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ISOMERIZATION OF LIGHT
NAPHTHA
Group No. 1 Batch: 2008-2009
Names Seat no.
MUHIB NASEER MANSURI CH-005
WAHAJ SHAFI CH-006
FARHAN AHMED LARIK CH-058
KHURRAM REHMAN NIZAMI CH-063
Internal Advisor: Sir Fahim Uddin
DEPARTMENT OF CHEMICAL ENGINEERING
NED UNIVERSITY OF ENGINEERING AND
TECHNOLOGY
Dedicated to
Our beloved Parents & Teachers
i
CERTIFICATE
This is to certify that the work in this project report on ISOMERIZATION OF
LIGHT NAPHTHA is entirely written by the following students under the
supervision of Mr. Fahim Uddin. This project is submitted to Department of
Chemical Engineering for the fulfillment of the Bachelor Degree in Chemical
Engineering.
Group No. 1 Batch: 2008-2009
Names Seat no.
MUHIB NASEER MANSOORI CH-005
WAHAJ SHAFI CH-006
FARHAN AHMED LARIK CH-058
KHURRAM REHMAN NIZAMI CH-063
___________ Internal Adviser
___________ ___________ Examiner – 1 Examiner – 2
DEPARTMENT OF CHEMICAL ENGINEERING
NED UNIVERSITY OF ENGINEERING AND
TECHNOLOGY
ii
ABSTRACT
Energy exploration and conservation is one of the most critical challenge faced by
today‘s engineering world. Engineers of various expertises are working all over the
world for developing new modes of power generation and energy conservation. This
surge includes not only to find the new sources of energy but rather more significantly
to enhance the efficiency of already existing resources by adopting more fruitful ways
of power generation and reducing the amount of waste. Conversion of low energy
fuels into high energy fuels is one of the key aspects in this regard.
Petroleum refinery sector is also facing this widespread challenge. De-bottle necking
of various refinery processes are being carried out. For refinery sector, bringing a
maximum amount or refinery product into gasoline pool has been an attractive choice
for years. This has been done by converting various straight run cuts of crude oil into
the gasoline cut which is only about 7% of the feed crude. Several processes including
alkylation, reforming, cracking and isomerization are carried out to enhance the
production of gasoline pool. In Pakistan, the refinery sector is in practice of exporting
Light straight run naphtha (LSR) which is one of the key products, where it is either
used in petrochemical industries or it processed to increase its octane rating thus
making it fit to be used as an automobile fuel.
Isomerization of light straight run naphtha has now been done worldwide to increase
its octane rating. The octane rating of LSR can be enhanced by converting the straight
chain paraffins into branched chains. However the benzene present in LSR is
hazardous for the environment due to its carcinogenicity. This problem can be solved
by saturating this benzene into cyclo-hexane. Consequently a combination of two
processes that is saturation of benzene into cyclo-hexane followed by isomerization of
normal paraffin into iso paraffin under the action of Platinum based on alumina
catalyst is developed.
This report will discuss in detail this process for the LSR produced from Atmospheric
distillation column at Pakistan Refinery Limited. This report will discuss process
history, chemistry of the process, material and energy balances, equipment design,
economics for the process and environmental and safety concerns.
iii
ACKNOWLEDGEMENT
Our first thanks is to Allah The Almighty, the most merciful who blessed us with the
strength to achieve our task and helped us in all ups and downs during the final year
project in particular and in circles of life in general.
This final year project will hopefully serve us as a milestone in signifying the essence
of Chemical Engineering design. This project was rather an expedition characterized
by the team work, as well as by help from various personnel. Henceforth we are in
debt to acknowledge their support and guidance in completion of our project.
First and foremost we would like to acknowledge our project facilitator Engineer
Fahim Uddin who supported us and always drew a helping hand when needed. Most
importantly encouraged us to attempt this project unconventionally and provide us
full autonomy to enhance our talent and abilities.
Secondly, we would like to express our gratitude and acknowledgement to the support
of Engineer Tariq Masood (Senior Engineer Pakistan Refinery Limited) and Engineer
Rashid Hafeez (Process Manager Pakistan Refinery Limited)
Apart from the above mentioned, we would also like to acknowledge the grand
support of Professor Dr. Tufail Ahmed (Dean Chemical and Process Engineering),
Professor Dr. Inayatullah Memon (Chairman DEC) and all the faculty members of
department of Chemical Engineering especially Prof. Dr. Shazia F. Ali, Mr. Asim
Mushtaq, Mr. Adeel-ur-Rehman and our class advisor Mr. Saad Nadeem for his time
by time encouragement.
Authors
iv
CONTENTS
ABSTRACT ii
ACKNOWLEDGEMENT iii
CONTENTS iv
LIST OF FIGURES viii
NOTATIONS x
CHAPTER 1
INTRODUCTION 01-12
1.1 Refinery Products 02
1.2 Automobile Fuels 06
1.3 Octane number 06
1.4 Processing of heavier and lighter hydrocarbons than C7 and C8 07
1.5 What is Isomerization? 10
CHAPTER 2
ISOMERIZATION TECHNIQUES 13-22
2.1 UOP‘S Penex Process 13
2.2 Process Description 19
2.3 Octane Comparison for Different Processes 22
CHAPTER 3
PROCESS DESCRIPTION 23-42
3.1 Simple Process Description 23
3.2 Process Chemistry 24
3.3 Reactions 26
3.4 Process Variables 30
v
3.5 Process Equipment 35
CHAPTER 4
CATALYST SELECTION 43-49
4.1 Catalyst 43
4.2 Types of Catalysts 43
4.3 Dual-Functional Isomerization Catalysts 45
4.4 Alumina Catalyst 46
4.5 Chlorinated-Alumina based Catalysts 48
4.6 Zeolites 48
4.7 Zeolite Characteristics 49
CHAPTER 5
MATERIAL BALANCE 50-65
5.1 Material Balance Equations 50
5.2 Mass Balance on Mixer M 101 53
5.3 Material Balance around Reactors R 101 & R 102 55
5.4 Material Balance around Stabilizer T 101 61
5.5 Material Balance around Scrubber T 102 64
CHAPTER 6
ENERGY BALANCE 66-93
6.1 Energy Balance Equations 66
6.2 Energy Balance Around Reactor R-101 66
6.3 Energy Balance Around Reactor R-102 72
6.4 Energy Balance Around Heat Exchanger E 101 78
6.5 Energy Balance Around Heat Exchanger E 102 85
vi
6.6 Energy Balance Around Stabilizer T 101 92
CHAPTER 7
PLANT DESIGN CALCULATIONS 94-118
7.1 Reactors And its Types 94
7.2 Algorithm for determining reaction mechanism and
rate-limiting step 95
7.3 Designing of Reactor R 101 97
7.4 Designing of Reactor R 102 99
7.5 Designing of Naphtha Feed Pump P 101 101
7.7 Designing of Heat Exchanger E 101 104
7.8 Designing of Stabilizer T-101 107
7.6 Designing of Hydrogen Feed Compressor K 101 113
CHAPTER 8
COST ESTIMATION 119-128
8.1 Cost Estimation 120
8.2 Cost Estimation of our plant 123
8.3 Economics of Plant Location 125
8.4 Plant Location and Site Selection 126
CHAPTER 9
ENVIRONMENT AND SAFETY 129-142
9.1 Definition of a Petroleum Refinery 129
9.2 Background 129
9.3 Processes involved in refining crude oil 130
vii
9.4 Environmental hazards of petroleum refineries 134
9.5 Material Safety Data Sheet 134
CHAPTER 10
INSTRUMENTATION AND CONTROL 143-151
10.1 Components of the Control System 144
10.2 Analysis of Measurement 144
10.3 Controller 145
10.4 Characteristics of Controller 145
10.5 Modes of Control 146
10.6 Alarms and Safety Trips 146
10.7 Control loops 146
10.8 Feed Back Control Loop 147
10.9 Feed Forward Control Loop 147
10.10 Ratio Control 147
10.11 Auctioneering Control Loop 148
10.12 Split Range Loop 148
10.13 Cascade Control Loop 148
10.14 Interlocks 148
10.15 Control of Heat Exchanger 148
REFERENCES 152
LIST OF APPENDICES 154
viii
LIST OF FIGURES
Number Figure Title Page Number
Figure 1.1 Crude Distillation Products 2
Figure 1.2 The isomerization reactions kinetics 11
Figure 1.3 Comparison of operating Conditions of Catalyst 12
Figure 2.1 Hydrocarbon Once-Through Penex Process 15
Figure 2.2 Block flow diagram of ―one through‖ process 17
Figure 2.3 Block flow diagram of process with DIP 18
Figure 2.4 DIP-Penex-DIH 19
Figure 2.5 Penex/Molex Process flow scheme 19
Figure 2.6 BFD of Molex Process 20
Figure 2.7 Octane Comparison for different Processes
{Feed RON = 60 to 70} 22
Figure 3.1 C5 paraffin equilibrium plot 26
Figure 3.2 Equilibrium composition of hexane isomers
in relation to temperature 26
Figure 3.3 Iso-pentane equilibrium curve 32
Figure 3.4 2-2Dimethyl butane Equilibrium curve 33
Figure 3.5 Equilibrium Curve 33
Figure 3.6 Process Flow Diagram 42
Figure 4.1 Dependence of n-paraffins conversion on
reaction temperature 43
ix
Figure 4.2 Aluminum Oxide 47
Figure 4.3 Characteristics of chlorinated alumina
Catalysts 48
Figure 4.4 Structure and dimension of different types
of zeolite 49
Figure 4.5 Catalysts Performance Curves 49
Figure 5.1 Thermodynamic equilibrium for the isomerization
of heptane 51
Figure 5.2 Thermodynamic equilibrium for the isomerization
of Butane, pentane and hexane 52
x
NOTATIONS
Rd Fouling Factor
μ Viscosity
Cp Specific Heat
Q Heat Duty
Ux Overall Heat Transfer Coefficient
Ax Surface area for heat transfer
Fa Factor Area
Nt Number of tubes
At Area of tubes
Gt Mass velocity
ht Film coefficient
Wa Mass flow rate of air
ha Film coefficient
da Density of air
Nmin Minimum no. of stages
S Separation Factor
Rmin Minimum reflux ratio
CFS Vapor flow rate
GPM Liquid flow rate
σ Surface Tension
ρv Vapor density
ρl Liquid density
α Relative Volatility
R Reflux ratio
S Tray spacing
hct Clear liquid height
Dh Hole diameter
xi
UN Superficial vapor velocity based on net area
AN Net area
SF Derating factor
Ad Down comer top area
At Total tower cross section area
Dt Tower diameter
Af Fractional hole area
hw Outlet weir height
hcl Clearance under the down comer
T Tray deck thickness
Lw Outlet weir length
Ql Liquid load
Adt Down comer top area
Adb Down comer bottom area
Ac Active area
hd Dry plate pressure drop
Cd Orifice coefficient
Uh Velocity through holes
Ah Hole area
Aa Active area
Hr Residual head
how Liquid head over the outlet weir
tr Down comer residence time
Φ Viscosity gradient correction
K Thermal Conductivity
B Correction Factor
Y Correction Factor
F Correction Factor
Fp Air pressure drop factor
DR Density ratio
N Number of rows of tube in direction of flow
ACFM Actual cubic feet per minute
xii
NR Modified Reynolds number
AR Area ratio of fin tube
S Specific gravity
de Equivalent diameter (inch)
De Equivalent diameter (ft)
H2 Hydrogen Gas
C1 Methane
C2 Ethane
C3 Propane
n C4 Normal Butane
n C5 Normal Pentane
n C6 Normal Hexane
n C7 Normal Heptane
i C4 Iso Butane
i C5 Iso Pentane
2 MP 2 Methyl Pentane
3 MP 3 Methyl Pentane
2, 2 DMB 2, 2 Di Methyl Butane
2,3DMB 2, 3 Di Methyl Butane
2 MH 2 Methyl Hexane
3 MH 3 Methyl Hexane
2, 2 DMP 2, 2 Di Methyl Pentane
2, 3 DMP 2, 3 Di Methyl Pentane
2, 4 DMP 2, 4 Di Methyl Pentane
3, 3 DMP 3, 3 Di Methyl Pentane
3 EP 3 Ethyl Pentane
xiii
C6H6 Benzene
C7H8 Toluene
CP Cyclo Pentane
MCP Methyl Cyclo Pentane
CH Cyclo Hexane
ECP Ethyl Cyclo Pentane
MCH Methyl Cyclo Hexane
2, 2, 3 TMB 2, 2, 3 Tri Methyl Butane
H2O Water
C2Cl4 Perchloro Ethylene
HCL Hydrochloric Acid
CHAPTER 1
INTRODUCTION
Chapter 1 Introduction
1
CHAPTER # 1
INTRODUCTION
The world of today puts great emphasis on the use of the available sources of energy
in the most economical way to meet the forthcoming challenges in the field of global
energy consumption. This has enhanced the need of not only developing methods of
efficient ways of utilizing a fuel but much more than that on developing fuels that are
more equipment friendly and environment friendly. Energy sectors are working not
only to find alternatives of conventional fossil fuels by replacing them with solar,
wind and geothermal energy sources but at the same time already existing fuels are
being made more efficient by treating them with various chemical and physical
processes.
In the field of automotive the fuel consumption is increasing day by day with the
decreasing prices of automotive for last few decades. This has forced the refinery
sector to acquire possible ways which may increase the percentage of the crude
distillate that can be used as gasoline. The gasoline cut that is obtained from the crude
oil contains hydrocarbons of C7 and C8 range. This range of hydrocarbons has better
compatibility with the operating conditions (temperature and pressure) of gasoline
engine and thus required rate of combustion is obtained in the gasoline engine using
them as fuels. This property of the fuel is distinguished by a quantity remarked as
octane number. Hence in gasoline engines a major criterion for selection of fuels is
its octane number.
For the reason mentioned above the crude refining sector turned its attention towards
the effective ways of increasing the octane number of fractions of crude distillate (not
C7and C8) by adopting different methods. The addition of small amount of TEL
(tetra ethyl lead) in the gasoline pool has a remarkable increase in the pool octane
number; this method was relatively very cheap and had been used for several years.
However the carcinogenity of the lead urged the environmental safety organizations
to put a ban on the use of TEL in the commercial gasoline. Ultimately a surge of
finding the alternative methods of increasing the octane number of the gasoline pool
Chapter 1 Introduction
2
raised in the refining sectors, methods such as Alkylation and Isomerization were
adopted for enhancing the octane ratings of the lighter ends of the crude distillate and
method of Cracking was adopted to convert heavier ends (above C8) distillate into
fractions of gasoline range. These different methods are being used in the refineries
throughout the world.
1.1 REFINERY PRODUCTS:
We shall firstly be discussing the types of the products that are obtained from a
refinery (general fractions of crude distillate) and their classification. Raw crude oil
obtained from the earth crust is pretreated to remove water and salt contents, then it is
distilled at atmospheric pressure to obtain a series of products having a specific
boiling range from 32 to 4300C.The residue from the atmospheric distillation column
is further fractionated in a vacuum distillation column. A list of these products is
given below:
Figure 1.1 Crude Distillation Products (Gary and Handwerk, 2001)
Light straight run naphtha and heavy straight run naphtha constitute about 3% to 4%
of the input crude. The range for naphtha is from C5 to C12. Light naphtha are the
hydrocarbon fractions of range C5 to C6 (including normal, iso and cyclo pentanes and
hexanes, olefins of C5 and C6 and benzene and its derivatives) whereas heavy naphtha
ranges from C7 to C10 (including gasoline, jet fuels and aviation fuels).
Crude oil is a complex liquid mixture made up of a vast number of hydrocarbon
compounds that consist mainly of carbon and hydrogen in differing proportions. In
addition, small amounts of organic compounds containing sulphur, oxygen, nitrogen
and metals such as vanadium, nickel, iron and copper are also present. Hydrogen to
Chapter 1 Introduction
3
carbon ratios affects the physical properties of crude oil. As the hydrogen to carbon
ratio decreases, the gravity and boiling point of the hydrocarbon compounds
increases.
Moreover, the higher the hydrogen to carbon ratio of the feedstock, the higher its
value is to a refinery because less hydrogen is required. The composition of crude oil,
on an elemental basis, falls within certain ranges regardless of its origin.
We shall be further discussing the types of the hydrocarbons that are obtained from
the refining of crude oil. These different hydrocarbons are then classified according to
their octane ratings. All types of crude oil give the following 4 major types of
hydrocarbons.
Paraffin
Olefins
Naphthenes
Aromatics
1.1.1 Paraffins: These are the hydrocarbons that have single bond between all carbons present in the
chain. They have a general formula of CnH2n+2. The range of carbons in this type is
from a single carbon to hundreds of carbon atoms.
These paraffins are further of two types:
a) Normal (n) paraffins
b) Iso paraffins
Normal paraffins (n-paraffins or n-alkanes) are unbranched straight-Chain molecules.
Each member of these paraffins differs from the next higher and the next lower
member by a –CH2– group called a methylene group. They have similar chemical and
physical properties, which change gradually as carbon atoms are added to the chain.
Iso paraffins (or iso alkanes) are branched-type hydrocarbons that exhibit Structural
isomerization.
Chapter 1 Introduction
4
1.1.2 Olefins:
These are the hydrocarbons that have either double or triple (at least one or more) or
both types of bondings between the carbon atoms. They have a general formula of
CnH2n.
Olefins, also known as alkenes, are unsaturated hydrocarbons containing carbon–
carbon double bonds. Compounds containing carbon–carbon triple bonds are known
as acetylenes, and are also known as biolefins or alkynes.
Olefins are not naturally present in crude oils but they are formed during the
conversion processes. They are more reactive than paraffins. The lightest alkenes are
ethylene (C2H4) and propylene (C3H6), which is important feedstock for the
petrochemical industry. The lightest alkyne is acetylene.
1.1.3 Naphthenes:
Hydrocarbons lying in this range have a cyclic or ring structure but with the limitation
that all the bonds among neighboring carbons are single, they have a general formula
of CnH2n.
The boiling point and densities of naphthenes are higher than those of alkanes having
the same number of carbon atoms. Naphthenes commonly present in crude oil are
rings with five or six carbon atoms. These rings usually have alkyl substituents
attached to them. Multi-ring naphthenes are Present in the heavier parts of the crude
Chapter 1 Introduction
5
oil. Examples of naphthenes are shown below
1.1.4 Aromatics:
These hydrocarbons have a cyclic structure along with alternative double bonds
between the carbons joined in the ring. Benzene is a six carbon containing compound
with alternative double and single bonds, benzene and its alternatives collectively
constitute this group of hydrocarbons.
Crude oils from various origins contain different types of aromatic compounds in
different concentrations. Light petroleum fractions contain mono-aromatics, which
have one benzene ring with one or more of the hydrogen atoms substituted by another
atom or alkyl groups. Examples of these compounds are toluene and xylene. Together
with benzene, such compounds are important petrochemical feedstock, and their
presence in gasoline increases the octane number.
Chapter 1 Introduction
6
1.2 AUTOMOBILE FUELS:
The wide range of the refinery products obtained are sorted to be used as the fuel for
different sectors. The cut of the refinery products used by the automobile sector is
heptane and octane. This selection is governed by the combustion properties and the
conditions provided by these engines to the fuel. One of the significant properties is
the octane number of the fuel.
