of thumb for mass baIance
A) Closed system: A closed system is one which does not have
flows in or out of the substance. Almost always, when one refers
to a close system it is implied to be closed to mass flow but not
to other flows such as energy or momentum. The equation for a
closed system is:
Accumulation = Generation
The opposite of a closed system is an open system in which
the substance is allowed to enter and/or leave the system.
The funnel in the example was an open system because
mass flowed in and out of it.
Process Engineering
By: Dr. H.Farzaneh
B) No generation: Certain quantities are always conserved in the
strict sense that they are never created or destroyed. These are
the most useful quantities to do balances on because then the
user does not need to worry about a generation term.
Accumulation = In ~ Out
The most commonly-used conserved quantities are mass
and energy. t is important to note, however, that though the
total mass and total energy in a system are conserved, the
mass of a single species is not (since it may be changed
into something else). Neither is the "heat" in a system if a
so-called "heat-balance" is performed.
Therefore one must be careful when deciding whether to
discard the generation term.
Process Engineering
By: Dr. H.Farzaneh
C) Steady State: A system which does not accumulate a substance
is said to be at steady-state. Often times, this allows the
engineer to avoid having to solve differential equations and
instead use algebra.
In ~ Out + Generation = 0
TOTAL mass is a conserved quantity (except in nuclear
reactions, let's not go there), as is the mass of any individual
species if there is no chemical reaction occurring in the
system.
Let us write the conservation equation at steady state for
such a case (with no reaction):
In ~ Out = 0
Process Engineering
By: Dr. H.Farzaneh
Now, there are two major ways in which mass can enter or
leave a system: diffusion and convection.
However, for large-scale systems such as the ones considered
here, in which the velocity entering the unit operations is fairly
large and the concentration gradient is fairly small, diffusion can
be neglected and the only mass entering or leaving the system
is due to convective flow :
Similar equation apply for the mass out. n this book generally
we use the symbol to signify a convective mass flow rate, in
units of mass / time. Since the total flow in is the sum of
individual flows, and the same with the flow out, the following
steady state mass baIance is obtained for the overall mass in
the system:
uA m Mass
in in
= =

0 =
in out
m m

m
Process Engineering
By: Dr. H.Farzaneh
ExampIe 16
Feed stream of pure liquid water enters an evaporator at a rate
of 0.5 kg/s.
Three streams come from the evaporator: a vapor stream and
two liquid streams.
The flow rate of the vapor stream was measured to be 4x10
6
L/min and its density was 4 g/m^3. The vapor stream enters a
turbine, where it loses enough energy to condense fully and
leave as a single stream.
One of the liquid streams is discharged as waste, the other is
fed into a heat exchanger, where it is cooled. This stream leaves
the heat exchanger at a rate of 1500 pounds per hour.
Calculate the flow rate of the discharge and the efficiency of the
evaporator.
Process Engineering
By: Dr. H.Farzaneh
Solution:
Step 1: Draw a Flowchart
The problem as it stands contains an awful lot of text, but it
won't mean much until you draw what is given to you. First, ask
yourself, what processes are in use in this problem?
Make a list of the processes in the problem:
Evaporator (A)
Heat Exchanger (B)
Turbine (C)
Process Engineering
By: Dr. H.Farzaneh
Label all your flows. Label them with any information you are
given.
Process Engineering
By: Dr. H.Farzaneh
Step 2: Make sure your units are consistent
The second step is to make sure all your units are consistent
and, if not, to convert everything so that it is. n this case, since
the principle that we'll need to use to solve for the flow rate of
the waste stream ( ) is conservation of mass, everything will
need to be on a mass-flow basis, and also in the same mass-
flow units.
For example:
3
m
s kg m
s kg m
m kg
s m
s L
m L
J
/ 1893 . 0
/ 2666 . 0
/ 004 . 0
/ 67 . 66
60
min 1
1000
1
min 1
10 4
5
2
3
2
3
3 6
2
=
=
=
=

Process Engineering
By: Dr. H.Farzaneh
Step 3: Relate your variables:
Since we have the mass flow rate of the vapor stream we can
calculate the efficiency of the evaporator directly:
Finding , as asked for in the problem, will be somewhat more
difficult.
One place to start is to write the mass balance on the
evaporator, since that will certainly contain the unknown we
seek. Assuming that the process is steady state we can write:
3 . 53
/ 5 . 0
/ 2666 . 0
1
2
= = =
s kg
s kg
m
m
efficiencv

4
m

0
0
6 4 2 1
=
=
m m m m
Out In

Process Engineering
By: Dr. H.Farzaneh
5-2- Component Mass BaIance
Most processes, of course, involve more than one input and/or
output, and therefore it must be learned how to perform mass
balances on . The basic idea remains the same though.
We can write a mass balance in the same form as the overall
balance for each component:
In ~ Out + Generation = Accumulation
For steady state processes, this becomes:
In ~ Out + generation = 0
And we can write a similar mass balance for any component of a
stream:
0
, , ,
= +
gen a out a in a
m m m

Process Engineering
By: Dr. H.Farzaneh
This looks like we have three equations here, but in reality only two
of them are independent because:
1) The sum of the masses of the components equals the total mass
2) The total mass generation due to reaction is always zero (by the
law of mass conservation)
Therefore, if we add up all of the mass balances for the
components we obtain the overall mass balance.
Therefore, we can choose any set of n equations we want, where n
is the number of components, but if we choose the overall mass
balance as one of them we cannot use the mass balance on one
of the components.
Process Engineering
By: Dr. H.Farzaneh
The choice of which balances to use depends on two particular
criteria:
1) Which components you have the most information on; if you don't
have enough information you won't be able to solve the equations
you write.
2) Which components you can make the most reasonable
assumptions about. For example, if you have a process involving
oxygen and water at low temperatures and pressures, you may
say that there is no oxygen dissolved in a liquid flow stream, so it
all leaves by another path.
This will simplify the algebra a good deal if you write the mass
balance on that component.
Process Engineering
By: Dr. H.Farzaneh
ExampIe 17
Suppose a stream containing ethanol and water (two fully miscible
compounds) flows into a distillation column at 100 kg/s. Two
streams leave the column: the vapor stream contains 80% ethanol
by mass and the liquid bottoms has an ethanol concentration of
4M. The total liquid stream flow rate is 20 kg/s.
Calculate the composition of the entrance stream.
Solution:
Step 1: Draw a Flowchart
The first step as always is to draw the flowchart, as described
previously. f you do that for this system, you may end up with
something like this, where x signifies mass fraction, [A] signifies
molarity of A, and numbers signify stream numbers.
Process Engineering
By: Dr. H.Farzaneh
Process Engineering
By: Dr. H.Farzaneh
Step 2: Convert Units
Now, we need to turn to converting the concentrations into
appropriate units. Since the total flow rates are given in terms of
mass, a unit that expresses the concentration in terms of mass of
the components would be most useful.
The vapor stream compositions are given as mass percents, which
works well with the units of flow. However, the liquid phase
concentration given in terms of a molarity is not useful for finding a
mass flow rate of ethanol (or of water).
Hence we must convert the concentration to something more
useful.
n order to convert the molarity into a mass fraction, then, we need
the molecular weight of ethanol and the density of a 4M ethanol
solution. The former is easy if you know the chemical formula of
ethanol: CH3CH2OH. Calculating the molecular weight (as you
did in chem class) you should come up with about 46 g/mol
Process Engineering
By: Dr. H.Farzaneh
Calculating the density involves plugging in mass fractions in and
of itself, so you'll end up with an implicit equation. Recall that one
method of estimating a solution density is to assume that the
solution is ideal (which it probably is not in this case, but if no data
are available or we just want an estimate, assumptions like these
are all we have, as long as we realize the values will not be
exact):
| | 195 . 0
1000
1
789
46 4
) (
1000
1
789
1
1000 00 . 1
789 789 . 0
1
3
2
3
2
2
=
|
|
|
|
.
|

\
|

+ = =

+ =
= =
= =
+ =
|
|
.
|

\
|
=

L
g
x
L
g
x
mol
g
L
mol MW
EtOH x
L
g
x
L
g
x
L
g
cm
g
L
g
cm
g
x x x
EtOH EtOH
SLN
EtOH
EtoH
EtOH EtOH
SLN
O H
EtOH
O H
O H
EtOH
EtOH
k
k
SLN

Process Engineering
By: Dr. H.Farzaneh
Step 3: Relate your Variables
Since we are seeking properties related to mass flow rates, we will
need to relate our variables with mass balances.
Remember that we can do a mass balance on any of the N
independent species and one on the overall mass, but since the
sum of the individual masses equals the overall only N ~ 1 of
these equations will be independent. t is often easiest
mathematically to choose the overall mass balance and N ~ 1
individual species balances, since you don't need to deal with
concentrations for the overall measurements.
Since our concentrations are now in appropriate units, we can do
any two mass balances we want. Lets choose the overall first:
321 . 0
) ( ) ( ) (
/ 80 / 20 / 100
0
1 ,
3 3 , 2 2 , 1 1 , 3 , 2 , 1 ,
2
3 2 1
=
+ = = + =
= =
=
a
a a a a a a
x
m x m x m x m m m
s kg s kg s kg m
m m m