1.3 OCTANE NUMBER: An octane number is a measure of the knocking tendency of gasoline fuels in spark
ignition engines. The ability of a fuel to resist auto-ignition during compression and
prior to the spark ignition gives it a high octane number.
The octane number of a fuel is determined by measuring its knocking value
compared to the knocking of a mixture of n-heptane and isooctane (2, 2, 4-rimethyl
pentane). Pure n-heptane is assigned a value of zero octane while isooctane is
assigned 100 octane. Hence, an 80 vol% isooctane mixture has an octane number of
80. Two octane tests can be performed for gasoline.
The motor octane number (MON) indicates engine performance at highway
conditions with high speeds (900 rpm).
On the other hand, the research octane number (RON) is indicative of low-speed
city driving (600 rpm).
The posted octane number (PON) is the arithmetic average of MON and RON. One
of the standard tests is ASTM D2700.
Chapter 1 Introduction
7
1.4 PROCESSING OF HEAVIER AND LIGHTER HYDROCARBONS THAN C7
AND C8:
The range commonly used in gasoline pool is the C7 and C8 hydrocarbons. However
some lighter ends and some heavier ends are converted into this range by processing
to accommodate the increasing demand of the automobile fuel. Some of the common
procedures are briefly discussed.
1.4.1 Alkylation:
The addition of an alkyl group to any compound is an alkylation reaction but in
petroleum refining terminology the term alkylation is used for the reaction of low
molecular weight olefins with an isoparaffins to form higher molecular weight
isoparaffins. Although this reaction is simply the reverse of cracking, the belief that
paraffin hydrocarbons are chemically inert delayed its discovery until about 1935.
The need for high-octane aviation fuels during World War II acted as a stimulus to the
development of the alkylation process for production of isoparaffinic gasoline of high
octane number. The need for high-octane aviation fuels during World War II acted
as a stimulus to the development of the alkylation process for production of
isoparaffinic gasoline of high octane number.
The reactions occurring in both processes are complex and the product has a rather
wide boiling range. By proper choice of operating conditions, most of the product can
be made to fall within the gasoline boiling range with motor octane numbers from 88
to 94 and research octane numbers from 94 to 99.
Alkylation processes using hydrofluoric or sulfuric acids as catalysts, only iso
paraffins with tertiary carbon atoms, such as isobutane or isopentane, react with the
olefins. In practice only isobutane is used because isopentane has a sufficiently high
octane number and low vapor pressure to allow it to be effectively blended directly
into finished gasoline.
The principal reactions which occur in alkylation are the combinations of olefins with
isoparaffins as follows:
Chapter 1 Introduction
8
The product streams leaving an alkylation unit are:
LPG grade propane liquid
Normal butane liquid
C5+ alkylate
Tar
1.4.2 Catalytic Reforming:
Catalytic reforming of heavy naphtha and isomerization of light naphtha constitute a
very important source of products having high octane numbers which are key
components in the production of gasoline, Environmental regulations limit on the
benzene content in gasoline. If benzene is present in the final gasoline it produces
carcinogenic material on combustion. Elimination of benzene forming hydrocarbons,
such as hexane will prevent the formation of benzene, and this can be achieved by
increasing the initial point of heavy naphtha. These light paraffinic hydrocarbons can
be used in an isomerization unit to produce high octane number isomers. Catalytic
reforming is the process of transforming C7–C10 hydrocarbons with low octane
numbers to aromatics and iso-paraffins which have high octane numbers. It is a highly
endothermic process requiring large amounts the straight run naphtha from the crude
distillation unit is hydrotreated to remove sulphur, nitrogen and oxygen which can all
deactivate the reforming catalyst. The hydrotreated naphtha (HTN) is fractionated into
light naphtha (LN), which Is mainly C5–C6, and heavy naphtha (HN) which is mainly
Chapter 1 Introduction
9
C7–C10 hydrocarbons. It is important to remove C6 from the reformer feed because it
will form benzene which is considered carcinogenic up on combustion. Light naphtha
(LN) is isomerized in the isomerization unit.
Light naphtha can be cracked if introduced to the reformer. Hydrogen, produced in
the reformer can be recycled to the naphtha hydrotreater, and the rest is sent to other
units demanding hydrogen.
In catalytic reforming the structure of the straight run cuts are altered by using several
techniques to make them lie within the gasoline range.
Reforming Reactions
Paraffin Dehydrogenation
Naphthene Dehydrogenation of Cyclohexanes
Isomerization
Isomerization is a mildly exothermic reaction and leads to the increase of an octane
number.
Dehydrocyclization
Chapter 1 Introduction
10
Hydrocracking Reactions
1.5 WHAT IS ISOMERIZATION:
Isomerization is the process in which light straight paraffins of low RON are
transformed into branched chain using proper catalysts. The paraffins used are C4, C5
and C6. The number of the carbon atoms remains constant but the octane number
increases. The naphtha obtained from the fractionation column of crude oil is
hydrotreated and further fractionated into heavier and light naphtha. Heavier naphtha
is (90-1900C) is used as a feed to the reforming unit. The light naphtha obtained (max
800C) is used as a feed for the isomerization unit. The reforming unit cannot treat
lighter naphtha because the C6 component of the paraffins tends to form benzene in
the reforming unit; this is an undesirable event as benzene concentrations in the
gasoline pool must be maintained down to a level because of its carcinogenity.
1.5.1 Thermodynamics of reaction:
The isomerization reactions are slightly exothermic and the reactions are carried out at
equilibrium (reversible reaction of significant level) the reaction equilibrium is
unaffected by the pressure variation as the number of moles on both sides remain
same. However kinetic studies have shown that a temperature of 125-1300C is
optimum for the reaction to be carried out.
Chapter 1 Introduction
11
Figure 1.2
1.5.2 Isomerization Reactions:
Isomerization is a reversible and slightly exothermic reaction:
The conversion to iso-paraffin is not complete since the reaction is equilibrium
conversion limited. It does not depend on pressure, but it can be increased by
lowering the temperature. However operating at low temperatures will decrease the
reaction rate. For this reason a very active catalyst must be used.
1.5.3 Isomerization Catalysts:
There are two types of isomerization catalysts
The standard Pt/chlorinated alumina
The Pt/zeolite catalyst.
Standard Isomerization Catalyst (Pt/chlorinated alumina)
This bi-functional nature catalyst consists of highly chlorinated alumina (8–15w%
chlorine) responsible for the acidic function of the catalyst. Platinum is deposited
(0.3–0.5 wt%) on the alumina matrix. Platinum in the presence of hydrogen will
prevent coke deposition, thus ensuring high catalyst activity. The reaction is
performed at low temperature at about 1300C.
To improve the equilibrium yield and to lower chlorine elution. The standard
isomerization catalyst is sensitive to impurities such as water and sulphur traces which
Chapter 1 Introduction
12
will poison the catalyst and lower its activity. For this reason, the feed must be
hydrotreated before isomerization. Furthermore, carbon tetrachloride must be injected
in to the feed to activate the catalyst. The pressure of the hydrogen in the reactor will
result in the elution of chlorine from the catalyst as hydrogenchloride. For all these
reasons, the zeolite catalyst, which is resistant to impurities, was developed.
1.5.4 Zeolite Catalyst:
Zeolites are crystallized silico-aluminates that are used to give an acidic function to
the catalyst. Metallic particles of platinum are impregnated on the surface of zeolites
and act as hydrogen transfer centres. The zeolite catalyst can resist impurities and
does not require feed pretreatment, but it does have lower activity and thus the
reaction must be performed at a higher temperature of 2500C. A comparison of the
operating conditions for the alumina and zeolite processes is shown
Figure 1.3 Comparison of operating Conditions of Catalyst
CHAPTER 2
ISOMERIZATION TECHNIQUES
Chapter 2 Isomerization Techniques
13
CHAPTER # 2
INTRODUCTION
2.1 UOP‘S PENEX PROCESS:
The Penex process has served as the primary isomerization technology for upgrading
C5/C6 light straight-run naphtha feeds since UOP introduced it in 1958. This process
has a wide range of operating configurations for optimum design flexibility and
feedstock processing capabilities.
The Penex process is a fixed-bed procedure that uses high activity chloride-promoted
catalysts to isomerize C5/C6 paraffins to higher octane branched components. The
reaction is conducted in the presence of a minor amount of hydrogen. Even though the
chloride is converted to hydrogen chloride, carbon steel construction is used
successfully because of the dry environment. For typical C5/C6 feeds, equilibrium will
limit the product to 83 to 86 RON (Research Octane Number) on a single
hydrocarbon pass basis.
The operating conditions are such that promote isomerization and minimize
hydrocracking. Operating conditions are not severe, as reflected by moderate
operating pressure, low temperature, and low hydrogen partial pressure requirements.
Ideally, this isomerization catalyst would convert all the feed paraffins to the high
octane-number branched structures: normal pentane (nC5) to isopentane (iC5) and
normal hexane (nC6) to 2,2- and 2,3-dimethylbutane. The reaction is controlled by a
thermodynamic equilibrium that is more favorable at low temperature.
Equipments Used in Penex Process:
Methanator feed effluent exchanger
Methanator feed steam exchanger
Methanator
Methanator knockout drum
Make-up gas dryers (2 in number)
Liquid feed dryer (2 in number)
Regenerant super heater
Chapter 2 Isomerization Techniques
14
Regenerant evaporator
Liquid feed surge drum
Charge pump (2 in number)
Chloride drum
Chloride injection pump (2 in number)
Combine feed exchanger (3 in number)
Reactors (2 in number)
Stabilizer column
Stabilizer re-boiler
Stabilizer overhead air cooler
Stabilizer overhead trim cooler
Stabilizer overhead separator
Stabilizer reflux pump (2 in number)
Net gas scrubber
Caustic circulation pump (2 in number)
Caustic tank
Water circulation pump (2 in number)
Water Tank
Water injection pump (2 in number)
Operation and Operating Conditions of some Penex Process Equipment:
2.1.1 Liquid Feed Driers Operation:
Hydro treated SR light naphtha at temperature 45 0C & pressure 4.5 kg/cm
2 is passed
through driers to control moisture at 1.0 ppmw in the feed. Drying medium is the
molecular sieves. There are two drier, one remain in operation while the other is on
regeneration. Isomerate is used as regenerant. Dry liquid feed is collected in feed
surge drum. Molecular sieves are regenerated by isomerate & there replacement
depends on the efficiency or after period of four year.
2.1.2 Make Up Gas Driers Operation:
Make up gas is dry by passing into dryers. Molecular sieves used as drying agents.
Dry gas is control at moisture < 1.0 ppmv. Before drying of gas CO & CO2 is
Chapter 2 Isomerization Techniques
15
removed from the makeup gas. It is accomplished by passing the gas through
Methanator. CO & CO2 are converted into methane in presence of Nickel oxide
catalyst. Nickel catalyst cannot be regenerated. It is replaced totally; its life is 4-5
years. Temperature & pressure of Methanator is maintained 220 °C & 27 kg/cm2.
2.1.3 Reactor Operations:
Combine liquid feed & make up gas is heated in pre-heat exchangers & chloride is
injected before entering the reactors. The Reactor System is typically designed to
operate at a minimum pressure of 31.6 Kg/cm2
(g). Lead reactor inlet temperatures
range from 131°C to 200°C and lag reactor inlet temperatures range from 142°C to
186°C. H2/HCBN mole ratio is maintained as 0.20 at reactors inlet & 0.05 at reactors
outlet.
2.1.4 Stabilizer Operation:
Reactor effluents passed through stabilizer where lighter gases & propane is separated
from the isomerate. Stabilizer column is operated at temperature 145 °C & pressure
18.0 kg/cm2.
2.1.5 Stabilizer Net Gas Scrubber Operation:
The purpose of net gas scrubbers is that to neutralize the net gas prior sending to fuel
gas header with caustic (strength is 10%wt). Operating parameters of net scrubbers is
that pressure is 6.5 kg/cm2 and temperature is 45 °C.
The most common Penex process is Hydrocarbon Once-Through Penex process.
2.1.6 Hydrocarbon Once-Through Penex Process:
Figure 2.1
Chapter 2 Isomerization Techniques
16
2.1.6.1 Process Description:
Hydrogen Once-Through Penex process flow scheme results in a substantial saving in
capital equipment and utility costs by eliminating product separator and recycle gas
compressor.
Light naphtha feed is charged to one of the two dryer vessels. These vessels are filled
with molecular sieves, which remove water and protect the catalyst. After mixing with
makeup hydrogen, the feed is heat-exchanged against reactor effluent. It then enters a
charge heater before entering the reactors.
Typically, two reactors in series are used to achieve high on-stream efficiency. The
catalyst can be replaced in one reactor while operation continues in the other. One
characteristic of the process is that catalyst deactivation begins at the inlet of the first
Reactor and proceeds slowly as a rather sharp front downward through the bed. The
adverse effect that such deactivation can have on unit on-stream efficiency is avoided
by installing two reactors in series. Each reactor contains 50% of the total required
catalyst. Piping and valving are arranged to permit isolation of the reactor containing
the spent catalyst while the second reactor remains in operation. After the spent
catalyst has been replaced, the relative processing positions of the two reactors are
reversed. During the short time when one reactor is off-line for catalyst replacement,
the second reactor is fully capable of maintaining continuous operation at design
throughput, yield, and conversion.
The reactor effluent flows to stabilizer after passing through the heat exchanger. The
stabilizer overhead vapors are caustic scrubbed for removal of the HCl formed from
organic chloride added to the reactor feed to maintain catalyst activity. After
scrubbing, the overhead gas then flows to fuel. The stabilized, isomerized liquid
product from the bottom of the column then passes to gasoline blending.
The Penex process (see below) uses the most active chlorided-alumina catalyst and
operates in the range 120-180°C.
Chapter 2 Isomerization Techniques
17
LHSV is set during the design phase of any isomerization project and reflects the
compromise between residence time and overall catalyst cost. At lower LHSVs, more
catalyst is loaded resulting in a longer residence time. As a result lower temperature
Operation is possible, resulting in a higher octane product.
System pressure is another variable and is considered in conjunction with the
hydrogen flow rate to the reactor. Chlorided-alumina is more active at higher
pressures. It requires only a slight excess over stoichiometric hydrogen, since the
catalyst does not produce coke. A Penex unit operates at about 30 to 32 bar with once-
through hydrogen.
Figure 2.2 (Block flow diagram of ―one through‖ process)
To achieve higher octane, UOP offers several schemes in which lower octane
components are separated and recycled back to the reactors. These recycle modes of
operation can lead to product octane as high as 93 RON.
2.1.7 Penex Process/DIH (De-isoHexanizer):
This flow scheme is same as Penex Process with an addition of deisohexanizer
column to recycle the methylpentanes, n-hexane, and some C6 cyclics. It is the lowest
cost option of the recycle flow schemes & provide high octane isomerate product,
especially on C6 rich feed.
Chapter 2 Isomerization Techniques
18
Figure 2.3 (Block flow diagram of process with DIP)
2.1.8 Penex Process With Recycle And Fractionation (DIP/Penex Process/DIH):
Separation and recycle of unconverted normal C5 and C6 paraffins and low octane C6
isoparaffins back to the reactor, produce a higher octane product. The most common
flow scheme uses a deisohexanizer (DIH) column to recycle methylpentanes, n-
hexane, and some C6 cyclics. It is the lowest capital cost option of the recycle flow
schemes and provides a higher octane isomerate product, especially on C6 rich feeds.
In the Penex/DIH process the stabilized isomerate is charged to a DIH column
producing an overhead product containing all the C5 and dimethylbutanes. Normal
hexane and some of the methylpentanes are taken as a side-cut and recycled back to
the reactors. The small amount of bottoms (C7+ and some C6 cyclics) can be sent to
gasoline blending or to a reformer
.
The addition of a deisopentanizer (DIP) or a super DIH will achieve the highest
octane from a fractionation hydrocarbon recycle flow scheme. In this scheme, both
low octane C5 and normal and isoparaffin C6 are recycled to the Penex reactors.
Figure 2.4 (DIP-Penex-DIH)
Chapter 2 Isomerization Techniques
19
2.1.9 Penex/Molex Process:
Figure 2.5 (Penex/Molex Process flow scheme)
2.2 PROCESS DESCRIPTION:
This flow scheme uses Molex technology for the economic separation and recycle of
n-paraffin from the reactor effluent.
The Molex process is an adsorptive separation method that utilizes molecular sieves
for the separation of n-paraffins from branched and cyclichydrocarbons. The
separation is effected in the liquid phase under isothermal conditions according to the
principles of the UOP Sorbex separations technology. Because the separation takes
place in the liquid phase, heating, cooling and power requirements are remarkably
low.
Sorbex is the name applied to a particular technique developed by UOP for separating
a component or group of components from a mixture in the liquid phase by selective
adsorption on a solid adsorbent.
Sorbex is a simulated moving bed adsorption process operating with all process
streams in the liquid phase and at constant temperature within the adsorbent bed. Feed
is introduced and components are adsorbed and separated from each other within the
bed. A separate liquid of different boiling point referred to as ‗desorbent‘ is used to
Chapter 2 Isomerization Techniques
20
displace the feed components from the pores of the adsorbent. Two liquid streams
emerge from the bed – an extract and a raffinate stream, both diluted with desorbent.
The desorbent is removed from both product streams by fractionation and is recycled
to the system.
The adsorbent is fixed while the liquid streams flow down through the bed. A shift in
the positions of liquid feed and withdrawal, in the direction of fluid flow through the
bed, simulates the movement of solid in the opposite direction. It is, of course,
impossible to move the liquid feed and withdrawal points continuously. However,
approximately the same effect can be produced by providing multiple Liquid access
lines to the bed, and periodically switching each net stream to the next adjacent line.
A liquid circulating pump is provided to pump liquid from the bottom outlet to the top
inlet of the adsorbent chamber. A fluid-directing device, known as a ‗rotary valve‘, is
also provided.
Figure 2.6 (BFD of Molex Process)
2.2.1 Operating Conditions Of Molex Process:
Molex unit involves three processes.
a) Adsorption
b) Purification
c) Desorption
Chapter 2 Isomerization Techniques
21
2.2.1.1 Adsorption Operation:
The adsorbent employed in Molex is a specially prepared molecular sieve with
selective pores. Molex feed enter the adsorbent chamber via rotary valve. Adsorbent
chamber is operated at pressure 15 kg/cm2.
2.2.1.2 Purification Operation:
Non-normal paraffins (iso-paraffins) are removed from the adsorption chamber &
purified in raffinate column. Operating temperature & pressure of raffinate column is
125 °C & 13.0 kg/cm2.
2.2.1.3 Desorption:
Operating temperature & pressure of the extract column 130 °C & 16.0 kg/cm2.
2.2.2 Penex-Plus Technology
The performance of the Penex process can be compromised when processing this
feedstock because benzene hydrogenation is a highly exothermic reaction. The heat
generated by the benzene hydrogenation reaction can cause the reactors to operate at
conditions that are less favorable for octane upgrading. For these applications, UOP
offers the Penex-Plus Technology.
It includes two reactor sections. The first section is designed to saturate the benzene to
cyclohexane. The second section is designed to isomerize the feed for an overall
octane increase. Each reactor is operated at conditions that favor the intended
reactions for maximum conversion.
Chapter 2 Isomerization Techniques
22
2.3 OCTANE COMPARISON FOR DIFFERENT PROCESSES:
Figure 2.7 (Octane Comparison for different Processes) {Feed RON = 60 to 70
CHAPTER 3
PROCESS DESCRIPTION
Chapter 3 Process Description
23
CHAPTER # 3
PROCESS DESCRIPTION
3.1 SIMPLE PROCESS DESCRIPTION:
The isomerization of light paraffins is an important industrial process to obtain
branched alkanes which are used as octane boosters in gasoline. Thus, isoparaffins are
considered an alternative to the use of oxygenate and aromatic compounds, whose
maximum contents are subjected to strict regulations in order to protect the
environment.
The UOP‘s Penex process is specifically designed for the catalytic isomerization of
pentane, hexanes, and mixtures thereof. The reactions take place in the presence of
hydrogen, over a fixed bed of catalyst, and at operating conditions that promote
isomerization and minimize hydrocracking. Operating conditions are not severe,
reaction takes place at moderate operating pressure, low temperature, and low
hydrogen partial pressure is required.
Light naphtha feed is charged to one of the two dryer vessels. These vessels are filled
with molecular sieves, which remove water and protect the catalyst. After mixing with
makeup hydrogen, the feed is heat-exchanged against reactor effluent. It then enters a
charge heater before entering the reactors. Two reactors normally operate in series.
The reactor effluent is cooled before entering the product stabilizer. Only a slight
excess of hydrogen above chemical consumption is used. The makeup hydrogen,
which can be of any reasonable purity, is typically provided by a catalytic reformer.
The stabilizer overhead vapors are caustic scrubbed for removal of the HCl formed
from organic chloride added to the reactor feed to maintain catalyst activity. After
scrubbing, the overhead gas then flows to fuel. The stabilized, isomerized liquid
product from the bottom of the column then passes to gasoline blending.
Ideally, this isomerization catalyst would convert all the feed paraffins to the high
octane- number branched structures: normal pentane (nC5) to isopentane (iC5) and
Chapter 3 Process Description
24
normal hexane (nC6) to 2,2- and 2,3-dimethylbutane. The reaction is controlled by a
thermodynamic equilibrium that is more favorable at low temperature.
With C5 paraffins, interconversion of normal pentane and isopentane occurs. The C6-
paraffin isomerization is somewhat more complex. Because the formation of 2- and 3-
methylpentane and 2,3-dimethylbutane is limited by equilibrium, the net reaction
involves mainly the conversion of normal hexane to 2,2-dimethylbutane. All the feed
benzene is hydrogenated to cyclohexane, and a thermodynamic equilibrium is
established between methylcyclopentane and cyclohexane. The octane rating shows
an appreciation of some 14 numbers.
3.2 PROCESS CHEMISTRY:
Isomerization mechanism and Kinetics Paraffin isomerization is most effectively
catalyzed by a dual-function catalyst containing a noble metal and an acid function.
The reaction is believed to proceed through an olefin intermediate that is formed by
the dehydrogenation of the paraffin on the metal site. We use butane for simplicity
CH3 — CH2 — CH2 — CH3 ↔ CH3 — CH2 — CH ═ CH2 + H2
These dual-functional hydro-isomerization catalysts which operate at very low
temperatures have stronger acid site. In this case it is possible that the necessary
carbonium ion is former by direct hydride ion abstraction from the paraffin by the
acid function of the catalyst:
CH3 — CH2 — CH ═ CH2 + [H+][A
-] → CH3 — CH2 — CH
+ — CH3 + A
Then carbonium ion undergoes skeletal isomerization. However this reaction proceeds
with difficulty because it requires the formation of a primary carbonium ion at some
point in the reaction. Nevertheless, the strong acidity of the isomerization catalyst
provides enough driving force for the reaction to proceed at high rates.
+ +
CH3 — CH2 — CH — CH3 → CH3 — C — CH3
│
CH3
The isoparaffinic carbonium ion is then converted to an olefin through loss of a proton
to the catalyst site.
Chapter 3 Process Description
25
+
CH3 — C — CH3 + A- → CH3 — C ═ CH2 + [H
+][A
-]
│ │
CH3 CH3
In the last step, the isoolefin intermediate is hydrogenated rapidly back to the
analogous isoparaffin:
CH3 — C ═ CH2 + H2 → CH3 — CH — CH3
│ │
CH3 CH3
Equilibrium limits the maximum conversion possible at any given set of conditions.
This maximum is a strong function of the temperature at which the conversion takes
place. A more favorable equilibrium exists at lower temperatures.
Figure 3.1 shows the equilibrium plot for the pentane system. The maximum
isopentane content increases from 64 mol % at 260°C to 82 mol % at 120°C (248°F).
Neopentane and cyclopentane have been ignored because they seem to occur only in
small quantities and are not formed under isomerization conditions.
The hexane equilibrium curve shown in Figure 3.2 is somewhat more complex than
that shown in Fig. 3.3. The methylpentanes have been combined because they have
nearly the same octane rating. The methylpentane content in the C6-paraffin fraction
remains nearly constant over the entire temperature range. Similarly, the fraction of
2,3-dimethylbutane is almost constant at about 9 mol % of the C6 paraffins.
Theoretically, as the temperature is reduced, 2,2-dimethylbutane can be formed at the
expense of normal hexane. This reaction is highly desirable because nC6 has a RON
of 30. The RON of 2,2- dimethylbutane is 93.
Chapter 3 Process Description
26
Figure 3.1 C5 paraffin equilibrium plot
Figure 3.2 Equilibrium composition of hexane isomers in relation to temperature.
3.3 REACTIONS:
The C5/C6 paraffin isomerization reactions which occur in Penex unit are shown
below:
Chapter 3 Process Description
27
3.3.1 Hexane Reactions
Normal Hexane 2-Methyl Pentane
CH3
CH3—CH2—CH2—CH2—CH2—CH3 ↔ CH3—CH—CH2—CH2—CH3
24.8 RON 73.4 RON
3-Methyl Pentane
CH3
CH3—CH2—CH2—CH2—CH2—CH3 ↔ CH3—CH2—CH—CH2—CH3
74.5 RON
2-2 Dimethyl Butane
CH3
CH3—CH2—CH2—CH2—CH2—CH3 ↔ CH3—C—CH2—CH3
CH3
91.8 RON
2-3 Dimethyl Butane
CH3
CH3—CH2—CH2—CH2—CH2—CH3 ↔ CH3—CH—CH—CH3
CH3
104.3RON
Chapter 3 Process Description
28
3.3.2 Pentane Reaction
Normal Pentane Iso-Pentane CH3
CH3—CH2—CH2—CH2—CH3 ↔ CH3—CH—CH2—CH3
61.8 RON 93.0 RON
3.3.2 Other Reactions
Apart from the paraffins isomerization reactions, there are several other important
reactions including:
Naphthene Ring Opening
Naphthene Isomerization
Benzene Saturation
Hydrocracking
3.3.2.2 Ring Openinig:
The three naphthenes which are typically present in feed are cyclopentane (CP),
methyl cyclopentane (MCP) and cyclohexane (OH). The naphthene rings will
hydrogenate to form paraffins. This ring opening reaction increases with increasing
reactor temperature. At typical isomerization reactor conditions the conversion of
naphthenes rings to paraffins will be on the order of 20-40 percent.
Chapter 3 Process Description
29
3.3.2.3 Naphthene Isomerization:
The naphthenes Methyl Cyclopentane (MCP) and Cyclo Hexane (CH) exists in
equilibrium. Naphthene isomerization will shift towards MCP production as
temperature is increased.
3.3.2.4 Benzene Saturation:
The catalyst will saturate benzene to cyclohexane. This reaction proceeds very
quickly and is achieved at very low temperatures. Saturation a benzene is not
equilibrium limited at the isomerization reactor conditions ant conversion should be
100%. The amount of heat generated by the saturation of benzene limits the amount
of benzene which can be tolerated in the feed. The isomerization section feed can
contain up to 5% benzene. The platinum function on the isomerization catalyst is
responsible for benzene saturation.
3.3.2.5 Hydrocracking:
Hydrocracking occurs in the reactors to a degree which depends on the feed quality
and severity of operation. Large molecules such a C7‘s tend to hydrocrack more easily
than smaller molecules. C5 and C6 paraffin will also hydrocrack to a certain extent. As
C5/C6 paraffin isomerization approaches equilibrium, the extent of hydrocracking
increases. If isomerization is pushed too hard, hydrocracking will reduce the liquid
yield and increase heat production. Methane, ethane, propane and butane are produced
as a result of hydrocracking.
Chapter 3 Process Description
30
Normal Heptane Propane i Butane CH3
CH3—CH2—CH2—CH2—CH2—CH2—CH3 → CH3—CH2—CH3 + CH3—CH—CH3
3.3.3 Chloride promoter:
The addition of the chloride promoter (perchloroethylene C2Cl4) to the process stream
is intended to maintain the acid function of the catalyst with chloride atoms (Cl). At a
reactor temperature of 105°C (220°F) or higher, the organic chloride will decompose
to HCl in the presence of the catalyst.
Perchloroethylene + Hydrogen → Hydrogen Chloride + Ethane
C2Cl4 + 5H2 → 4HCl + C2H6
3.3.4 Caustic Scrubbing Reactions:
The hydrogen chloride formed in the isomerization reactors is neutralized in the
Stabilizer Net Gas Scrubber, by means of an acid-base reaction between sodium
hydroxide (NaOH) and hydrogen chloride (HCl). The result of this neutralization
reaction is sodium chloride (NaCl) and water. The strength of the caustic should be
monitored by determining the total alkalinity of the solution. Report the concentration
of strong base as wt% NaOH.
HCl + NaOH NaCl + H2O
3.4 PROCESS VARIABLES:
In the normal operation of a Penex Unit, having once set the operating pressure fresh
feed rate and makeup hydrogen flows, it is usually only necessary to adjust the reactor
inlet temperatures.
Once the catalyst has been loaded into the unit, the manner in which the catalyst it
placed in seance and the treatment it receives when in service will to a large extent
influence its effectiveness for making quality product as well as the length of service
Chapter 3 Process Description
31
it will give. In making any changes to the operation, the welfare of the catalyst must
be given prime consideration for it can be regarded as the heart of the operation or
which the quality of the results obtained will depend.
3.4.1 Reactor Temperature:
In general, reactor temperature is the main process control. A definite upper limit
exists for the amount of iso-paraffins which can exist in the reactor product at any
given outlet temperature, as shown in Figures 3.3, 3.4 and 3.5. This is the equilibrium
imposed by thermodynamics, and can be reached only after an infinity length of time,
i.e. with an infinitely large reactor. In practice, therefore, the product will contain less
than this equilibrium concentration of iso-paraffins. As reactor temperature is raised
to increase the rate of isomerization, the equilibrium composition will be approached
more closely. At excessively high temperatures, the concentration of iso-paraffins in
the product will actually decrease because of the downward shift in equilibrium curve,
even though the high temperature gives a high reaction rate.
The use of temperatures higher than necessary to achieve a reasonably close approach
to equilibrium accomplishes nothing other than to increase the amount of
hydrocracking. Extremely high temperatures may lead to an increased rate of carbon
laydown on the catalyst; however, the carbon forming propensity of the catalyst is
inherently so low that excessive hydrocracking would normally be encountered before
carbon formation problems would develop. It is recommended, however, that UOP be
consulted before temperatures above about 204°C (400°F) are employed.
A typical C5/C6 Penex Unit has two series reactors with provision for independent
temperature control. The first reactor system effects the bulk of the isomerization so
long as most of the catalyst therein is still active. Any benzene in the feed it
hydrogenated in the first reactor, even when the catalyst therein has lost its activity
with respect to paraffin isomerization. Some conversion, ring opening, of cyclohexane
and methyl Cyclopentane to hexanes also occurs, as does some hydrocracking of C7 to
C3 and C4. These three reactions (benzene hydrogenation, naphthene ring opening to
hexane, and C7 hydrocracking) are exothermic and, for a typical feed stock contribute
more to the temperature rise in the first reactor that does paraffin isomerization, which
is also exothermic.
Chapter 3 Process Description
32
Normally, the first reactor system will be operated at such a temperature as to
maximize the concentration of isopentane and 2,2 dimethyl butane in its effluent. The
concentrations attainable and the required outlet temperature will be influenced by the
amount of active catalyst present and by the amount of C6 cyclic and C7 components
present in the feed, higher the temperatures being required with high concentrations of
these components in the feed. By this procedure, the required operating temperature
on the second reactor system is reduced and it is possible to operate under conditions
where the equilibrium is more favorable.
Figure 3.3 Iso-pentane equilibrium curve
Chapter 3 Process Description
33
Figure 3.4 2-2Dimethyl butane Equilibrium curve
Figure 3.5 Equilibrium Curve
Chapter 3 Process Description
34
3.4.2 Liquid Hourly Space Velocity:
This term, commonly shortened to LHSV, is defined as the volumetric hourly flow of
reactor charge divided by the volume of catalyst contained in the reactors in
consistent units. The design LHSV for C5/C6 Penex operation is normally between 1
and 2. Increasing the LHSV beyond this will lead to lower product isomer ratios.
In order to avoid excessive reactor severity, the Penex reactor LHSV should always
be maintained above 0.5 hr-1
overall or 1.0 LHSV minimum per reactor.
3.4.3 Hydrogen to Hydrocarbon Mole Ratio:
This ratio is defined as the number of moles hydrogen at the reactor outlet per mole of
reactor charge passing over the catalyst, and is specified at 0.05 moles H2/mole
HCBN. The primary purpose of maintaining the ratio at or above the design is to
avoid carbon deposition on the catalyst and maintain enough H2 for the reactions to
proceed. If necessary, the reactor charge rate is to be reduced to maintain the design
hydrogen to hydrocarbon ratio. The H2/HCBN ratio is determined by measuring the
total mole of hydrogen in the stabilizer overhead gas and dividing by the total moles
of fresh feed feedstock.
3.4.4 Pressure:
C5/C6 Penex Units are normally designed to operate at 31.6 kg/cm2
gauge (450 psig)
at the reactor outlet. Methylcyclopentane and cyclohexane appear to adsorb on the
catalyst and reduce the rate of isomerization reactions. Higher pressure helps to offset
this effect of the C6 cyclic compounds. Lowering the unit pressure or operating at a
slightly lower level would not affect the catalyst life but the extent of isomerization
would be influenced.
3.4.5 Catalyst Promoter:
To sustain catalyst activity, the addition of chloride is necessary. At no time should
the plant be operated for longer than six hours without the injection of chloride.
Whenever there is a catalyst chloride deficiency, the product isomer ratios will
decrease (although not necessarily instantaneously), other things being equal.
Restarting the injection of chloride will tend to return the activity of the catalyst to its
previous level, but it is possible that full activity will not be restored if a decline in
Chapter 3 Process Description
35
activity as a result no chloride injection has been observed. Isomerization grade
perchloroethylene (C2Cl4) is UOP's recommended source of chloride.
3.5 PROCESS EQUIPMENTS:
3.5.1 Sulfur Guard Bed:
The purpose of the sulfur guard bed is to protect the Penex catalyst from sulfur in the
liquid feed. The hydrotreater will remove most of the sulfur in the Penex feed. The
guard bed reduces the sulfur to a safe level for operation and serves as insurance
against upsets in the NHT which could result in higher that formal level of sulfur in
the feed.
The guard bed is loaded with an adsorbent, a nickel containing extrudate designed to
chemisorb sulfur from the liquid feed. The feedstock is heated to the required
temperature for sulfur removal, usually 121 °C (250°F), and passed down flow over
the adsorbent.
Once sulfur breakthrough occurs, normally after one year or so of operation, the guard
bed is taken off line and reloaded with fresh adsorbent. The Penex Unit need not be
shut down during the short period of time required to reload the guard bed so long as
the NHT is performing properly.
3.5.2 Liquid Feed Driers:
The purpose of the liquid feed driers is to ensure that the hydrocarbon stream from the
treating section is dry before entering the Penex Unit.
The driers are operated in series except when they are in the regeneration mode when
at that time only one will be in service.
The hydrotreated C5/C6 stream is introduced to the liquid feed drier at the bottom and
passes up flow through the molecular sieve desiccant and exits at the top. The flow is
then routed through one of the drier crossovers to the other liquid feed drier. The flow
through the liquid feed drier is also in the up flow pattern. The dried hydrocarbon is
then routed to feed surge drum. Over a period of time, the drier in the lead position
Chapter 3 Process Description
36
will become spent as indicated by the moisture analyzer located between the two
driers. At this time, it will become necessary to regenerate this drier. The driers
should be regenerated on a schedule frequent enough to avoid moisture breakthrough.
The spent drier is taken out of service by closing the appropriate block valves. The
second series drier is now alone in service as the only drier drying the feed. The
moisture analyzer tap is switched to monitor this in service drier. After the drier
regeneration has been completed, it is now ready for service. A switch is made such
that the regenerated drier takes the tail position with the in-service drier remaining as
the lead drier. Over a period of time the lead drier will become spent and is now set
up far regeneration with the tail drier now being the only one in service. This will be
the manner in which these driers will be lined up for process flow.
3.5.3 Make-up Gas Driers:
Make-up gas must be dried in order to protect the catalyst. The two gas driers operate
in the same manner as the liquid feed driers. The driers operate up flow, in series. The
dried hydrogen is then sent to the reactor circuit on flow control. The hydrogen is also
used for pressure control in the feed surge drum and, for startup, in the stabilizer.
3.5.4 Feed Surge Drum:
The purpose of this drum is to provide liquid feed surge capacity for the Penex Unit.
Dried feed from the liquid feed driers is routed to this drum. The feed surge drum is
blanketed with dry hydrogen gas originating from the outlet of the make-up gas driers
with the feed surge drum pressure being controlled by a PRC.
3.5.5 Reactor Exchanger Circuit:
The dried liquid feed from the feed surge drum is pumped by either of the t reactor
charge pumps through the reactor exchanger circuit on flow control. The reactor
exchanger circuit consists of the cold combined feed exchanger, the hot combined
feed exchanger and the reactor charge heater.
Prior to the entry of the liquid hydrocarbon into the cold combined feed exchanger, it
combines with the makeup hydrogen stream. After combining, the mix hydrocarbon-
Chapter 3 Process Description
37
hydrogen stream passes through the exchanger circuit in the order previously
mentioned.
The cold combined feed exchanger is equipped with a bypass which can be used to
regulate the amount of combined feed preheat. The bypass is regulated with a board
mounted control valve to maintain reactor charge heater control. The combined feed
is further preheated by exchange with a portion of the lead reactor effluent in the hot
combined feed exchanger.
A small quantity of catalyst promoter (perchloroethylene) is added upstream of the
reactor charge heater. This promoter is pumped into the process by either of two
injection pumps. The catalyst promoter is stored in a nitrogen blanketed storage drum.