H
2
O
Process Engineering
By: Dr. H.Farzaneh
5-3- MuItipIe Components in MuItipIe Processes
n the vast majority of chemical processes, in which some raw
materials are processed to yield a desired end product or set of
end products, there will be more than one raw material entering
the system and more than one unit operation through which the
product must pass in order to achieve the desired result.
The calculations for such processes, as you can probably guess,
are considerably more complicated than those either for only a
single component, or for a single-operation process.
Therefore, several techniques have been developed to aid
engineers in their analyses.
For more complex problems than the single-component or single-
operation problems that have been explored, it is essential that
you have a method of determining if a problem is even solvable
given the information that you have.
Process Engineering
By: Dr. H.Farzaneh
There are three ways to describe a problem in terms of its solvability:
1) f the problem has a finite (not necessarily unique!) set of
solutions then it is called well-defined.
2) The problem can be over determined (also known as over
specified), which means that you have too much information and it
is either redundant or inconsistent. This could possibly be fixed by
consolidating multiple data into a single function or, in extreme
cases, a single value (such as a slope of a linear correlation), or it
could be fixed by removing an assumption about the system that
one had made.
3) The problem can be underdetermined (or underspecified), which
means that you don't have enough information to solve for all your
unknowns. There are several ways of dealing with this. The most
obvious is to gather additional information, such as measuring
additional temperatures, flow rates, and so on until you have a
well-defined problem.
Process Engineering
By: Dr. H.Farzaneh
The method of analyzing systems to see whether they are over or
under-specified, or if they are well-defined, is called a degree of
freedom analysis. t works as follows for mass balances on a single
process:
1) From your flowchart, determine the number of unknowns in the
process. What qualifies as an unknown depends on what you're
looking for, but in a material balance calculation, masses and
concentrations are the most common. n equilibrium and energy
balance calculations, temperature and pressure also become
important unknowns. n a reactor, you should include the conversion
as an unknown unless it is given OR you are doing an atom
balance.
2) Subtract the number of Equations you can write on the process. This
can include mass balances, energy balances, equilibrium
relationships, relations between concentrations, and any equations
derived from additional information about the process.
3) The number you are left with is the degrees of freedom of the
process.
Process Engineering
By: Dr. H.Farzaneh
Multiple-process systems are tougher but not undoable. Here is
how to analyze them to see if a problem is uniquely solvable:
1) Label a flowchart completely with all the relevant unknowns.
2) Perform a degree of freedom analysis on each unit operation, as
described above.
3) Add the degrees of freedom for each of the operations.
4) Subtract the number of variables in intermediate streams, i.e.
streams between two unit operations. This is because each of
these was counted twice, once for the operation it leaves and
once for the one it enters.
The number you are left with is the process degrees of freedom,
and this is what will tell you if the process as a whole is
overspecified, underspecified, or well-defined.
Process Engineering
By: Dr. H.Farzaneh
Once you have determined that your problem is solvable, you still
need to figure out how you'll solve for your variables. This is the
suggested method.
A) Find a unit operation or combination of unit operations for which
the degrees of freedom are zero.
B) Calculate all of the unknowns involved in this combination.
C) Recalculate the degrees of freedom for each process, treating the
calculated values as known rather than as variables.
D) Repeat these steps until everything is calculated (or at least that
which you seek)
Process Engineering
By: Dr. H.Farzaneh
ExampIe 18
Consider a process in which raw oranges are processed into
orange juice. A possible process description follows:
1) The oranges enter a crusher, in which all of the water contained
within the oranges is released.
2) The now-crushed oranges enter a strainer. The strainer is able to
capture 90% of the solids, the remainder exit with the orange juice
as pulp.
The velocity of the orange juice stream was measured to be 30
m/s and the radius of the piping was 8 inches.
Calculate: a) The mass flow rate of the orange juice product. b)
The number of oranges per year that can be processed with this
process if it is run 8 hours a day and 360 days a year. gnore
changes due to unsteady state at startup.
Use the following data: Mass of an orange: 0.4 kg Water content
of an orange: 80% Density of the solids: Since its mostly sugars,
its about the density of glucose, which is 1.54g /cm
3
Process Engineering
By: Dr. H.Farzaneh
Step 1: Draw a Flowchart
This time we have multiple processes so it's especially important to
label each one as its given in the problem.
Process Engineering
By: Dr. H.Farzaneh
Step 2: Degree of Freedom analysis
Recall that for each stream there are C independent unknowns,
where C is the number of components in the individual stream.
These generally are concentrations of C-1 species and the total
mass flow rate, since with C-1 concentrations we can find the last
one, but we cannot obtain the total mass flow rate from only
concentration.
Let us apply the previously described algorithm to determining if
the problem is well-defined.
On the strainer:
There are 6 unknowns: m2, xS2, m3, xS3, m4, and xS4
We can write 2 independent mass balances on the overall system
(one for each component).
We are given a conversion and enough information to write the
mass flow rate in the product in terms of only concentration of one
component (which eliminates one unknown). Thus we have 2
additional pieces of information.
Thus the degrees of freedom of the strainer are 6-2-2 = 2 DOF
Process Engineering
By: Dr. H.Farzaneh
On the crusher:
There are 3 unknowns (m1, m2, and xS2).
We can write 2 independent mass balances.
Thus the crusher has 3-2 = 1 DOF
Therefore for the system as a whole:
Sum of DOF for unit operations = 2 + 1 = 3 DOF
Number of intermediate variables = 2 (m2 and xS2)
Total DOF = 3 - 2 = 1 DOF.
Hence the problem is underspecified
Process Engineering
By: Dr. H.Farzaneh
So how to we solve it?
n order to solve an underspecified problem, one way we can
obtain an additional specification is to make an assumption. What
assumptions could we make that would reduce the number of
unknowns (or equivalently, increase the number of variables we
do know)?
The most common type of assumption is to assume that
something that is relatively insignificant is zero.
n this case, one could ask: will the solid stream from the strainer
contain any water? t might, of course, but this amount is probably
very small compared to both the amount of solids that are
captured and how much is strained, provided that it is cleaned
regularly and designed well. f we make this assumption, then this
specifies that the mass fraction of water in the waste stream is
zero (or equivalently, that the mass fraction of solids is one).
Therefore, we know one additional piece of information and the
degrees of freedom for the overall system become zero.
Process Engineering
By: Dr. H.Farzaneh
Step 3: Convert Units
This step should be done after the degree of freedom analysis,
because that analysis is independent of your unit system, and if
you don't have enough information to solve a problem (or worse,
you have too much), you shouldn't waste time converting units
and should instead spend your time defining the problem more
precisely and/or seeking out appropriate assumptions to make.
Here, the most sensible choice is either to convert everything to
the cgs system or to the m-kg-s system, since most values are
already in metric. Here, the latter route is taken.
3 3
4
1540 54 . 1
2032 . 0
100
1 54 . 2
8
m
kg
cm
g
m
cm
m
in
cm
in r
S
= =
= =