The combined feed is finally brought up to the desired temperature in the reactor
charge heater by a temperature controller which resets the exchanger‘s heat medium
flow. The charge heater is equipped with an automatic shutdown which is activated by
low feed or low makeup gas flow.
After exiting the reactor charge heater, the heated combined stream then flows into
the first reactor.
3.5.6 Regenerant Vaporizer:
The regenerant vaporizer uses low pressure steam to heat the regenerant stream before
it reaches the electric superheater. The vaporizer is an upright heat exchanger which
uses bayonet type tubes that have been strength welded and fully rolled. This heater is
equipped with a level indicator and a high level alarm, and is designed to operate with
the top portion of the tubes uncovered. Low pressure steam on the inside of the
bayonet tubes transfers heat to the regenerant on the outside of the bayonet tubes. This
arrangement allows hot stream in the tip of the bayonet tube to transfer heat to the
vaporized regenerant stream, giving it several degrees of superheat. This prevents the
regenerant from condensing which could damage the electric bundles in the super
heater when operating.
Chapter 3 Process Description
38
3.5.7 Regenerant Superheater:
The regenerant superheater, raises the temperature of the vaporized regenerate to a
temperature of 315°C (600°F). The regenerant stream is heated by Inconel electric
elements, which are capable of reaching temperatures of over 600°C (1112°F).The
regenerant entering the superheater must be in the vapor phase to avoid damaging the
electric bundles when power is applied to the superheater.
3.5.8 Isomerization Reactors:
The reactors are the heart of the process. The operation of them is such that, reactor
will be placed in series with the other reactor. At various times throughout the unit's
history it will be possible to have either reactor in the lead or tail position. A single
reactor bypass allows operation of one reactor only during startup or partial catalyst
replacement. Thermocouples are inserted into the catalyst bed of each reactor to
monitor the activity of the catalyst in conjunction with product ratios.
After exiting the reactor charge heater, the heated combined stream then flows to the
first reactor. Upon exiting the first reactor, the stream then passes to the hot combined
feed exchanger where the first reactor's heat of reaction is partially removed. The
degree of temperature removal can be achieved by adjusting the amount of exchanger
by-passing with a temperature controller. This temperature controller fixes the lag
reactor's inlet temperature.
The partially cooled stream is then routed to the second reactor where the find process
reactions are completed.
The reactors are equipped with hydrogen purge lines which are located at the inlet of
each reactor. The hydrogen purge is used to remove hydrocarbon from a reactor
which is to be unloaded or to pressurize a reactor. A hydrogen quench line is located
at the lead reactor inlet header to aid in cooling the catalyst during a temperature
excursion as well as removing hydrocarbon. The quench is controlled by an HIC with
flow indication.
Chapter 3 Process Description
39
In case of a high reactor temperature emergency, the reactors are equipped with
depressuring lines to the flare system. The reactors are depressured from the outlet of
the lag reactor. The depressuring line is equipped with two motorized o pneumatically
operated valves which can be operated from the control room once the reactors have
been isolated from the charge heater and stabilizer.
After exiting the second reactor, the stream is then routed to the tube side of the cold
combined feed exchanger. The cold combined feed exchanger tube side effluent is
then routed to the stabilizer on pressure control.
3.5.9 Stabilizer:
The purpose of this column is to separate any dissolved hydrogen, HCI and cracked
gases (C1, C2, and C3's) from the isomerate.
The feed to this column is routed hot directly from the cold CFX before entering the
stabilizer.
The column is reboiled by either steam or hot oil. The reboiler heat input is controlled
by an FRC on the heating medium. The amount of heat input is adjusted to maintain
sufficient reflux to adequately strip the HCl and light ends from the stabilizer bottoms
material. The typical design external reflux to feed ratio is approximately 0.5 on a
volume basis and is recommended as a starting point.
The stabilizer column overhead vapor, consisting of the light hydrocarbon
components of the column's feed, is routed to an air or water cooled condenser and
then to the stabilizer receiver. To maintain pressure control on the column, gas is
vented on pressure control to the stabilizer gas scrubber. Liquid is pumped from the
receiver on level control with the stabilizer reflux pump. All liquid from the stabilizer
overhead receiver is refluxed to the column on tray No. 1.
Bottoms product is routed to storage on level control after first being cooled in the
stabilizer bottoms cooler. If the stabilizer bottoms is sent to a deisohexanizer it is not
cooled, but is charged hot to the column. Part of the stabilizer bottoms is used for
regenerating the driers.
Chapter 3 Process Description
40
3.5.10 Stabilizer Net Gas Scrubber:
The function of the Stabilizer Net Gas Scrubber is to neutralize the hydrogen chloride
present in the Stabilizer off Gas prior to its entry into the fuel gas system o the flare
header. The HCI is formed in the reactor section and then vented off through the
Stabilizer Overhead Receiver, to the Stabilizer Net Gas Scrubber.
In this vessel, the off gas from the Stabilizer Receiver is contacted through a liquid
level and later with a counter current flow of caustic solution (10 wt. % NaOH) which
reacts with HCl to form sodium chloride and water. The entry point for the off gas is
located at the bottom of the scrubber, and consists of a monel distributor with small
holes to allow even gas distribution. The bottom distributor and the inlet flange are
both made of monel to prevent corrosion, resulting from contact with high
concentrations of HCl in an aqueous environment. The vessel is constructed of killed
carbon steel.
The top portion of the vessel is filled with 25mm (1‘‘) Carbon Raschig Rings, which
provide a good contact area for the interaction of the liquid caustic and the acidic
overhead gas. The packing in the scrubbing section is held in place by a support
orating on the bottom and a hold down grating on the top.
The incoming gas is contacted with the caustic in the bottom portion of the scrubber
or "reservoir" section. This is where most of the HCl is removed before it reaches the
top portion or the scrubbing section of the column. A high level of caustic solution is
usually kept in the reservoir section of the column to ensure that there is always an
ample supply of caustic for circulation. A pump is used to circulate the caustic to the
two infection points on the scrubber column. One injection point if located at the top
of the packed section (a spray nozzle or slot type distributor) ant the other is located
just below the packed section (a spray nozzle or ring type distributor). The purpose of
the lower spray distributor is to direct the caustic flow to the conical walls of the
scrubber to keep the walls wetted with caustic. The design flow of caustic should be
continuously maintained to each distributor to ensure goof flow distribution.
Chapter 3 Process Description
41
A water wash section may be included above the circulating caustic to remove
entrained caustic from the net gas. Circulating water monitored by an FI is passed
over a bed of 25mm (1‘‘) Carbon Raschig Rings at design rate. Makeup water is
added to overflow a chimney trap tray which replaces water lost to saturating the dry
gas in the caustic inventory section. The water is typically changed out if the caustic
strength reaches 2 wt. % NaOH in the circulating water or if caustic entrainment is
observed.
3.5.11 Pumps:
Centrifugal pumps are used for several applications in the Penex Unit. Common
applications for the centrifugal pumps are for reactor charge pumps, reflux pumps for
the fractionation columns, and caustic recirculation pumps. Proportioning pumps are
used for chloride injection into the feed stream and make-up water to the net gas
scrubber.
Pumps used in hydrocarbon service use tandem seals with API 52 seal plans. In this
application the seal oil circulation is established by way of a siphon. The seal oil is
contained in a reservoir where it can be pumped to and from the pump seal. The oil is
continuously pumped between the two seals. In the event of a seal failure,
hydrocarbon will leak into the oil system and cause a pressure increase in the
reservoir. The seal oil reservoir is equipped with a pressure alarm and pressure gauge
to alert the operator to a seal failure. The reservoir is usually vented to flare through
an orifice plate.
CHAPTER 4
CATALYST SELECTION
Chapter 4 Catalyst Selection
43
CHAPTER # 4
CATALYST SELECTION
4.1 CATALYST:
Substance that changes the rate of reaction but does not take part in reaction.
4.2 TYPES OF CATALYSTS:
The schemes of proposing processes are analogous generally. The differences are
defines by performances of usable catalysts due to their type. Main parameter which
is the octane number of produced isomerate depends on process temperature. That‘s
why we will dwell on the issue of thermodynamic of isomerization reaction. First of
all hydrocarbons isomerization reaction is balanced reaction, and equilibrium yield of
isoparaffins increases with temperature reducing, but it can be reached only after an
―infinite residence time‖ of the feed in reaction zone or an equivalent very small value
for LHSV. On the other hand an increase in temperature always corresponds to an
increase in reaction velocity. So that at low temperature the actual yield will be far
below the equilibrium yield, because of low reaction velocity. On the contrary, at
higher temperature, the equilibrium yield will be more easily reached, due to a high
reaction rate. Consequently, at higher temperature the yield of isoparaffins is limited
by the thermodynamic equilibrium, and at lower temperature it is limited by low
reaction rate (kinetic limitation) (Figure 4.1)
Figure 4.1 Dependence of n-paraffins conversion on reaction temperature
Chapter 4 Catalyst Selection
44
Paraffin-isomerization catalysts fall mainly into two principal categories: those based
on Friedel-Crafts catalysts as classically typified by aluminum chloride and hydrogen
chloride and dual-functional hydro isomerization catalysts.
4.2.1 First Generation Catalysts:
The Friedel-Crafts catalysts represented a first-generation system. Although they
permitted operation at low temperature, and thus a more favorable isomerization
equilibrium, they lost favor because these systems were uneconomical and difficult to
operate. High catalyst consumption and a relatively short life resulted in high
maintenance costs and a low on-stream efficiency.
4.2.2 Second Generation Catalysts:
These problems of first generation systems were solved with the development of
second-generation dual-functional hydro isomerization catalysts. These catalysts
included a metallic hydrogenation component in the catalyst and operated in a
hydrogen environment. However, they had the drawback of requiring a higher
operating temperature than the Friedel-Crafts systems.
4.2.3 Third Generation Catalysts:
The desire to operate at lower temperatures, at which the thermodynamic equilibrium
is more favorable, dictated the development of third-generation catalysts. The
advantage of these low-temperature [below 200°C (392°F)] catalysts contributed to
the relative nonuse of the high-temperature versions. Typically, these noble-metal,
fixed-bed catalysts contain a component to provide high catalytic activity. They
operate in a hydrogen environment and employ a promoter. Because hydrocracking of
light gases is slight, liquid yields are high.
An improved version of these third-generation catalysts is used in the Penex process.
Paraffin isomerization is most effectively catalyzed by a dual-function catalyst
containing a noble metal and an acid function. The reaction is believed to proceed
through an olefin intermediate that is formed by the dehydrogenation of the paraffin
on the metal site.
Chapter 4 Catalyst Selection
45
4.2.4 Aluminum Chloride:
The isomerization catalysts employed during World War II were all of the Friedel
Crafts type. Those which contained aluminum chloride only were either a
hydrocarbon/aluminum chloride complex (the so-called sludge process) or they were
manufactured in-situ by deposition onto a support such as alumina or bauxite. They
were intended to operate at very low temperatures [49-129°C (120-265°F)] and to
approach the very favorable equilibrium composition characteristic of these
temperatures.
The catalyst tended to consume itself by reaction with the feedstock and/or product.
When temperature was raised a little in an effort to compensate for loss of catalyst
and to speed the reaction to effect more isomerization, light fragments were formed
by cracking and these, when vented caused an excessive loss of the HCI promoter.
Corrosion of downstream equipment was also commonplace, due to the solubility of
aluminum chloride in hydrocarbon, to its relatively high volatility and to the difficulty
of removing it from the product by caustic washing. Aluminum chloride deposition in
and plugging of reboiler tubes was not uncommon.
4.3 DUAL-FUNCTIONAL HYDROISOMERIZATION CATALYSTS:
4.3.1 Hydro-isomerization catalysts [above 199°c (390°f)]: The operational problems which had characterized the Friedel-Crafts type
isomerization plants, the advent of catalytic reforming which not only made hydrogen
generally available in refineries but also demonstrated the practicality of using noble
metal containing catalysts on a large scale, and the octane numbed race which postwar
high compression engines initiated all combined in the 1950's to spawn a spate of
hydro-isomerization processes. These catalysts generally contained a noble metal and
some halide, operated at temperatures between about 299°C (560°F) and
temperatures approaching those characteristic of catalytic reforming, employed
recycle hydrogen to prevent catalyst carbonization and utilized either no promoter or
traces at most. In general, they did not require an especially dry feedstock but did
benefit from a low sulfur content feedstock. Most achieved a close approach to the
equilibrium characteristic of their particular operating temperature.
Chapter 4 Catalyst Selection
46
Because of their high operating temperatures and their necessarily low conversions to
iso-paraffins, these high temperature catalysts were quickly replaced with the advent
of the ―third generation‖ low temperature catalysts.
4.3.2 Hydro-isomerization catalysts [below 199°c (390°f)]: Low temperature is considered rather arbitrarily for catalyst classification purposes as
anything below 199°C (390°F) operating temperature. Typically these are fixed bed
catalysts containing a supported noble metal and a component to provide acidity in
the catalytic sense. They operate in a hydrogen atmosphere and may employ a catalyst
promoter whose concentration in the reactor may range from parts per million to
substantially higher levels. They generally all require a dry, low sulfur feedstock;
however, they may differ importantly in their tolerance of certain types and molecular
weights of hydrocarbons. Hydrocracking to light gases is generally slight, so liquid
product yields are high. The type of catalyst used in the Penex unit is of this type.
The acid function is the support itself and some examples include acid zeolites,
chlorided alumina and amorphous silica alumina. Noble metals have a positive effect
on the activity and stability of the catalyst. However they have a low resistance to
poisoning by sulfur and nitrogen compounds present in the processed cuts.
In order to prepare a suitable catalyst for hydroconversion of alkanes, good balance
between the metal and acid functions must be obtained. Rapid molecular transfer
between the metal and acid sites is necessary for selective conversion of alkanes into
desirable products.
4.4 ALUMINA CATALYST:
Alumina or aluminum oxide (AlR2ROR3R) is a chemical compound with melting
point of about 2000°C and sp. gr. of about 4.0. It is insoluble in water and organic
liquids and very slightly soluble in strong acids and alkalies. Alumina occurs in two
crystalline forms. Alpha alumina is composed of colorless hexagonal crystals with the
properties given above; gamma alumina is composed of minute colorless cubic
Chapter 4 Catalyst Selection
47
crystals with sp. gr. of about 3.6 that are transformed to the alpha form at high
temperatures. Figure (4.2) shows the shape of AlR2ROR3R [Ulla, 2003].
The most common form of crystalline alumina, α-aluminum oxide, is known as
corundum. If a trace of the element is present it appears red, it is known as ruby, but
all other colorations fall under the designation sapphire. The primitive cell contains
two formula units of aluminum oxide. The oxygen ions nearly form a hexagonal
close-packed structure with aluminum ions filling two-thirds of the octahedral
interstices.
Typical alumina characteristics include:
Good strength and stiffness
Good hardness and wear resistance
Good corrosion resistance
Good thermal stability
Excellent dielectric properties (from DC to GHz frequencies)
Low dielectric constant
Low loss tangent
Figure 4.2 Aluminum Oxide
Chapter 4 Catalyst Selection
48
4.5 CHLORINATED-ALUMINA BASED CATALYSTS: These are the most active and supply the highest isomerize yield and isomerize
octane.
Figure 4.3 Characteristics of chlorinated alumina catalysts
4.6 ZEOLITES:
Zeolites are micro porous crystalline solids with well-defined structures. Generally
they contain silicon, aluminum and oxygen in their framework and cations, water
and/or other molecules within their pores. Zeolites occur naturally as minerals or
synthetic, Figure (4.3) shows the shape of different types of zeolites [Matthew, 2008].
Because of their unique porous properties, zeolites are used in a variety of
applications with a global market of several million tons per annum. In the western
world, major uses are in petrochemical cracking, ion-exchange (water softening and
purification), and in the separation and removal of gases and solvents. Other
applications are in agriculture, animal husbandry and construction. They are often
also referred to as molecular sieves [Danny, 2002].
Zeolites have the ability to act as catalysts for chemical reactions which take place
within the internal cavities. An important class of reactions is that catalyzed by
hydrogen-exchanged zeolites, whose framework-bound protons give rise to very high
acidity. This is exploited in many organic reactions, including crude oil cracking,
isomerization and fuel synthesis [Jirong, 1990].
4.5.1 Zeolite Characteristics:
Well-defined crystalline structure.
High internal surface areas (>600 mP2P/g).
Chapter 4 Catalyst Selection
49
Uniform pores with one or more discrete sizes.
Good thermal stability.
Highly acidic sites when ion is exchanged with protons.
Ability to sorb and concentrate hydrocarbons.
Figure 4.4 Structure and dimension of different types of zeolite
Figure 4.5
CHAPTER 5
MATERIAL BALANCE
Chapter 5 Material Balance
50
CHAPTER # 5
MATERIAL BALANCE
5.1 Material Balance:
Material balances are important first step when designing a new process or analyzing
an existing one. They are almost always prerequisite to all other calculations in the
solution of process engineering problems.
Material balances are nothing more than the application of the law of conservation of
mass, which states that mass can neither be created nor destroyed. Thus, you cannot,
for example, specify an input to a reactor of one ton of naphtha and an output of two
tons of gasoline or gases or anything else. One ton of total material input will only
give one ton of total output,
i.e. total mass of input = total mass of output.
5.1.1 Conservation Law:
+ = + ±
The quantity S can be any one of the following quantities:
Mass
Energy
Momentum
Component Mass (Mole)
5.1.2 Total Mass Balance: Since mass is always conserved, the balance equation for the total mass (m) of a given
system is:
Rate of mass in - Rate of mass out = rate of mass accumulation 5.1.3 Component Balance: The mass balance for a component A is generally written in terms of number of moles
of A. Thus the component balance is:
Flow of Flow of Rate of Rate of
moles (A) + mole of (A) + Generation of = Accumulation of
in out moles of (A) moles of (A)
Total flow rate of (S) into the system
Generation rate of (S) within system
Amount of (S) exchanged with the surrounding
Total flow rate of (S) out of the system
Accumulation rate of (S) within system
Chapter 5 Material Balance
51
Basis:
Naphtha Feed Stream
600 Barrel of Naphtha per stream day to be Isomerized
Mass flow rate = 25000 kg/hr
Molecular Weight = 83.085
Density = 660 kg/m3
Hydrogen Feed Stream
Mass flow rate = 732 kg/hr
Molecular Weight = 7.907
Density = 1.215 kg/m3
Equilibrium Data: Equilibrium Conversions are taken from the following curves
Figure 5.1 Thermodynamic equilibrium for the isomerization of heptane
Chapter 5 Material Balance
52
Figure 5.2 Thermodynamic equilibrium for the isomerization of Butane, pentane and hexane
Chapter 5 Material Balance
53
5.2 Mass Balance on Mixer
Stream 3
Components Molecular
Mass
Mass
Fraction
Mass Flow
Rate
Molar Flow
Rate
n C4 58.00 0.0267 667.50 11.51
n C 5 72.00 0.1673 4182.50 58.09
n C 6 86.00 0.1589 3971.25 46.18
n C7 100.00 0.0929 2321.75 23.22
i C 5 72.00 0.1077 2693.25 37.41
2 MP 86.00 0.0750 1875.25 21.81
3 MP 86.00 0.0482 1204.25 14.00
2,2 DMB 86.00 0.0056 138.75 1.61
2,3DMB 86.00 0.0121 301.75 3.51
2 MH 100.00 0.0373 931.65 9.32
3 MH 100.00 0.0373 931.40 9.31
2,2 DMP 100.00 0.0027 68.40 0.68
2,3 DMP 100.00 0.0112 279.15 2.79
2,4 DMP 100.00 0.0057 141.65 1.42
3,3 DMP 100.00 0.0018 43.93 0.44
3 EP 100.00 0.0028 69.90 0.70
C6H6 78.00 0.0253 632.50 8.11
C7H8 92.00 0.0288 719.25 7.82
CP 70.00 0.0118 295.50 4.22
MCP 84.00 0.0400 998.75 11.89
CH 84.00 0.0387 967.25 11.51
ECP 98.00 0.0028 70.00 0.71
MCH 98.00 0.0598 1494.50 15.25
Total 1.00 25000.08 301.51
Chapter 5 Material Balance
54
Stream 2
Components Molecular
Mass
Volume
fraction
Mole
Fraction Mass
Mass
Fraction Mass Flow
Rate
Molar Flow Rate
H2 2 0.78 0.780 1.56 0.1980 144.91 72.4569
C1 16 0.099 0.099 1.58 0.2010 147.14 9.1964
C2 30 0.064 0.064 1.92 0.2437 178.36 5.9452
C3 44 0.038 0.038 1.67 0.2122 155.32 3.5299
n-C4 58 0.008 0.008 0.46 0.0589 43.10 0.7431
i-C4 58 0.008 0.008 0.46 0.0589 43.10 0.7431
n-C5 72 0.002 0.002 0.14 0.0183 13.38 0.1858
i-C5 72 0.001 0.001 0.07 0.0091 6.69 0.0929
Total 1.00 1.00 7.88 1.00 732.00 92.8934
Stream 4
Components Molecular
Mass
Mass
Fraction
Mole
Fraction
Mass Flow
Rate
Molar Flow
Rate
H2 2.00 0.0056 0.1837 144.91 72.4569 C1 16.00 0.0057 0.0233 147.14 9.1964 C2 30.00 0.0069 0.0151 178.36 5.9452 C3 44.00 0.0060 0.0090 155.32 3.5299
n C4 58.00 0.0276 0.0311 710.60 12.2518 n C 5 72.00 0.1631 0.1478 4195.88 58.2761
n C 6 86.00 0.1543 0.1171 3971.25 46.1773
n C7 100.00 0.0902 0.0589 2321.75 23.2175
i-C4 58.00 0.0017 0.0019 43.10 0.7431
i C 5 72.00 0.1049 0.0951 2699.94 37.4991 2 MP 86.00 0.0729 0.0553 1875.25 21.8052 3 MP 86.00 0.0468 0.0355 1204.25 14.0029
2,2 DMB 86.00 0.0054 0.0041 138.75 1.6134 2,3DMB 86.00 0.0117 0.0089 301.75 3.5087
2 MH 100.00 0.0362 0.0236 931.65 9.3165 3 MH 100.00 0.0362 0.0236 931.40 9.3140
2,2 DMP 100.00 0.0027 0.0017 68.40 0.6840 2,3 DMP 100.00 0.0108 0.0071 279.15 2.7915 2,4 DMP 100.00 0.0055 0.0036 141.65 1.4165 3,3 DMP 100.00 0.0017 0.0011 43.93 0.4393
3 EP 100.00 0.0027 0.0018 69.90 0.6990 C6H6 78.00 0.0246 0.0206 632.50 8.1090
C7H8 92.00 0.0280 0.0198 719.25 7.8179 CP 70.00 0.0115 0.0107 295.50 4.2214
MCP 84.00 0.0388 0.0301 998.75 11.8899 CH 84.00 0.0376 0.0292 967.25 11.5149 ECP 98.00 0.0027 0.0018 70.00 0.7143
MCH 98.00 0.0581 0.0387 1494.50 15.2500
Total 1.00 1.00 25732.08 394.40
Chapter 5 Material Balance
55
5.3 Material Balance around Reactors:
Chapter 5 Material Balance
56
Stream 7
Components
Molecular
Mass Mass
Fraction Mole
Fraction Mass Flow
Rate Molar Flow
Rate
H2 2.00 0.0056 0.1837 144.91 72.4569
C1 16.00 0.0057 0.0233 147.14 9.1964
C2 30.00 0.0069 0.0151 178.36 5.9452
C3 44.00 0.0060 0.0090 155.32 3.5299
n C4 58.00 0.0276 0.0311 710.60 12.2518
n C 5 72.00 0.1631 0.1478 4195.88 58.2761
n C 6 86.00 0.1543 0.1171 3971.25 46.1773
n C7 100.00 0.0902 0.0589 2321.75 23.2175
i-C4 58.00 0.0017 0.0019 43.10 0.7431
i C 5 72.00 0.1049 0.0951 2699.94 37.4991
2 MP 86.00 0.0729 0.0553 1875.25 21.8052
3 MP 86.00 0.0468 0.0355 1204.25 14.0029
2,2 DMB 86.00 0.0054 0.0041 138.75 1.6134
2,3DMB 86.00 0.0117 0.0089 301.75 3.5087
2 MH 100.00 0.0362 0.0236 931.65 9.3165
3 MH 100.00 0.0362 0.0236 931.40 9.3140
2,2 DMP 100.00 0.0027 0.0017 68.40 0.6840
2,3 DMP 100.00 0.0108 0.0071 279.15 2.7915
2,4 DMP 100.00 0.0055 0.0036 141.65 1.4165
3,3 DMP 100.00 0.0017 0.0011 43.93 0.4393
3 EP 100.00 0.0027 0.0018 69.90 0.6990
C6H6 78.00 0.0246 0.0206 632.50 8.1090
C7H8 92.00 0.0280 0.0198 719.25 7.8179
CP 70.00 0.0115 0.0107 295.50 4.2214
MCP 84.00 0.0388 0.0301 998.75 11.8899
CH 84.00 0.0376 0.0292 967.25 11.5149
ECP 98.00 0.0027 0.0018 70.00 0.7143
MCH 98.00 0.0581 0.0387 1494.50 15.2500
H2O 18.00 0.0000 0.0000 0.00 0.0000
C2Cl4 94.00 3.000E-06 0.0000 7.50E-05 7.98E-07
Total 1.00 1.00 25732.08 394.40
Chapter 5 Material Balance
57
Stream 8
Components Molecular
Mass Mass
Fraction Mole
Fraction Mass Flow
Rate Molar Flow
Rate
H2 2.00 0.0013 0.0482 32.6411 16.3205
C1 16.00 0.0057 0.0272 147.4071 9.2129
C2 30.00 0.0070 0.0177 179.3759 5.9792
C3 44.00 0.0062 0.0107 159.0078 3.6138
n C4 58.00 0.0137 0.0180 353.4739 6.0944
n C 5 72.00 0.0394 0.0416 1013.8848 14.0817
n C 6 86.00 0.0362 0.0320 932.4828 10.8428
n C7 100.00 0.0072 0.0055 185.7398 1.8574
i-C4 58.00 0.0154 0.0202 396.9166 6.8434
i C 5 72.00 0.2321 0.2451 5971.2138 82.9335 2 MP 86.00 0.1192 0.1054 3066.6213 35.6584 3 MP 86.00 0.0730 0.0646 1879.3603 21.8530
2,2 DMB 86.00 0.0455 0.0403 1171.2736 13.6195 2,3DMB 86.00 0.0287 0.0254 738.5866 8.5882
2 MH 100.00 0.0600 0.0457 1545.0732 15.4507 3 MH 100.00 0.0497 0.0378 1279.6610 12.7966
2,2 DMP 100.00 0.0162 0.0123 416.6620 4.1666 2,3 DMP 100.00 0.0307 0.0233 789.9341 7.8993 2,4 DMP 100.00 0.0136 0.0104 350.6071 3.5061 3,3 DMP 100.00 0.0116 0.0088 299.3171 2.9932
3 EP 100.00 0.0045 0.0034 116.3349 1.1633 C6H6 78.00 0.0000 0.0000 0.6325 0.0081 C7H8 92.00 0.0000 0.0000 0.7192 0.0078 CP 70.00 0.0080 0.0087 206.8498 2.9550
MCP 84.00 0.0252 0.0228 649.1867 7.7284 CH 84.00 0.0663 0.0601 1707.1082 20.3227 ECP 98.00 0.0027 0.0021 69.9999 0.7143
MCH 98.00 0.0733 0.0569 1886.2642 19.2476 2,2,3 TMB 100.00 0.0072 0.0055 185.7398 1.8574
H2O 18.00 0.0000 0.0000 0.0000 0.0000 C2Cl4 94.00 1.00E-06 0.0000 0.0257 0.0003 HCL 36.50 2.30E-05 0.0000 0.5918 0.0162
Total 1.00 1.0000 25732.69 338.32
Chapter 5 Material Balance
58
Chapter 5 Material Balance
59
Stream 9
Components
Molecular
Mass
Mass
Fraction
Mole
Fraction
Mass Flow
Rate
Molar Flow
Rate
H2 2.00 0.0013 0.0482 32.6411 16.3205
C1 16.00 0.0057 0.0272 147.4071 9.2129
C2 30.00 0.0070 0.0177 179.3759 5.9792
C3 44.00 0.0062 0.0107 159.0078 3.6138
n C4 58.00 0.0137 0.0180 353.4739 6.0944
n C 5 72.00 0.0394 0.0416 1013.8848 14.0817
n C 6 86.00 0.0362 0.0320 932.4828 10.8428
n C7 100.00 0.0072 0.0055 185.7398 1.8574
i-C4 58.00 0.0154 0.0202 396.9166 6.8434
i C 5 72.00 0.2321 0.2451 5971.2138 82.9335
2 MP 86.00 0.1192 0.1054 3066.6213 35.6584
3 MP 86.00 0.0730 0.0646 1879.3603 21.8530
2,2 DMB 86.00 0.0455 0.0403 1171.2736 13.6195
2,3DMB 86.00 0.0287 0.0254 738.5866 8.5882
2 MH 100.00 0.0600 0.0457 1545.0732 15.4507
3 MH 100.00 0.0497 0.0378 1279.6610 12.7966
2,2 DMP 100.00 0.0162 0.0123 416.6620 4.1666
2,3 DMP 100.00 0.0307 0.0233 789.9341 7.8993
2,4 DMP 100.00 0.0136 0.0104 350.6071 3.5061
3,3 DMP 100.00 0.0116 0.0088 299.3171 2.9932
3 EP 100.00 0.0045 0.0034 116.3349 1.1633
C6H6 78.00 0.0000 0.0000 0.6325 0.0081
C7H8 92.00 0.0000 0.0000 0.7192 0.0078
CP 70.00 0.0080 0.0087 206.8498 2.9550
MCP 84.00 0.0252 0.0228 649.1867 7.7284
CH 84.00 0.0663 0.0601 1707.1082 20.3227
ECP 98.00 0.0027 0.0021 69.9999 0.7143
MCH 98.00 0.0733 0.0569 1886.2642 19.2476
2,2,3 TMB 100.00 0.0072 0.0055 185.7398 1.8574
H2O 18.00 0.0000 0.0000 0.0000 0.0000
C2Cl4 94.00 1.00E-06 0.0000 2.57E-02 2.74E-04
HCL 36.50 2.30E-05 0.0000 5.92E-01 1.62E-02
Total 1.00 1.0000 25732.69 338.32
Chapter 5 Material Balance
60
Stream 10
Hydrogen to Hydrocarbon Ratio at the outlet of R-102
Should be 0.05
H2 : HC Ratio 0.05
Components
Molecular
Mass
Mass
Fraction
Mole
Fraction
Mass Flow
Rate
Molar Flow
Rate
H2 2.00 0.0013 0.0479 32.3827 16.1914
C1 16.00 0.0057 0.0272 147.1509 9.1969
C2 30.00 0.0069 0.0176 178.3647 5.9455
C3 44.00 0.0060 0.0104 155.3259 3.5301
n C4 58.00 0.0041 0.0054 106.5960 1.8379
n C 5 72.00 0.0079 0.0083 202.8658 2.8176
n C 6 86.00 0.0029 0.0026 74.6026 0.8675
n C7 100.00 0.0004 0.0003 9.2875 0.0929
i-C4 58.00 0.0251 0.0330 647.1486 11.1577
i C 5 72.00 0.2637 0.2787 6784.4979 94.2291
2 MP 86.00 0.1293 0.1144 3327.8947 38.6965
3 MP 86.00 0.0781 0.0691 2010.0155 23.3723
2,2 DMB 86.00 0.0600 0.0531 1544.3494 17.9576
2,3DMB 86.00 0.0323 0.0286 831.8794 9.6730
2 MH 100.00 0.0605 0.0460 1556.3009 15.5630
3 MH 100.00 0.0510 0.0388 1313.1645 13.1316
2,2 DMP 100.00 0.0173 0.0132 446.4043 4.4640
2,3 DMP 100.00 0.0325 0.0247 836.4138 8.3641
2,4 DMP 100.00 0.0142 0.0108 365.4858 3.6549
3,3 DMP 100.00 0.0124 0.0094 317.9081 3.1791
3 EP 100.00 0.0049 0.0037 125.6286 1.2563
C6H6 78.00 0.0000 0.0000 0.0019 0.0000
C7H8 92.00 0.0000 0.0000 0.0026 0.0000
CP 70.00 0.0080 0.0087 206.8608 2.9552
MCP 84.00 0.0252 0.0229 649.2215 7.7288
CH 84.00 0.0663 0.0601 1707.1996 20.3238
ECP 98.00 0.0027 0.0021 70.0037 0.7143
MCH 98.00 0.0733 0.0569 1886.3652 19.2486
2,2,3 TMB 100.00 0.0077 0.0059 198.7522 1.9875
H2O 18.00 0.0000 0.0000 0.0000 0.0000
C2Cl4 94.00 1.00E-06 0.0000 0.0257 0.0003
HCL 36.50 2.30E-05 0.0000 0.5918 0.0162
Total 1.00 1.0000 25732.69 338.14
Chapter 5 Material Balance
61
5.4 Material Balance around Stabilizer T 101:
Chapter 5 Material Balance
62
Stream 11
Components
Molecular
Mass
Mass
Fraction
Mole
Fraction
Fraction
Mass Flow
Rate
Molar Flow
Rate
H2 2.00 0.0013 0.0479 32.3835 16.1917
C1 16.00 0.0057 0.0272 147.1544 9.1971
C2 30.00 0.0069 0.0176 178.3689 5.9456
C3 44.00 0.0060 0.0104 155.3296 3.5302
n C4 58.00 0.0041 0.0054 106.5985 1.8379
n C 5 72.00 0.0079 0.0083 202.8706 2.8176
n C 6 86.00 0.0029 0.0026 74.6044 0.8675
n C7 100.00 0.0004 0.0003 9.2877 0.0929
i-C4 58.00 0.0251 0.0330 647.1641 11.1580
i C 5 72.00 0.2637 0.2787 6784.6607 94.2314
2 MP 86.00 0.1293 0.1144 3327.9746 38.6974
3 MP 86.00 0.0781 0.0691 2010.0637 23.3728
2,2 DMB 86.00 0.0600 0.0531 1544.3865 17.9580
2,3DMB 86.00 0.0323 0.0286 831.8994 9.6732
2 MH 100.00 0.0605 0.0460 1556.3382 15.5634
3 MH 100.00 0.0510 0.0388 1313.1960 13.1320
2,2 DMP 100.00 0.0173 0.0132 446.4150 4.4641
2,3 DMP 100.00 0.0325 0.0247 836.4339 8.3643
2,4 DMP 100.00 0.0142 0.0108 365.4946 3.6549
3,3 DMP 100.00 0.0124 0.0094 317.9158 3.1792
3 EP 100.00 0.0049 0.0037 125.6316 1.2563
C6H6 78.00 0.0000 0.0000 0.0019 0.0000
C7H8 92.00 0.0000 0.0000 0.0026 0.0000
CP 70.00 0.0080 0.0087 206.8658 2.9552
MCP 84.00 0.0252 0.0229 649.2371 7.7290
CH 84.00 0.0663 0.0601 1707.2405 20.3243
ECP 98.00 0.0027 0.0021 70.0053 0.7143
MCH 98.00 0.0733 0.0569 1886.4105 19.2491
2,2,3 TMB 100.00 0.0077 0.0059 198.7570 1.9876
H2O 18.00 0.0000 0.0000 0.0000 0.0000
C2Cl4 94.00 1.000E-06 8.096E-07 2.573E-02 2.738E-04
HCL 36.50 2.300E-05 4.795E-05 5.919E-01 1.622E-02
Total 1.00 1.0000 25733.31 338.15
Chapter 5 Material Balance
63
Stream 13
Components Molecular
Mass
Mass
Fraction
Mole
Fraction
Mass Flow
Rate
Molar Flow
Rate
H2 2.00 0.0245 0.3332 32.6412 16.3206
C1 16.00 0.1105 0.1881 147.4076 9.2130
C2 30.00 0.1344 0.1221 179.3766 5.9792
C3 44.00 0.1191 0.0738 159.0084 3.6138
n C4 58.00 0.0779 0.0366 103.9217 1.7918
i-C4 58.00 0.4828 0.2268 644.3509 11.1095
i C 5 72.00 0.0508 0.0192 67.8235 0.9420
C2Cl4 94.00 1.000E-06 8.970E-07 2.440E-02 2.595E-04
HCL 36.50 2.300E-05 5.313E-05 5.611E-01 1.537E-02
Total 1.00 1.00 1335.12 48.99
Stream 14
Components
Molecular
Mass
Mass
Fraction
Mole
Fraction
Mass Flow
Rate
Molar Flow
Rate
n C4 58.00 0.0001 0.0001 2.1210 0.0366
n C 5 72.00 0.0083 0.0097 202.7881 2.8165
n C 6 86.00 0.0031 0.0030 74.6027 0.8675
n C7 100.00 0.0004 0.0003 9.2875 0.0929
i C 5 72.00 0.2752 0.3223 6714.8678 93.2621
2 MP 86.00 0.1364 0.1337 3327.8996 38.6965
3 MP 86.00 0.0824 0.0808 2010.0184 23.3723
2,2 DMB 86.00 0.0633 0.0621 1544.3517 17.9576
2,3DMB 86.00 0.0341 0.0334 831.8807 9.6730
2 MH 100.00 0.0638 0.0538 1556.3032 15.5630
3 MH 100.00 0.0538 0.0454 1313.1664 13.1317
2,2 DMP 100.00 0.0183 0.0154 446.4049 4.4640
2,3 DMP 100.00 0.0343 0.0289 836.4150 8.3642
2,4 DMP 100.00 0.0150 0.0126 365.4864 3.6549
3,3 DMP 100.00 0.0130 0.0110 317.9086 3.1791
3 EP 100.00 0.0051 0.0043 125.6288 1.2563
C6H6 78.00 0.0000 0.0000 0.0019 0.0000
C7H8 92.00 0.0000 0.0000 0.0026 0.0000
CP 70.00 0.0085 0.0102 206.8611 2.9552
MCP 84.00 0.0266 0.0267 649.2224 7.7288
CH 84.00 0.0700 0.0702 1707.2021 20.3238
ECP 98.00 0.0029 0.0025 70.0038 0.7143
MCH 98.00 0.0773 0.0665 1886.3680 19.2487
2,2,3 TMB 100.00 0.0081 0.0069 198.7525 1.9875
H2O 18.00 0.000E+00 0.0000 0.0000 0.0000
Total 1.00 1.00 24397.55 289.35
Chapter 5 Material Balance
64
5.5 MATERIAL BALANCE AROUND SCRUBBER:
Material Balance Around Scrubber T-102
/ hr 48.75
kmole
/hr
Stream 16 0.59 kg / hr
0.02 kmole/hr
Stream 13 1334.53 kg / hr
48.75 kmole/hr
Chapter 5 Material Balance
65
Stream 13
Components Molecular
Mass Mass
Fraction Mole
Fraction Mass Flow
Rate Molar Flow
Rate
H2 2.00 0.0245 0.3332 32.6412 16.3206
C1 16.00 0.1105 0.1881 147.4076 9.2130
C2 30.00 0.1344 0.1221 179.3766 5.9792
C3 44.00 0.1191 0.0738 159.0084 3.6138
n C4 58.00 0.0779 0.0366 103.9217 1.7918
i-C4 58.00 0.4828 0.2268 644.3509 11.1095
i C 5 72.00 0.0508 0.0192 67.8235 0.9420 C2Cl4 94.00 1.000E-06 8.970E-07 2.440E-02 2.595E-04
HCL 36.50 2.300E-05 5.313E-05 5.611E-01 1.537E-02
Total 1.00 1.00 1335.12 48.99
Stream 15
Components Molecular
Mass Mass
Fraction Mole
Fraction Mass Flow
Rate Molar Flow
Rate
H2 2.00 0.0245 0.3332 32.6412 16.3206
C1 16.00 0.1105 0.1881 147.4076 9.2130
C2 30.00 0.1344 0.1221 179.3766 5.9792
C3 44.00 0.1191 0.0738 159.0084 3.6138
n C4 58.00 0.0779 0.0366 103.9217 1.7918
i-C4 58.00 0.4828 0.2268 644.3509 11.1095
i C 5 72.00 0.0508 0.0192 67.8235 0.9420 C2Cl4 94.00 0.0000 0.0000 0.0000 0.0000
HCL 36.50 0.0000 0.0000 0.0000 0.0000
NaCl 40.00 2.400E-05 5.403E-05 5.855E-01 1.563E-02
Total 1.00 1.00 1335.12 48.99
CHAPTER 6
ENERGY BALANCE
Chapter 6 Energy Balance
66
CHAPTER # 6
ENERGY BALANCE
The First Law of Thermodynamics is a statement of energy conservation. Although
energy cannot be created or destroyed, it can be converted from one form to another
(for example, internal energy stored in molecular bonds can be converted into kinetic
energy; potential energy can be converted to kinetic or to internal energy, etc.).