Process Engineering
By: Dr. H.Farzaneh
Step 4: Relate your variables
First we have to relate the velocity and area given to us to the
mass flow rate of stream 4, so that we can actually use that
information in a mass balance. From chapter 2, we can start with
the equation:
Hence, we have the equation we need with only concentrations
and mass flow rates:
1000
1
1540
1 1
1297 . 0 30
1297 . 0 2032 . 0
4 4 4 4
4
4 4
2 2
4
S S
W
S
S
S
n n n n
x x x x
m
m A
m A u

+ =

+ =
=
= =
=

4
4 4
8915 . 3
1000
1
1540
: 1
m
x x
Equation
S S

+
Process Engineering
By: Dr. H.Farzaneh
Now we have an equation but we haven't used either of our two
(why two?) independent mass balances yet. We of course have a
choice on which two to use.
n this particular problem, since we are directly given information
concerning the amount of solid in stream 4 (the product stream), it
seems to make more sense to do the balance on this component.
Since we don't have information on stream 2, and finding it would
be pointless in this case (all parts of it are the same as those of
stream 1), lets do an overall-system balance on the solids:
) ( 1 ) 2 . 0 9 . 0 ( 2 . 0 : 2
) ( ) ( ) (
0
4 4 1 1
4 4 3 3 1 1
, ,
S
S S S
out S in S
x m m m Eqaution
x m x m x m
m m



+ =
+ =
=

With assumption that stream 3 is pure solids (no water) and hence
x
S3
= 1
Process Engineering
By: Dr. H.Farzaneh
Finally, we can utilize one further mass balance, so let's use the
easiest one: the overall mass balance. This one again assumes
that the total flow rate of stream 3 is equal to the solids flow rate.
We now have three equations in three unknowns so the problem
is solvable. This is where all those system-solving skills will come
in handy.
f you don't like solving by hand, there are numerous computer
programs out there to help you solve equations like this, such as
MATLAB, POLYMATH, and many others. You'll probably want to
learn how to use the one your school prefers eventually so why
not now?
Using either method, the results are:
4 1 1
2 . 0 9 . 0 : 3 m m m Equation + =
0244 . 0
07 . 3925
4786
4
4
1
=
=
=
S
x
s
kg
m
s
kg
m

Process Engineering
By: Dr. H.Farzaneh
We're almost done here, now we just have to calculate the
number of oranges per year.
vear
orange
oduction Yearlv
vear
dav wk
dav
hr wk
hr
s
kg
orange
s
kg
11
10 24 . 1 Pr
360 8 3600
4 . 0
1 4786
=

Process Engineering
By: Dr. H.Farzaneh
6- AnaIyze a RecycIe System
The biggest difference between recycle and non-recycle systems
is that the extra splitting and recombination points must be taken
into account, and the properties of the streams change from
before to after these points.
Process Engineering
By: Dr. H.Farzaneh
The "extra" stream between the splitting and recombination point
must be taken into account, but the way to do this is not to do a
mass balance on the process, since the recycle stream itself does
not go into the process, only the recombined stream does.
nstead, we take it into account by performing a mass balance on
the recombination point and one on the splitting point.
A) Assumptions at the SpIitting Point:
The recombination point is relatively unpredictable because the
composition of the stream leaving depends on both the
composition of the feed and the composition of the recycle stream .
However, the spliitng point is special because when a stream is
split, it generally is split into two streams with equal composition.
This is a piece of information that counts towards "additional
information" when performing a degree of freedom analysis.
Process Engineering
By: Dr. H.Farzaneh
B) Assumptions at the Recombination Point
The recombination point is generally not specified like the splitting
point, and also the recycle stream and feed stream are very likely
to have different compositions.
The important thing to remember is that you can generally use the
properties of the stream coming from the splitting point for the
stream entering the recombination point, unless it goes through
another process in between (which is entirely possible).
Degree of freedom analyses are similar for recycle systems to
those for other systems, but with a couple important points that the
engineer must keep in mind:
1) The recombination point and the splitting point must be counted in
the degree of freedom analysis as "processes", since they can
have unknowns that aren't counted anywhere else
Process Engineering
By: Dr. H.Farzaneh
2) When doing the degree of freedom analysis on the splitting point,
you should not label the concentrations as the same but leave
them as separate unknowns until after you complete the DOF
analysis in order to avoid confusion, since labeling the
concentrations as identical "uses up" one of your pieces of
information and then you can't count it.
As an example, let's do a degree of freedom analysis on the
hypothetical system above, assuming that all streams have two
components:
i) Recombination Point: 6 variables (3 concentrations and 3 total flow
rates) - 2 mass balances = 4 DOF
ii) Process: Assuming it's not a reactor and there's only 2 streams,
there's 4 variables and 2 mass balances = 2 DOF
iii) Splitting Point: 6 variables - 2 mass balances - 1 knowing
compositions are the same - 1 splitting ratio = 2 DOF
So the total is 4 + 2 + 2 - 6 (in-between variables) = 2 DOF
Process Engineering
By: Dr. H.Farzaneh
The way to make a plan is generally as follows:
1) Draw a completely labeled flow chart for the process.
2) Do a DOF analysis to make sure the problem is solvable.
3) f it is solvable, a lot of the time, the best place to start with a recycle
system is with a set of overall system balances, sometimes in
combination with balances on processes on the border. The reason
for this is that the overall system balance cuts out the recycle stream
entirely, since the recycle stream does not enter or leave the system
as a whole but merely travels between two processes, like any other
intermediate stream. Often, the composition of the recycle stream is
unknown, so this simplifies the calculations a good deal.
4) Find a set of independent equations that will yield values for a
certain set of unknowns (this is often most difficult the first time;
sometimes, one of the unit operations in the system will have 0 DOF
so start with that one. Otherwise it'll take some searching.)
5) Considering those variables as known, do a new DOF balance until
something has 0 DOF. Calculate the variables on that process.
6) Repeat until all processes are specified completely.
Process Engineering
By: Dr. H.Farzaneh
ExampIe 19
A mixture of 50% A and 50% B enters a separation process that is
capable of splitting the two components into two streams: one
containing 60% of the entering A and half the B, and one with 40%
of the A and half the B (all by mass):
f 100 kg/hr of feed containing 50% A by mass enters the
separator, what are the concentrations of A in the exit streams?
m
4
xA
4
Process Engineering
By: Dr. H.Farzaneh
Step 1: Do a Degree of Freedom Analysis
Recall that you must include the recombination and splitting points
in your analysis.
i) Recombination point: 4 unknowns - 2 mass balances = 2 degrees
of freedom
ii) Separator: 6 unknowns (nothing is specified) - 2 independent
pieces of information - 2 mass balances = 2 DOF
iii) Splitting point: 6 unknowns (again, nothing is specified) - 2 mass
balances - 1 assumption that concentration remains constant - 1
splitting ratio = 2 DOF
iv) Total = 2 + 2 + 2 - 6 = 0. Thus the problem is completely specified.
Process Engineering
By: Dr. H.Farzaneh
Step 3: Devise a Plan and Carry it Out
First, look at the entire system, since none of the original
processes individually had 0 DOF.
Overall mass balance on A
Overall mass balance on B
We have 4 equations and 2 unknowns at this point. This is where
the problem solving requires some ingenuity. First, lets see what
happens when we combine this information with the splitting ratio
and constant concentration at the splitter:
Splitting Ratio
Constant concentration
6 6 2 2
100 5 . 0
A A
x m x m
hr
kg
+ =
) 1 ( ) 1 ( 50
6 6 2 2 A A
x m x m
hr
kg
+ =
2
3
m
3 6 A A
x x =
Process Engineering
By: Dr. H.Farzaneh
Plugging these into the overall balances we have:
On A:
On total:
Again we have more equations than unknowns but we know how
to relate everything in these two equations to the inlet
concentrations in the separator. This is due to the conversions we
are given:
60% of entering A goes into stream 2 means
40% of entering A goes into stream 3 means
50% of entering B goes into stream 2 means
50% of entering B goes into stream 3 means
Spend some time trying to figure out where these equations come
from, it's all definition of mass fraction and translating words into
algebraic equations.
3
3
2 2
2
50
A A
x
m
x m