Energy can also be transferred from one point to another, or from one body to a
second body. Energy transfer can occur by flow of heat, by transport of mass
(transport of mass is otherwise known as convection), or by performance of work.
The general energy balance for a process can be expressed in words as:
Accumulation of Energy in System =
Input of Energy into System – Output of Energy from System
6.1 ENERGY BALANCE AROUND REACTOR R-101:
Chapter 6 Energy Balance
67
6.1.1 Molar Composition
Components STREAM IN STREAM OUT
Mol% Mol%
H2 18.3713 4.8240
C1 2.3317 2.7232
C2 1.5074 1.7673
C3 0.8950 1.0682
n C4 3.1064 1.8014
n C 5 14.7758 4.1623
n C 6 11.7082 3.2049
n C7 5.8868 0.5490
i-C4 0.1884 2.0228
i C 5 9.5079 24.5136
2 MP 5.5287 10.5400 3 MP 3.5504 6.4593 2,2 DMB 0.4091 4.0257 2,3DMB 0.8896 2.5385 2 MH 2.3622 4.5669 3 MH 2.3616 3.7824 2,2 DMP 0.1734 1.2316 2,3 DMP 0.7078 2.3349 2,4 DMP 0.3592 1.0363 3,3 DMP 0.1114 0.8847 3 EP 0.1772 0.3439
C6H6 2.0560 0.0024
C7H8 1.9822 0.0023 CP 1.0703 0.8734 MCP 3.0147 2.2844 CH 2.9196 6.0070 ECP 0.1811 0.2111 MCH 3.8666 5.6892 223TMB 0.0000 0.5490 H2O 0.0000 0.0000 C2Cl4 0.0000 0.0001
HCL 0.00E+00 4.79E-03
Chapter 6 Energy Balance
68
6.1. 2 Heat of Formation
Components ∆Hf° Reactants ∆Hf°Products
Heat of formation at 25 C
ni ∆Hf° ni∆Hf° ni ∆Hf° ni∆Hf°
kmol/hr kJ/kmole kJ/hr kmol/hr kJ/kmole kJ/hr
H2 72.49 0 0.00 16.32 0 0.00
C1 9.20 -74900 -689130.06 9.21 -74900 -690056.81
C2 5.95 -84738 -504013.73 5.98 -84738 -506670.71
C3 3.53 -103890 -366894.77 3.61 -103890 -375443.21
n C4 12.26 -126190 -1546760.31 6.09 -126190 -769057.96
n C 5 58.30 -146490 -8540779.57 14.08 -146490 -2062855.48
n C 6 46.20 -167290 -7728550.98 10.84 -167290 -1813915.64
n C7 23.23 -187890 -4364338.62 1.86 -187890 -348990.26
i-C4 0.74 -134590 -100066.10 6.84 -134590 -921061.70
i C 5 37.52 -154590 -5799653.70 82.93 -154590 -12820832.96
2 MP 21.82 -174390 -3804360.11 35.66 -174390 -6218533.77
3 MP 14.01 -171690 -2405262.73 21.85 -171690 -3751986.83
2,2 DMB 1.61 -185690 -299724.59 13.62 -185690 -2529025.09
2,3DMB 3.51 -177890 -624452.89 8.59 -177890 -1527774.43
2 MH 9.32 -195090 -1818390.34 15.45 -195090 -3014315.96
3 MH 9.32 -192390 -1792743.05 12.80 -192390 -2461966.49
2,2 DMP 0.68 -206290 -141167.13 4.17 -206290 -859541.38
2,3 DMP 2.79 -199390 -556852.69 7.90 -199390 -1575066.62
2,4 DMP 1.42 -202090 -286391.89 3.51 -202090 -708549.55
3,3 DMP 0.44 -201690 -88633.00 2.99 -201690 -603699.30
3 EP 0.70 -189790 -132724.11 1.16 -189790 -220794.33
C6H6 8.11 82977 673167.24 0.01 82977 672.86
C7H8 7.82 50029 391303.01 0.01 50029 391.13
CP 4.22 -77288 -326415.54 2.96 -77288 -228388.25
MCP 11.90 -106790 -1270303.26 7.73 -106790 -825326.23
CH 11.52 -123190 -1419169.36 20.32 -123190 -2503582.59
ECP 0.71 -127190 -90891.70 0.71 -127190 -90850.88
MCH 15.26 -154890 -2363156.82 19.25 -154890 -2981292.20
223TMB 0.00 -204890 0.00 1.86 -204890 -380566.37
H2O 0.00 -241814 -0.19 0.00 -241814 0.00
C2Cl4 0.00 -100488 0.00 0.00 -100488 -27.51
HCL 0.00 -100488 0 0.02 -100488 -1629.40 NaOH 0.00 0 0.00 0.00
TOTAL 394.58 -45996357 338.34 -50790738
Chapter 6 Energy Balance
69
6.1.3 For reactants
Cp of Gas at 25° C to 170° C
Components n
i x
i ∫CpGdT xii∫CpGdT
kmole/hr Mol% kJ/kmole kJ/kmole
H2 72.49
18.37 4214.10 774.1861
C1 9.20
2.33
5746.43 133.9922
C2 5.95
1.51
9020.95 135.9811
C3 3.53
0.90
12889.61 115.3638
n C4 12.26
3.11
16918.74 525.5668
n C 5 58.30
14.78 20860.70 3082.3384
n C 6 46.20
11.71 24834.86 2907.7137
n C7 23.23
5.89
28805.94 1695.7378
i-C4 0.74
0.19
16967.58 31.9710
i C 5 37.52
9.51
20771.74 1974.9472 2 MP 21.8
2 5.53
25105.30 1387.9933 3 MP 14.0
1 3.55
24821.51 881.2673 2,2 DMB 1.6
1 0.41
24901.95 101.8659 2,3DMB 3.5
1 0.89
24640.13 219.2063 2 MH 9.3
2 2.36
29441.95 695.4734 3 MH 9.3
2 2.36
28781.12 679.6809 2,2 DMP 0.6
8 0.17
29355.81 50.9110 2,3 DMP 2.7
9 0.71
-4163.13 -29.4658 2,4 DMP 1.4
2 0.36
28781.12 103.3678 3,3 DMP 0.4
4 0.11
28781.12 32.0539 3 EP 0.7
0 0.18
28781.12 51.0089
C6H6 8.11
2.06
15030.04 309.0205 C7H8 7.8
2 1.98
18801.43 372.6870 CP 4.2
2 1.07
15761.36 168.6997 MCP 11.9
0 3.01
20285.01 611.5245 CH 11.5
2 2.92
19945.76 582.3328 ECP 0.7
1 0.18
24921.30 45.1340 MCH 15.2
6 3.87
24238.46 937.2080 223TMB 0.0
0 0.00
28927.16 0.0000 H2O 0.0
0 0.00
0.00
0.0000 C2Cl4 0.0
0 0.00
0.00
0.0000 HCL 0.0
0 0.00
0 0.0000 NaOH 0.0
0 0.00
0 0.0000 TOTAL 394.58 10
0 18577.77
Chapter 6 Energy Balance
70
6.1.4 For products
Cp of gas at 25°C to 175°C
Components ni xi ∫CpGdT xii∫CpGdT kmole/hr Mol% kJ/kmole kJ/kmole
H2 16.32 4.82 4360.15 210.336 C1 9.21 2.72 5965.68 162.456 C2 5.98 1.77 9379.74 165.772 C3 3.61 1.07 13407.51 143.216 n C4 6.09 1.80 17592.94 316.917 n C 5 14.08 4.16 21695.55 903.033 n C 6 10.84 3.20 25828.32 827.781 n C7 1.86 0.55 29957.92 164.473 i-C4 6.84 2.02 17647.22 356.964 i C 5 82.93 24.51 21607.06 5296.669 2 MP 35.66 10.54 26111.09 2752.097 3 MP 21.85 6.46 25814.45 1667.445 2,2 DMB 13.62 4.03 25905.34 1042.861 2,3DMB 8.59 2.54 25632.22 650.678 2 MH 15.45 4.57 30627.01 1398.720 3 MH 12.80 3.78 29932.92 1132.194 2,2 DMP 4.17 1.23 30545.77 376.194 2,3 DMP 7.90 2.33 -4377.30 -102.206 2,4 DMP 3.51 1.04 29932.92 310.204 3,3 DMP 2.99 0.88 29932.92 264.824 3 EP 1.16 0.34 29932.92 102.929 C6H6 0.01 0.00 15649.22 0.375 C7H8 0.01 0.00 19568.49 0.452 CP 2.96 0.87 16429.78 143.505 MCP 7.73 2.28 21129.78 482.683 CH 20.32 6.01 20790.13 1248.866 ECP 0.71 0.21 25959.49 54.808 MCH 19.25 5.69 25243.14 1436.140 223TMB 1.86 0.55 30093.11 165.215 H2O 0.00 0.00 0.00 0.000 C2Cl4 0.00 0.00 0.00 0.000 HCL 0.02 0.00 0 0.000 NaOH 0.00 0.00 0 0.000
TOTAL 338.34 100 21675.600
Chapter 6 Energy Balance
71
6.1.5 Heat of reaction
∆Hrxn = ∆Hprd - ∆Hrea
∆Hprd = ni∆Hf° + nT∫CpGdT
now,
∆Hprd = -50790738 +
∆Hprd = -43457097 kJ/hr
now,
∆Hrea = ni∆Hf° + nT∫CpGdT
∆Hrea = -45996357 + 7330467.333
∆Hrea = -38665890 kJ/hr
SO,
∆Hrxn = ∆Hprd - ∆Hrea
∆Hrxn = -43457097 - -38665890
∆Hrxn = -4791208 kJ/hr
∆Hrxn = -5.E+06 kJ/hr
6.1.6 For cooling coils
Components ni xi ∫CpLdT n∫CpLdT
kmole/hr Mol% kJ/kmole K kJ/hr Water 2900.00 100.00 1510.00 4379000
Total 4379000
Heat Gained By Cooling Water = Heat generated by Reactions
4.379E+06 kJ/hr = -4.791E+06 kJ/hr
Chapter 6 Energy Balance
72
6.2 ENERGY BALANCE AROUND REACTOR R-102:
Chapter 6 Energy Balance
73
6.2.1 Molar Composition
Components STREAM IN STREAM OUT
Mol% Mol%
H2 4.8240 4.7884
C1 2.7232 2.7199
C2 1.7673 1.7583
C3 1.0682 1.0440
n C4 1.8014 0.5435
n C 5 4.1623 0.8333
n C 6 3.2049 0.2565
n C7 0.5490 0.0275
i-C4 2.0228 3.2998
i C 5 24.5136 27.8671
2 MP 10.5400 11.4440
3 MP 6.4593 6.9121
2,2 DMB 4.0257 5.3107
2,3DMB 2.5385 2.8607
2 MH 4.5669 4.6026
3 MH 3.7824 3.8835
2,2 DMP 1.2316 1.3202
2,3 DMP 2.3349 2.4736
2,4 DMP 1.0363 1.0809
3,3 DMP 0.8847 0.9402
3 EP 0.3439 0.3715
C6H6 0.0024 0.0000
C7H8 0.0023 0.0000
CP 0.8734 0.8740
MCP 2.2844 2.2857
CH 6.0070 6.0105
ECP 0.2111 0.2113
MCH 5.6892 5.6925
223TMB 0.5490 0.5878
H2O 0.0000 0.0000
C2Cl4 0.0001 0.0001
HCL 0.0048 0.0048 NaOH 0.0000 0.0000
Chapter 6 Energy Balance
74
6.2.2 Heat of Reaction
Components ∆Hf° Reactants ∆Hf°Products
Heat of formation at 25oC
ni ∆Hf° ni∆Hf° ni ∆Hf° ni∆Hf°
kmole/hr kJ/kmole kJ/hr kmole/hr kJ/kmole kJ/hr H2 16.32 0 0.00 16.20 0 0.00 C1 9.21 -74900 -690056.81 9.20 -74900 -689222.26 C2 5.98 -84738 -506670.71 5.95 -84738 -504081.16 C3 3.61 -103890 -375443.21 3.53 -103890 -366943.86 n C4 6.09 -126190 -769057.96 1.84 -126190 -232045.09 n C 5 14.08 -146490 -2062855.48 2.82 -146490 -412970.40 n C 6 10.84 -167290 -1813915.64 0.87 -167290 -145197.88 n C7 1.86 -187890 -348990.26 0.09 -187890 -17459.69 i-C4 6.84 -134590 -921061.70 11.16 -134590 -1502531.13 i C 5 82.93 -154590 -12820832.96 94.28 -154590 -14574755.94 2 MP 35.66 -174390 -6218533.77 38.72 -174390 -6751921.51 3 MP 21.85 -171690 -3751986.83 23.38 -171690 -4014954.53 2,2 DMB 13.62 -185690 -2529025.09 17.97 -185690 -3336340.09 2,3DMB 8.59 -177890 -1527774.43 9.68 -177890 -1721663.04 2 MH 15.45 -195090 -3014315.96 15.57 -195090 -3037828.49 3 MH 12.80 -192390 -2461966.49 13.14 -192390 -2527762.64 2,2 DMP 4.17 -206290 -859541.38 4.47 -206290 -921385.12 2,3 DMP 7.90 -199390 -1575066.62 8.37 -199390 -1668626.89 2,4 DMP 3.51 -202090 -708549.55 3.66 -202090 -739009.55 3,3 DMP 2.99 -201690 -603699.30 3.18 -201690 -641535.51 3 EP 1.16 -189790 -220794.33 1.26 -189790 -238559.35 C6H6 0.01 82977 672.86 0.00 82977 2.04 C7H8 0.01 50029 391.13 0.00 50029 1.40 CP 2.96 -77288 -228388.25 2.96 -77288 -228521.45 MCP 7.73 -106790 -825326.23 7.73 -106790 -825807.58 CH 20.32 -123190 -2503582.59 20.33 -123190 -2505042.75 ECP 0.71 -127190 -90850.88 0.71 -127190 -90903.86 MCH 19.25 -154890 -2981292.20 19.26 -154890 -2983030.96 223TMB 1.86 -204890 -380566.37 1.99 -204890 -407443.50 H2O 0.00 -241814 0.00 0.00 -241814 0.00 C2Cl4 0.000273748 -100488 -27.51 0.00 -100488 -27.52 HCL 0.016214908 0 0 0.02 0 0.00 NaOH NaOOOH
0 0 0 0.00 0 0.00 TOTAL 338.34 -50789109 338.34 -51085568
Chapter 6 Energy Balance
75
6.2.3 For Reactants Cp of Gas 25
oC to 120
oC
Components ni xi ∫CpGdT xii∫CpGdT
kmolw/hr Mol% kJ/kmole kJ/kmole H2 16.32 4.82 2755.90 132.95 C1 9.21 2.72 3631.20 98.88 C2 5.98 1.77 5602.91 99.02 C3 3.61 1.07 7969.39 85.13 n C4 6.09 1.80 10499.69 189.14 n C 5 14.08 4.16 12918.82 537.72 n C 6 10.84 3.20 15382.42 493.00 n C7 1.86 0.55 17844.04 97.97 i-C4 6.84 2.02 10504.74 212.49 i C 5 82.93 24.51 12837.25 3146.87 2 MP 35.66 10.54 15538.33 1637.73 3 MP 21.85 6.46 15374.77 993.11 2,2 DMB 13.62 4.03 15375.37 618.96 2,3DMB 8.59 2.54 15219.10 386.34 2 MH 15.45 4.57 18178.23 830.19 3 MH 12.80 3.78 17822.99 674.14 2,2 DMP 4.17 1.23 18070.27 222.55 2,3 DMP 7.90 2.33 -2304.75 -53.81 2,4 DMP 3.51 1.04 17822.99 184.70 3,3 DMP 2.99 0.88 17822.99 157.68 3 EP 1.16 0.34 17822.99 61.29 C6H6 0.01 0.00 9189.32 0.22 C7H8 0.01 0.00 11547.23 0.27 CP 2.96 0.87 9515.48 83.11 MCP 7.73 2.28 12346.59 282.04 CH 20.32 6.01 12055.61 724.18 ECP 0.71 0.21 15166.19 32.02 MCH 19.25 5.69 14782.92 841.03 223TMB 1.86 0.55 17857.25 98.04 H2O 0.00 0.00 0.00 0.00 C2Cl4 0.00 0.00 0.00 0.00 HCL 0.02 0.00 0.00 0.00 NaOH 0.00 0.00 0.00 0.00
TOTAL 338.34 100 369150.25 12866.97
Chapter 6 Energy Balance
76
6.2.4 For Products Cp of Gas 25
oC to 123
oC
Components ni xi ∫CpGdT xii∫CpGdT
kmolw/hr Mol% kJ/kmole kJ/kmole H2 16.20 4.79 2843.26 136.147 C1 9.20 2.72 3754.15 102.108 C2 5.95 1.76 5799.15 101.967 C3 3.53 1.04 8251.04 86.140 n C4 1.84 0.54 10867.99 59.070 n C 5 2.82 0.83 13374.02 111.441 n C 6 0.87 0.26 15924.28 40.853 n C7 0.09 0.03 18472.49 5.074 i-C4 11.16 3.30 10875.05 358.851 i C 5 94.28 27.87 13291.37 3703.923 2 MP 38.72 11.44 16086.56 1840.947 3 MP 23.38 6.91 15916.28 1100.144 2,2 DMB 17.97 5.31 15920.31 845.485 2,3DMB 9.68 2.86 15758.11 450.789 2 MH 15.57 4.60 18822.99 866.342 3 MH 13.14 3.88 18451.11 716.553 2,2 DMP 4.47 1.32 18714.89 247.072 2,3 DMP 8.37 2.47 -2402.39 -59.425 2,4 DMP 3.66 1.08 18451.11 199.434 3,3 DMP 3.18 0.94 18451.11 173.473 3 EP 1.26 0.37 18451.11 68.552 C6H6 0.00 0.00 9521.25 0.001 C7H8 0.00 0.00 11960.61 0.001 CP 2.96 0.87 9867.22 86.235 MCP 7.73 2.29 12796.14 292.482 CH 20.33 6.01 12500.07 751.319 ECP 0.71 0.21 15718.56 33.206 MCH 19.26 5.69 15319.17 872.051 223TMB 1.99 0.59 18490.44 108.684 H2O 0.00 0.00 0.00 0.000 C2Cl4 0.00 0.00 0.00 0.000 HCL 0.02 0.00 0.00 0.000 NaOH 0.00 0.00 0.00 0.000