+ =
) 1 (
2
) 1 ( 50
3
3
2 2 A A
x
m
x m + =

4 4 2 2
6 . 0 m x x m
A A
=
4 4 3 3
4 . 0 m x x m
A A
=
4 4 2 2
) 1 ( 5 . 0 ) 1 ( m x x m
A A
=
4 4 3 3
) 1 ( 5 . 0 ) 1 ( m x x m
A A
=
Process Engineering
By: Dr. H.Farzaneh
Plugging in all of these into the existing balances, we finally
obtain 2 equations in 2 unknowns:
Solving these equations gives:
Once these values are known, you can choose to do a balance
either on the separator or on the recombination point, since both
now have 0 degrees of freedom. We choose the separator
because that leads directly to what we're looking for
) 1 (
2
4 . 0
) 1 ( 5 . 0 50 :
2
4 . 0
6 . 0 50 :
4 4 4 4
4 4 4 4
A A
A A
x m x m B on
x m x m A on
+ =
+ =


484 . 0 17 . 129
4 4
= =
A
x
hr
kg
m
Process Engineering
By: Dr. H.Farzaneh
The mass balances on the separator can be solved using the
same method as that without a recycle system, the results are:
Now we can assess how effective the recycle is. The
concentration of A in the liquid stream was reduced, by a small
margin of 0.016 mole fraction. However, this extra reduction
came at a pair of costs: the flow rate of dilute stream was
significantly reduced: from 50 to 29.165 kg/hr! This limitation is
important to keep in mind and also explains why we bother
trying to make very efficient separation processes.
429 . 0 165 . 29
2
429 . 0 33 . 58
530 . 0 83 . 70
3 6
3
6
3 3
2 2
= = = =
= =
= =
A A
A
A
x x
hr
kg m
m
x
hr
kg
m
x
hr
kg
m

Process Engineering
By: Dr. H.Farzaneh
7- Energy baIance
Energy balances can be calculated on the basis of external energy
used per kilogram of product, or raw material processed, or on dry
solids or some key component.
The most common important energy form is heat energy and the
conservation of this can be illustrated by considering operations
such as heating and drying.
n these, enthalpy (total heat) is conserved and as with the mass
balances so enthalpy balances can be written round the various
items of equipment or process stages, or round the whole plant,
and it is assumed that no appreciable heat is converted to other
forms of energy such as work.
Process Engineering
By: Dr. H.Farzaneh
Heat BaIance
Process Engineering
By: Dr. H.Farzaneh
7-1- OveraII steady - state energy baIance
Some important points:
i) f the system is closed AND at steady state that means the total
heat flow must equal the total work done in magnitude, and be
opposite in sign. However, according to another law of
thermodynamics, the second law, it is impossible to change ALL
of the heat flow into work, even in the most ideal case.