TOTAL 338.34 100 13298.917
Chapter 6 Energy Balance
77
6.2.5 Heat of reaction
∆Hrxn = ∆Hprd - ∆Hrea
∆Hprd
=
ni∆Hf°
+ nT∫CpGdT
now,
∆Hprd = -51085568 + 4499509.04
∆Hprd
=
-46586059.29
kJ/hr
now,
∆Hrea = ni∆Hf° + nT∫CpGdT
∆Hrea
=
-50789109
+
4353361.694
∆Hrea
=
-46435747
kJ/hr
so, ∆Hrxn = ∆Hprd - ∆Hrea
∆Hrxn = -46586059 - -46435747
∆Hrxn = -2.E+05 kJ/hr
6.2.6 For cooling coils
Components ni xi ∫CpGdT n∫CpLdT
kmole/hr Mol% kJ/kmole K kJ/hr Water 95.00 100.00 1510.00 143450
Total 143450
Heat Gained By Cooling Water = Heat generated by Reaction
1.435E+05 kJ/hr = -1.503E+05 kJ/hr
Chapter 6 Energy Balance
78
6.3 ENERGY BALANCE AROUND HEAT EXCHANGER E 101:
E-101 TUBE SIDE SHELL SIDE
Temperature (0
C) Inlet Temperature 36.84 123
Outlet Temperature 70 93.63
Boiling Point 5.901 44.5039
Pressure (kPa) Inlet Pressure 2400 2200
Outlet Pressure 2370 2100
Average Pressure
vapor Fraction in 0.205 0.0917
vapor Fraction out 0.249 0.0678
vapor Fraction avg 0.227 0.07975
Constant
Heat of Vaporization 78945.18 87741.00 (kJ/kmole)
Chapter 6 Energy Balance
79
6.3.1 Molar Composition:
Components
Stream No.3 Stream No.4 Stream No.10 Stream No.11
Mol% Mol% Mol% Mol%
H2 18.3713 18.3713 4.7884 4.7884
C1 2.3317 2.3317 2.7199 2.7199
C2 1.5074 1.5074 1.7583 1.7583
C3 0.8950 0.8950 1.0440 1.0440
n C4 3.1064 3.1064 0.5435 0.5435
n C 5 14.7758 14.7758 0.8333 0.8333
n C 6 11.7082 11.7082 0.2565 0.2565
n C7 5.8868 5.8868 0.0275 0.0275
i-C4 0.1884 0.1884 3.2998 3.2998
i C 5 9.5079 9.5079 27.8671 27.8671 2 MP 5.5287 5.5287 11.4440 11.4440 3 MP 3.5504 3.5504 6.9121 6.9121 2,2 DMB 0.4091 0.4091 5.3107 5.3107 2,3DMB 0.8896 0.8896 2.8607 2.8607 2 MH 2.3622 2.3622 4.6026 4.6026 3 MH 2.3616 2.3616 3.8835 3.8835 2,2 DMP 0.1734 0.1734 1.3202 1.3202 2,3 DMP 0.7078 0.7078 2.4736 2.4736 2,4 DMP 0.3592 0.3592 1.0809 1.0809 3,3 DMP 0.1114 0.1114 0.9402 0.9402 3 EP 0.1772 0.1772 0.3715 0.3715
C6H6 2.0560 2.0560 0.0000 0.0000 C7H8 1.9822 1.9822 0.0000 0.0000
CP 1.0703 1.0703 0.8740 0.8740
MCP 3.0147 3.0147 2.2857 2.2857
CH 2.9196 2.9196 6.0105 6.0105
ECP 0.1811 0.1811 0.2113 0.2113
MCH 3.8666 3.8666 5.6925 5.6925 223TMB 0.0000 0.0000 0.5878 0.5878
H2O 0.0000 0.0000 0.0000 0.0000
C2Cl4 0.0000 0.0000 0.0001 0.0001
HCL 0.0000 0.0000 0.0048 0.0048 NaOH 0.0000 0.0000 0.0000 0.0000
Total 100 100 100 100
Chapter 6 Energy Balance
80
6.3.2 Tube Side
Components ni xi liquid
Fraction ∫CpLdT xii∫CpLdT
kmole/hr Mol% kJ/kmole K kJ/kmole K
H2 72.49 18.37 0.0170 163840.79 2784.06634
C1 9.20 2.33 0.0077 127630.87 988.271101
C2 5.95 1.51 0.0111 7264.71 80.3047805
C3 3.53 0.90 0.0090 4742.84 42.4946293
n C4 12.26 3.11 0.0360 5055.50 182.108916
n C 5 58.30 14.78 0.1810 5890 1065.39389
n C 6 46.20 11.71 0.1469 6853.99 1006.81056
n C7 23.23 5.89 0.0745 7784.82 579.918369
i-C4 0.74 0.19 0.0021 5168.13 10.9664692
i C 5 37.52 9.51 0.1160 5884.95 682.360958
2 MP 21.82 5.53 0.0691 6811.58 470.452231
3 MP 14.01 3.55 0.0444 6688.65 297.186824
2,2 DMB 1.61 0.41 0.0051 6649.77 33.8243427
2,3DMB 3.51 0.89 0.0111 6642.84 73.7434272
2 MH 9.32 2.36 0.0298 7826.38 233.617288
3 MH 9.32 2.36 0.0299 7701.81 230.101309
2,2 DMP 0.68 0.17 0.0022 7802.27 17.0513012
2,3 DMP 2.79 0.71 0.0089 7631.96 68.2607597
2,4 DMP 1.42 0.36 0.0045 7904.69 35.7737834
3,3 DMP 0.44 0.11 0.0014 7552.68 10.6206163
3 EP 0.70 0.18 0.0022 7689.52 17.2390551
C6H6 8.11 2.06 0.0258 4748.36 122.37503
C7H8 7.82 1.98 0.0251 5456.22 137.127268
CP 4.22 1.07 0.0133 4556.56 60.4014987
MCP 11.90 3.01 0.0379 5625.98 213.162185
CH 11.52 2.92 0.0368 5477.83 201.410753
ECP 0.71 0.18 0.0023 6587.94 15.1176227
MCH 15.26 3.87 0.0490 6545.43 320.449969
223TMB 0.00 0.00 0.0000 7490.68 0
H2O 0.00 0.00 0.0000 2496.55 0
C2Cl4 0.00 0.00 0.0000 -5566.74 0
HCL 0.00 0.00 0.0004 0.0000 0
NaOH 0.00 0.00 0.0000 0.0000 0
TOTAL 394.58 100.00 1.00 464434.24 7715.01
Chapter 6 Energy Balance
81
Components ni xi Vapor
Fraction ∫CpGdT xii∫CpGdT
kmole/hr Mol% kJ/kmole K kJ/kmole K
H2 72.49 18.37 0.7923 960.45 760.9602
C1 9.20 2.33 0.0801 1231.83 98.6947
C2 5.95 1.51 0.0297 1871.97 55.5301
C3 3.53 0.90 0.0088 2651.24 23.4494
n C4 12.26 3.11 0.0130 3505.53 45.4545
n C 5 58.30 14.78 0.0254 4303.76 109.3437
n C 6 46.20 11.71 0.0083 5125.09 42.3745
n C7 23.23 5.89 0.0018 5945.75 10.8981
i-C4 0.74 0.19 0.0010 3498.95 3.4979
i C 5 37.52 9.51 0.0200 4268.77 85.4095
2 MP 21.82 5.53 0.0050 5172.99 25.8335
3 MP 14.01 3.55 0.0029 5122.97 14.9625
2,2 DMB 1.61 0.41 0.0005 5108.03 2.3304
2,3DMB 3.51 0.89 0.0008 5057.87 4.2946
2 MH 9.32 2.36 0.0009 6035.99 5.3863
3 MH 9.32 2.36 0.0009 5936.93 5.0777
2,2 DMP 0.68 0.17 0.0001 5984.00 0.5420
2,3 DMP 2.79 0.71 0.0003 -700.73 -0.1885
2,4 DMP 1.42 0.36 0.0002 5936.93 1.0988
3,3 DMP 0.44 0.11 0.0000 5936.93 0.2739
3 EP 0.70 0.18 0.0001 5936.93 0.3638
C6H6 8.11 2.06 0.0013 3025.39 4.0382
C7H8 7.82 1.98 0.0005 3818.32 1.8633
CP 4.22 1.07 0.0014 3098.21 4.3221
MCP 11.90 3.01 0.0020 4049.71 8.0060
CH 11.52 2.92 0.0016 3930.95 6.2002
ECP 0.71 0.18 0.0000 4973.82 0.2319
MCH 15.26 3.87 0.0012 4857.50 5.6009
223TMB 0.00 0.00 0.0000 5931.16 0.0000
H2O 0.00 0.00 0.0000 0.00 0.0000
C2Cl4 0.00 0.00 0.0000 0.00 0.0000
HCL 0.00 0.00 0.0000 0.00 0.0000
NaOH 0.00 0.00 0.0000 0 0.0000
TOTAL 394.58 100.00 1.00 122577.23 300.97
Chapter 6 Energy Balance
82
6.3.3 Shell Side
Components ni xi liquid
Fraction ∫CpLdT xii∫CpLdT
kmole/hr Mol% kJ/kmole K kJ/kmole K
H2 16.20 4.79 0.0126 -199512.06 -2514.64852
C1 9.20 2.72 0.0143 -279046.67 -3994.81536
C2 5.95 1.76 0.0136 -14568.75 -198.505567
C3 3.53 1.04 0.0095 -6659.42 -63.2080384
n C4 1.84 0.54 0.0054 -5626.65 -30.3939262
n C 5 2.82 0.83 0.0087 -5.96E+03 -51.844729
n C 6 0.87 0.26 0.0028 -6894.52 -19.223717
n C7 0.09 0.03 0.0003 -7634.15 -2.48558706
i-C4 11.16 3.30 0.0324 -6170.29 -199.987136
i C 5 94.28 27.87 0.2898 -6036.68 -1749.62666
2 MP 38.72 11.44 0.1221 -6805.47 -830.901233
3 MP 23.38 6.91 0.0739 -6650.91 -491.458483
2,2 DMB 17.97 5.31 0.0564 -6632.83 -373.849325
2,3DMB 9.68 2.86 0.0305 -6613.38 -201.695991
2 MH 15.57 4.60 0.0498 -7801.45 -388.551913
3 MH 13.14 3.88 0.0420 -7632.19 -320.811117
2,2 DMP 4.47 1.32 0.0142 -7800.55 -111.039608
2,3 DMP 8.37 2.47 0.0267 -7551.44 -201.977523
2,4 DMP 3.66 1.08 0.0116 -7890.58 -91.9132828
3,3 DMP 3.18 0.94 0.0102 -7563.20 -76.915539
3 EP 1.26 0.37 0.0040 -7595.10 -30.4626677
C6H6 0.00 0.00 0.0000 -4675.81 0
C7H8 0.00 0.00 0.0000 -5385.02 0
CP 2.96 0.87 0.0092 -4701.57 -43.2365038
MCP 7.73 2.29 0.0246 -5691.74 -139.988369
CH 20.33 6.01 0.0648 -5623.11 -364.213341
ECP 0.71 0.21 0.0023 -6637.69 -15.1551398
MCH 19.26 5.69 0.0618 -6628.75 -409.653369
223TMB 1.99 0.59 0.0064 -7355.24 -46.8487831
H2O 0.00 0.00 0.0000 -2241.28 0
C2Cl4 0.00 0.00 0.0000 -5566.74 0
HCL 0.02 0.00 0.0004 0.0000 0 NaOH 0.00 0.00 0.0000 0.0000 0
TOTAL 338.33 100.00 1.00 -673158.11 -11929.58
Chapter 6 Energy Balance
83
Components ni xi Vapor
Fraction ∫CpGdT xii∫CpGdT
kmole/hr Mol% kJ/kmole K kJ/kmole K
H2 16.20 4.79 0.3974 -768.02 -305.229
C1 9.20 2.72 0.1548 -1060.10 -164.112
C2 5.95 1.76 0.0570 -1676.96 -95.562
C3 3.53 1.04 0.0194 -2401.60 -46.630
n C4 1.84 0.54 0.0054 -3146.11 -16.970
n C 5 2.82 0.83 0.0044 -3884.61 -17.250
n C 6 0.87 0.26 0.0007 -4624.54 -3.431
n C7 0.09 0.03 0.0000 -5363.89 -0.254
i-C4 11.16 3.30 0.0389 -3159.54 -122.906
i C 5 94.28 27.87 0.1691 -3871.29 -654.638
2 MP 38.72 11.44 0.0385 -4677.25 -180.028
3 MP 23.38 6.91 0.0218 -4621.61 -100.737
2,2 DMB 17.97 5.31 0.0209 -4643.51 -97.089
2,3DMB 9.68 2.86 0.0099 -4593.80 -45.345
2 MH 15.57 4.60 0.0084 -5494.82 -46.326
3 MH 13.14 3.88 0.0069 -5360.15 -36.822
2,2 DMP 4.47 1.32 0.0030 -5485.32 -16.370
2,3 DMP 8.37 2.47 0.0045 788.53 3.541
2,4 DMP 3.66 1.08 0.0024 -5360.15 -12.992
3,3 DMP 3.18 0.94 0.0018 -5360.15 -9.652
3 EP 1.26 0.37 0.0006 -5360.15 -3.382
C6H6 0.00 0.00 0.0000 -2814.73 0.000
C7H8 0.00 0.00 0.0000 -3513.06 0.000
CP 2.96 0.87 0.0038 -2964.10 -11.284
MCP 7.73 2.29 0.0062 -3803.45 -23.468
CH 20.33 6.01 0.0140 -3747.10 -52.430
ECP 0.71 0.21 0.0003 -4673.08 -1.360
MCH 19.26 5.69 0.0085 -4541.58 -38.697
223TMB 1.99 0.59 0.0013 -5395.11 -6.827
H2O 0.00 0.00 0.0000 0.00 0.000
C2Cl4 0.00 0.00 0.0000 0.00 0.000
HCL 0.02 0.00 0.0000 0 0.000 NaOH 0.00 0.00 0.0000 0 0.000
TOTAL 338.33 1.00 -167.974
Chapter 6 Energy Balance
84
6.3.4 Calculations:
TUBE SIDE
Total Enthalpy = Sensible Heat of Liquid + Latent Heat + Sensible Heat of Vapor
HT = HL + HV + HG
HG = n∫CpGdT
HG = 118755.937 kJ/hr
HV = n λ
HV = 1370608.32 kJ/hr
HL = n∫CpLdT
HL = 3044189.64 kJ/hr
HT = 4533553.9 kJ/hr
HT = 4.53E+06 kJ/hr
SHELL SIDE Total Enthalpy = Sensible Heat of Liquid + Latent Heat + Sensible Heat of Vapor
HT = HL + HV + HG
HG = n∫CpGdT
HG = -56830.9023 kJ/hr
HV = n λ
HV = -709486.596 kJ/hr
HL = n∫CpLd
HL = -4036164.38 kJ/hr HT
=
-4802481.88 kJ/hr
HT = -4.80E+06 kJ/hr
Heat Gained By Tube Side = Heat Lost By Shell Side
4.534E+06 kJ/hr = -4.802E+06 kJ/hr
Chapter 6 Energy Balance
85
6.4 ENERGY BALANCE AROUND HEAT EXCHANGER E 102:
E-102 TUBE SIDE SHELL SIDE
Temperature (0
C) Inlet Temperature 70 175
Outlet Temperature 147 120
Boiling Point 5.901 30.43
Pressure (kPa) Inlet Pressure 2370 2269
Outlet Pressure 2330 2210
Average Pressure
vapor Fraction in 0.2146 0.3641
vapor Fraction out 0.3489 8.61E-02 vapor Fraction avg 0.28175 0.2251
Boiling Point 5.901 30.43 Constant
Heat of Vaporization 10589.08 -23473.32
(kJ/kmole)
Chapter 6 Energy Balance
86
6.4.1 Molar Composition:
Components Stream No.3 Stream No.4 Stream No.10 Stream No.11
Mol% Mol% Mol% Mol%
H2 18.3713 18.3713 4.8240 4.8240
C1 2.3317 2.3317 2.7232 2.7232
C2 1.5074 1.5074 1.7673 1.7673
C3 0.8950 0.8950 1.0682 1.0682
n C4 3.1064 3.1064 1.8014 1.8014
n C 5 14.7758 14.7758 4.1623 4.1623
n C 6 11.7082 11.7082 3.2049 3.2049
n C7 5.8868 5.8868 0.5490 0.5490
i-C4 0.1884 0.1884 2.0228 2.0228
i C 5 9.5079 9.5079 24.5136 24.5136 2 MP 5.5287 5.5287 10.5400 10.5400 3 MP 3.5504 3.5504 6.4593 6.4593 2,2 DMB 0.4091 0.4091 4.0257 4.0257 2,3DMB 0.8896 0.8896 2.5385 2.5385 2 MH 2.3622 2.3622 4.5669 4.5669 3 MH 2.3616 2.3616 3.7824 3.7824 2,2 DMP 0.1734 0.1734 1.2316 1.2316 2,3 DMP 0.7078 0.7078 2.3349 2.3349 2,4 DMP 0.3592 0.3592 1.0363 1.0363 3,3 DMP 0.1114 0.1114 0.8847 0.8847 3 EP 0.1772 0.1772 0.3439 0.3439
C6H6 2.0560 2.0560 0.0024 0.0024 C7H8 1.9822 1.9822 0.0023 0.0023 CP 1.0703 1.0703 0.8734 0.8734 MCP 3.0147 3.0147 2.2844 2.2844 CH 2.9196 2.9196 6.0070 6.0070 ECP 0.1811 0.1811 0.2111 0.2111 MCH 3.8666 3.8666 5.6892 5.6892 223TMB 0.0000 0.0000 0.5490 0.5490 H2O 0.0000 0.0000 0.0000 0.0000 C2Cl4 0.0000 0.0000 0.0001 0.0001 HCL 0.0000 0.0000 0.0048 0.0048 NaOH 0.0000 0.0000 0.0000 0.0000
Total 100 100 100 100
Chapter 6 Energy Balance
87
6.4.2 Tube Side
Components ni xi liquid
Fraction ∫CpLdT xii∫CpLdT