= + + + + + + 0 )
2
1
( )
2
1
(
,
2
,
2
s f out i in i
W Q H gh m v m H gh m v m

Process Engineering
By: Dr. H.Farzaneh
ii) n an adiabatic system with no work done, the total amount of
energy carried by mass flows is equal between those flowing in
and those flowing out.
However, that DOES NOT imply that the temperature remains the
same, as we will see in a later section. Some substances have a
greater capacity to hold heat than others, hence the term heat
capacity.
iii) f the conditions inside the system change over time, then we
CANNOT use this form of the energy balance.
The next section has information on what to do in the case that
the energetic of the system change.
Process Engineering
By: Dr. H.Farzaneh
7-2- Unsteady-state Energy BaIance
Following the logic from the mass balance, we obtain for the
accumulation:
Therefore, we have:
Like in the case of the mass balance, we can only consider the
totaI energy change over a totaI amount of time using this
equation. To do this, we multiply the entire equation above by the
time change from some starting point to the point of interest.

= + + + + + + on accumulati W Q H gh m v m H gh m v m
s f out i in i

,
2
,
2
)
2
1
( )
2
1
(
t
E E
t svs t t svs
A

A + , ,

A

= + + + + + +
A +
t
E E
W Q H gh m v m H gh m v m
t svs t t svs
s f out i in i
, ,
,
2
,
2
)
2
1
( )
2
1
(

Process Engineering
By: Dr. H.Farzaneh
Now we need some definitions
1) is the total heat flow over the time period
2) is the total shaft work over the time period
3) is the TOTAL mass flow into (or out of) the system
due to stream i during the time period.
4) is the TOTAL enthalpy carried into (or out of) the
system due to stream i during the time period.
The major assumption here is that the enthalpies, heat flow rates,
and shaft work on the left hand side of the equals sign must either
be constant, or the average value over the whole time period must
be used, in order for this equation to be valid.
t Q Q A =

t W W
s s
A =

i i
m t m A = A

t H H
i
A =

Process Engineering
By: Dr. H.Farzaneh
Whether this assumption is valid or not depends on the situation
(for example, it depends on whether the process feeding mass to
your process is itself at steady state or not).
With these in mind, we multiply by delta t in order to obtain the
following, unsteady state energy balance
t svs t t svs s f
out i in i
E E W Q
H mgh mv H mgh mv
, ,
,
2
,
2
)
2
1
( )
2
1
(
= +
+ + A + A + A + A

A +
Process Engineering
By: Dr. H.Farzaneh
ExampIe 20
A textile dryer is found to consume 4 m
3
/hr of natural gas with a
calorific value of 800 kJ/mole. f the throughput of the dryer is 60 kg
of wet cloth per hour, drying it from 55% moisture to 10% moisture,
estimate the overall thermal efficiency of the dryer taking into
account the latent heat of evaporation only.
Solution:
60 kg of wet cloth contains 60 x 0.55kg water = 33 kg moisture and
60 x (1-0.55) = 27 kg bone dry cloth.
As the final product contains 10% moisture, the moisture in the
product is 27/9= 3 kg
And so Moisture removed / hr = 33 - 3 = 30 kg/hr
Process Engineering
By: Dr. H.Farzaneh
Latent heat of evaporation = 2257 kJ/Kg
Heat necessary to supply = 30 x 2257 = 6.8 x 10
4
kJ/hr
Assuming the natural gas to be at standard temperature and
pressure at which 1 mole occupies
22.4liters.
Rate of flow of natural gas = 4 m3/hr = (4 x 1000)/22.4= 179 moles/hr
Heat available from combustion = 179 x 800 = 14.3x 10
4
kJ/hr
Approximate thermal efficiency of dryer = heat needed / heat used
= 6.8 x 10
4
/ 14.3x 10
4
= 48%
Process Engineering
By: Dr. H.Farzaneh
ExampIe 21 10000 lb/h of a mixture consisted of 40% Benzene
(Bz) and 60% BzCl is fed into a distillation column at 70 0F. The
overhead product containing 99.5% Bz. The bottom product
should be contained 1% Bz. Cooled water enters to condenser at
60 0F and leaves that at 140 0F. n reboiler, saturated steam is
consumed at 280 0F. Reflux ratio is 6 to 1. Assume, reboiler and
condenser work at atmospheric pressure and calculated
temperatures for condenser and reboiler are 178 0F and 268 0F
consequently. Also, outflow Bz fraction from reboiler is 3.9%
Calculate:
1) Overhead and bottom product flow rate
2) Reflux ratio flow rate
3) nlet flow to reboiler and
4) Consumed saturated steam and cooled water
Process Engineering
By: Dr. H.Farzaneh
F= 10000 lb/h
70 F 0.4 Bz
B
0.01 Bz
P
0.995 Bz
V
f
R
V
b
60 F
140 F
280 F
Sat. Steam
Process Engineering
By: Dr. H.Farzaneh
h lb B
h lb P
P P
B P
Bx Px Fx
B P
B P F
B P F
/ 6040
/ 3960
) 01 . 0 )( 10000 ( ) 995 . 0 ( ) 4 . 0 ( 10000
) 01 . 0 ( ) 995 . 0 ( ) 4 . 0 ( 10000
10000
=
=
+ =
+ =
+ =
+ =
+ =
Mass BaIance around the coIumn
Condenser:
h lb P R J
h lb P R or
P
R
f
/ 27720 3960 23760
/ 23760 ) 3960 ( 6 6 6
= + = + =
= = = =
Process Engineering
By: Dr. H.Farzaneh
) 039 . 0 ( ) 01 . 0 ( 6040
6040
b L
b
b B L
b
J Lx
J L
J Bx Lx
J B L
+ =
+ =
+ =
+ =
ReboiIer
We have three variables and just two equations. Therefore, energy
balance should be used.
At reference temperature 70 F:
} } }
+ =
178
70
268
70
178
70
dt Cp F dt Cp B dt Cp P Q Q
F B P condenser steam
Process Engineering
By: Dr. H.Farzaneh
| |
h Btu Q
h O H lb W
W
T T WC H J
Q H Q H
condenser
p on vapori:ati f
water water condenser condenser
/ 10 71 . 4
/ 10 89 . 5
) 60 140 )( 1 ( ) 005 . 0 ( 140 ) 995 . 0 ( 170 27720
) ( ) (
6
2
4
1 2
=
=
= +
= A
= A = A
Condenser
h lb
H
Q
Steam h Btu Q
h
Btu
lb
Btu
h
lb
lb
Btu
h
lb
Q
Ave ClB: B:
on vapori:ati
steam
steam
steam
/ 5760
932
10 31 . 5
/ 10 31 . 5
10 71 . 4 ) 3 . 68 ( 6040 ) 9 . 46 ( 3960
3 . 68 68 1 . 88
9 . 46 2 . 36 47
6
6
6
=

=
A
= =
+ + =
lb
Btu
H
P
A
Steam consumption
Process Engineering
By: Dr. H.Farzaneh
( ) ( ) | | ) 0 ( 154 01 . 0 126 99 . 0 ) 20 ( 39 . 0 ( 10 31 . 5
268
) ( ) (
6
B J L
h
Btu
F e temperatur reference At
H B H J T LCp Q
b
B J b L steam
b
+ + = +
A + A + A =
ReboiIer
Bz
ClBz
Temperature reduction in reboiler
Refer to mass baIance around the reboiIer
( ) ( ) | | ) 0 ( 154 01 . 0 126 99 . 0 ) 20 ( 39 . 0 ( 10 31 . 5
6
B J L
h
Btu
b
+ + = +
) 039 . 0 ( ) 01 . 0 ( 6040
6040
b L
b
b B L
b
J Lx
J L
J Bx Lx
J B L
+ =
+ =
+ =
+ =
Now we have 3 equations 3 variabIes set !
h lb J
h lb L
b
/ 39300
/ 453490
=
=
Process Engineering
By: Dr. H.Farzaneh
References
D.M.Himmelblau, Basic Principles and calculations in chemical
engineering, John Wiley and Sons,1993
Wayne C. Turner Energy Management Handbook, John Wiley and
Sons,2002
Felder, R.M. and R.W. Rousseau. Elementary Principles of Chemical
Processes. New York, Wiley, (2000
Scott Miller Dennis Pegden. NTRODUCTON TO MANUFACTURNG
SMULATONProceedings of the 2000 Winter Simulation ConferenceJ. A.
Joines, R. R. Barton, K. Kang, and P. A. Fishwick, eds