kmole/hr Mol% kJ/kmole K kJ/kmole K H2 72.49 18.37 0.0170 524673.28 8915.51612 C1 9.20 2.33 0.0077 758742.22 5875.091135 C2 5.95 1.51 0.0111 39811.05 440.075118 C3 3.53 0.90 0.0090 17954.99 160.8721251 n C4 12.26 3.11 0.0360 15009.50 540.6714188 n C 5 58.30 14.78 0.1810 1.57E+04 2835.3435 n C 6 46.20 11.71 0.1469 18107.01 2659.813793 n C7 23.23 5.89 0.0745 20036.58 1492.595104 i-C4 0.74 0.19 0.0021 16529.78 35.07521004 i C 5 37.52 9.51 0.1160 15866.01 1839.666534 2 MP 21.82 5.53 0.0691 17855.82 1233.239608 3 MP 14.01 3.55 0.0444 17448.62 775.2681686 2,2 DMB 1.61 0.41 0.0051 17398.60 88.49878246 2,3DMB 3.51 0.89 0.0111 17347.93 192.5827109 2 MH 9.32 2.36 0.0298 20470.78 611.0525945 3 MH 9.32 2.36 0.0299 20020.43 598.1359298 2,2 DMP 0.68 0.17 0.0022 20459.10 44.7119097 2,3 DMP 2.79 0.71 0.0089 19805.23 177.1392678 2,4 DMP 1.42 0.36 0.0045 20693.98 93.6535025 3,3 DMP 0.44 0.11 0.0014 19844.47 27.90540672 3 EP 0.70 0.18 0.0022 19919.07 44.65634249 C6H6 8.11 2.06 0.0258 12272.22 316.2807209 C7H8 7.82 1.98 0.0251 14132.02 355.1701859 CP 4.22 1.07 0.0133 12335.95 163.5246758 MCP 11.90 3.01 0.0379 14925.56 565.5136593 CH 11.52 2.92 0.0368 14827.71 545.1904029 ECP 0.71 0.18 0.0023 17405.47 39.94105385 MCH 15.26 3.87 0.0490 17395.98 851.6697922 223TMB 0.00 0.00 0.0000 19272.40 0 H2O 0.00 0.00 0.0000 5875.66 0 C2Cl4 0.00 0.00 0.0000 -5566.74 0 HCL 0.00 0.00 0.0004 0.0000 0 NaOH 0.00 0.00 0.0000 0.0000 0
TOTAL 394.58 100.00 1.00 1776537.03 22638.42
Chapter 6 Energy Balance
88
Components ni xi Vapor
Fraction ∫CpGdT xii∫CpGdT
kmole/hr Mol% kJ/kmole K kJ/kmole K
H2 72.49 18.37 0.7923 2240.16 1774.8758
C1 9.20 2.33 0.0801 3099.31 248.3173
C2 5.95 1.51 0.0297 4906.03 145.5322
C3 3.53 0.90 0.0088 7026.70 62.1490
n C4 12.26 3.11 0.0130 9204.49 119.3501
n C 5 58.30 14.78 0.0254 11364.60 288.7354
n C 6 46.20 11.71 0.0083 13529.06 111.8589
n C7 23.23 5.89 0.0018 15691.84 28.7620
i-C4 0.74 0.19 0.0010 9243.86 9.2411
i C 5 37.52 9.51 0.0200 11326.69 226.6241 2 MP 21.82 5.53 0.0050 13683.03 68.3319 3 MP 14.01 3.55 0.0029 13520.74 39.4895 2,2 DMB 1.61 0.41 0.0005 13586.11 6.1982 2,3DMB 3.51 0.89 0.0008 13440.61 11.4123 2 MH 9.32 2.36 0.0009 16073.41 14.3433 3 MH 9.32 2.36 0.0009 15681.00 13.4115 2,2 DMP 0.68 0.17 0.0001 16047.89 1.4536 2,3 DMP 2.79 0.71 0.0003 -2332.94 -0.6275 2,4 DMP 1.42 0.36 0.0002 15681.00 2.9021 3,3 DMP 0.44 0.11 0.0000 15681.00 0.7234 3 EP 0.70 0.18 0.0001 15681.00 0.9608
C6H6 8.11 2.06 0.0013 8238.34 10.9963 C7H8 7.82 1.98 0.0005 10281.35 5.0173 CP 4.22 1.07 0.0014 8682.12 12.1120 MCP 11.90 3.01 0.0020 11136.05 22.0152 CH 11.52 2.92 0.0016 10976.71 17.3133 ECP 0.71 0.18 0.0000 13682.27 0.6378 MCH 15.26 3.87 0.0012 13295.61 15.3305 223TMB 0.00 0.00 0.0000 15784.86 0.0000 H2O 0.00 0.00 0.0000 0.00 0.0000 C2Cl4 0.00 0.00 0.0000 0.00 0.0000 HCL 0.00 0.00 0.0000 0.00 0.0000 NaOH 0.00 0.00 0.0000 0 0.0000
TOTAL 394.58 100.00 1.00 326452.92 917.79
Chapter 6 Energy Balance
89
6.4.3 Shell Side
Components ni xi liquid
Fraction ∫CpLdT xii∫CpLdT
kmole/hr Mol% kJ/kmole K kJ/kmole K
H2 16.32 4.82 0.0075 -456122.95 -3408.41681
C1 9.21 2.72 0.0077 -909163.18 -7029.54256
C2 5.98 1.77 0.0082 -48009.05 -391.363277
C3 3.61 1.07 0.0067 -18809.95 -126.759605
n C4 6.09 1.80 0.0147 -13693.05 -201.275326
n C 5 14.08 4.16 0.0411 -1.24E+04 -508.97138
n C 6 10.84 3.20 0.0364 -14260.24 -518.854674
n C7 1.86 0.55 0.0069 -15486.31 -106.757685
i-C4 6.84 2.02 0.0156 -15880.13 -246.956911
i C 5 82.93 24.51 0.2348 -12690.75 -2980.16715
2 MP 35.66 10.54 0.1162 -13913.02 -1616.61507
3 MP 21.85 6.46 0.0722 -13550.51 -977.749908
2,2 DMB 13.62 4.03 0.0429 -13520.48 -580.567259
2,3DMB 8.59 2.54 0.0279 -13468.91 -376.203287
2 MH 15.45 4.57 0.0560 -15940.33 -892.872845
3 MH 12.80 3.78 0.0466 -15503.51 -722.528748
2,2 DMP 4.17 1.23 0.0146 -15904.92 -232.571117
2,3 DMP 7.90 2.33 0.0287 -15304.59 -438.49287
2,4 DMP 3.51 1.04 0.0124 -16066.59 -198.80811
3,3 DMP 2.99 0.88 0.0107 -15485.36 -166.463623
3 EP 1.16 0.34 0.0042 -15373.62 -64.8511144
C6H6 0.01 0.00 0.0000 -9508.10 0
C7H8 0.01 0.00 0.0000 -10953.97 0
CP 2.95 0.87 0.0091 -9784.23 -88.6629931
MCP 7.73 2.28 0.0263 -11667.38 -306.572716
CH 20.32 6.01 0.0712 -12119.17 -863.057646
ECP 0.71 0.21 0.0027 -13571.47 -36.3929815
MCH 19.25 5.69 0.0722 -13677.27 -987.079201
223TMB 1.86 0.55 0.0066 -14725.77 -97.3980337
H2O 0.00 0.00 0.0000 -4268.44 0
C2Cl4 0.00 0.00 0.0000 -5566.74 0
HCL 0.02 0.00 0.0004 0.0000 0
NaOH 0.00 0.00 0.0000 0.0000 0
TOTAL 338.33 100.00 1.00 -1786381.51 -18726.20
Chapter 6 Energy Balance
90
Components ni xi Vapor
Fraction ∫CpGdT xii∫CpGdT
kmolw/hr Mol% kJ/kmole K kJ/kmole K
H2 16.32 4.82 0.1194 -1604.25 -77.390
C1 9.21 2.72 0.0612 -2334.47 -63.572
C2 5.98 1.77 0.0344 -3776.83 -66.749
C3 3.61 1.07 0.0176 -5438.13 -58.089
n C4 6.09 1.80 0.0238 -7093.26 -127.777
n C 5 14.08 4.16 0.0426 -8776.73 -365.314
n C 6 10.84 3.20 0.0244 -10445.90 -334.784
n C7 1.86 0.55 0.0031 -12113.88 -66.507
i-C4 6.84 2.02 0.0283 -7142.48 -144.477
i C 5 82.93 24.51 0.2632 -8769.80 -2149.795
2 MP 35.66 10.54 0.0866 -10572.76 -1114.364
3 MP 21.85 6.46 0.0515 -10439.68 -674.335
2,2 DMB 13.62 4.03 0.0357 -10529.97 -423.901
2,3DMB 8.59 2.54 0.0210 -10413.12 -264.339
2 MH 15.45 4.57 0.0277 -12448.77 -568.529
3 MH 12.80 3.78 0.0225 -12109.92 -458.050
2,2 DMP 4.17 1.23 0.0083 -12475.50 -153.645
2,3 DMP 7.90 2.33 0.0140 2072.56 48.392
2,4 DMP 3.51 1.04 0.0070 -12109.92 -125.499
3,3 DMP 2.99 0.88 0.0054 -12109.92 -107.140
3 EP 1.16 0.34 0.0020 -12109.92 -41.642
C6H6 0.01 0.00 0.0000 -6459.90 -0.155
C7H8 0.01 0.00 0.0000 -8021.26 -0.185
CP 2.95 0.87 0.0081 -6914.30 -60.392
MCP 7.73 2.28 0.0167 -8783.19 -200.641
CH 20.32 6.01 0.0407 -8734.52 -524.684
ECP 0.71 0.21 0.0011 -10793.30 -22.788
MCH 19.25 5.69 0.0303 -10460.21 -595.106
223TMB 1.86 0.55 0.0036 -12235.86 -67.176
H2O 0.00 0.00 0.0000 0.00 0.000
C2Cl4 0.00 0.00 0.0000 0.00 0.000
HCL 0.02 0.00 0.0000 0 0.000
NaOH 0.00 0.00 0.0000 0.000
TOTAL 338.33 100.00 1.00 -1982.823
Chapter 6 Energy Balance
91
6.4.4 Calculations:
TUBE SIDE
Total Enthalpy = Sensible Heat of Liquid + Latent Heat + Sensible Heat of Vapor
HT = HL + HV + HG
HG = n∫CpGdT
HG = 362142.117 kJ/hr
HV = n λ
HV = 4178240.08 kJ/hr
HL = n∫CpLdT
HL = 8932666.754 kJ/hr
HT = 13473048.95 kJ/hr
HT = 1.35E+07 kJ/hr
SHELL SIDE Total Enthalpy = Sensible Heat of Liquid + Latent Heat + Sensible Heat of Vapor
HT = HL + HV + HG
HG = n∫CpGdT
HG = -670852.8413 kJ/hr
HV = n λ
HV = -7941779.131 kJ/hr
HL = n∫CpLd
HL = -6335675.669 kJ/hr HT
=
-14948307.64 kJ/hr
HT = -1.49E+07 kJ/hr
Heat Gained By Tube Side = Heat Lost By Shell Side
1.347E+07 kJ/hr = -1.495E+07 kJ/hr
Chapter 6 Energy Balance
92
6.5 ENERGY BALANCE AROUND STABILIZER T-101
Energy balance around the stabilizer has been performed following the mass balance.
The reboiler duty and the condenser duties are calculated and the results are verified.
Heat in + Heat generated = Heat out + Heat consumed
Since there is no heat generation and consumption, therefore,
Heat in = Heat out.
The enthalpy of the feed entering (Hin) the column from reference temperature
Tr = 120oC
Hin = 0
The distillate temperature is Td = 115oC
The bottom‘s temperature is Tb = 125oC
Chapter 6 Energy Balance
93
The enthalpy of the distillate from reference temperature of 120oC is
Hd = -308 kW
The enthalpy of bottom product is
Hb = 96 kW
The reboiler duty can be calculated as
Qreb = V x λ
Qreb = 260 kW
The saturated steam flow rate for reboiling at 1 bar is
ms= Qreb/hs
ms =0.13 kg/s
The cooling duty of the condenser is
Qcon = (L+D) x Cp x (Tavg – Td)
Qcon = 50 kW
The flow rate of cooling water available at 40 oC
mc = Qcon/ (Cp) (Tavg – Td)
mc = 2.38 kg/s
CHAPTER 7
PLANT DESIGN CALCULATIONS
Chapter 7 Plant Design Calculations
94
CHAPTER # 7
PLANT DESIGN CALCULATIONS
7.1 REACTOR
Types of Reactors The most common types of Reactors are
1. Fixed bed Reactor
2. Fluidized bed Rector
3. Stirrer tank Reactor
Fixed bed reactor can be further classified on the biases of either heat is supplied
during reaction or not.
i. Adiabatic
ii. Non adiabatic
The reactions taking place within the reactor may be in gas phase or there might a
case of trickle operation. For gas phase reactions some important reactor
configurations are as under.
1. Single adiabatic bed
2. Radial flow
3. Adiabatic beds in series with intermediate cooling or heating
4. Direct-fired non-adiabatic
Except reactor type and configuration some other factors are important like ,
Distribution system and Sporting ceramic balls which also serves for uniform
distribution of flow as well. Our Reactor in this case is non-isothermal adiabatic
reactor with basket type distribution system and standard ceramic balls installation.
Detailed calculations of distribution system is given in design calculations.
Chapter 7 Plant Design Calculations
95
7.2 ALGORITHM FOR DETERMINING REACTION MECHANISM AND
RATE-LIMITING STEP:
Adsorption
Surface Reaction
Desorption
Assume surface reaction is
rate limiting
If the surface reaction is
limiting then:
Site balance:
Substituting for CN-S, CI-S, and CV into CT = CV (1 + KN PN + KI PI) :
Chapter 7 Plant Design Calculations
96
where KP is the thermodynamic equilibrium constant for the reactor.
Linearizing the Initial Rate:
Chapter 7 Plant Design Calculations
97
Reactor R-101 Design
Reaction n-Butane n-Pentane n-Hexane n-Heptane
K 8.5 7.9 6.7 5.5
KN 1.12 1.2 1.6 1.75
KI 13 11 9 8
Pressure P 2300 kPa
Temperature T 443 K
Compressibility Factor Z 0.8392
Universal Gas Constant R 8.314 kPa/kmol K
Molar Flow rate Fo 394.58 kmol/hr
Volume Flow Rate 530.26 m3/hr
Overall Concentration 744.13 mol/dm3 Stream 7
Components
Mole Fraction Molar Flow
Rate Volumetric Flow Fao
Concentration CAo
Conversion X
n-Butane 0.0309 12.19 16.38 22.9936 0.5 n-Pentane 0.1476 58.25 78.27 109.8335 0.75
n-Hexane 0.117 46.18 62.04 87.0632 0.765 n-Heptane 0.0588 23.22 31.18 43.7548 0.919
WB 209.9 kg WH 281.823 kg
WP
357.159
kg
WHe
330.038
kg
WT
1178.92
kg
V Weight of catalyst x 1.6 packing density
1.6 is a designing factor for catalytic Reactor
V 2.3727 m3
Chapter 7 Plant Design Calculations
98
PRESSURE DROP IN REACTOR R-101
Using ERGUN equation for the pressure drop in packed bed reactors
For the given reactor Length to dia Ratio L/D 5.000 Diameter D 0.845 m 2.773 ft Length L 4.227 m 13.864 ft
Area A 0.561 m2 6.039 ft2
Volume V 2.373 m3 83.726 ft3
For Feed of R-101
Density ρ 73.560 kg/m3 4.586 lb/ft3
Molecular Mass M 65.410
Inlet Molar Flow Rate Fo 394.580 kmol/h 109.606 mol/s
Outlet Molar Flow Rate F 338.3 kmol/h 93.972 mol/s
Pressure P 2300.000 kPa 48049.741 lbf/ft2
Temperature T 170.000 C 443.000 K
Viscosity μ 8.320E-06 lb/ft s
Compressibility Factor Z 0.839
Mass Flux G 12.772 kg/m2 s 2.612 lb/ft2
s
βo 475.371 α 0.000
dy/dw 1.12451E-05 1/y
y
0.986664298
Pressure at outlet P 2269.327886 kPa Pressure Drop ∆P
30.672
kPa
Chapter 7 Plant Design Calculations
99
Reactor R-102 Design
Reaction n-Butane n-Pentane n-Hexane n-Heptane
K 8.5 7.9 6.7 5.5 KN 1.12 1.2 1.6 1.75 KI 13 11 9 8
Pressure P 2210 kPa
Temperature T 393 K
Compressibility Factor Z 0.9808
Universal Gas Constant R 8.314 kPa/kmol K
Molar Flow rate Fo 338.32 kmol/hr
Volume Flow Rate 490.59 m3/hr
Overall Concentration 689.62 mol/dm3 Stream 9
Components
Mole Fraction Molar Flow
Rate Volumetric Flow Fao
Concentration CAo
Conversion X
n-Butane 0.0180 6.09 8.84 12.4227 0.4201 n-Pentane 0.0416 14.08 20.42 28.7040 0.7183 n-Hexane 0.0320 10.84 15.72 22.1019 0.7263 n-Heptane 0.0055 1.86 2.69 3.7861 0.9067
WB 391.619 kg WH 937.904 kg
WP
920.785
kg
WHe
1547.613
kg
WT
3797.921
kg
V Weight of catalyst x 1.6 packing density
1.6 is a designing factor for catalytic Reactor
V 7.64 m3
Chapter 7 Plant Design Calculations
100
PRESSURE DROP IN REACTOR R-102
Using ERGUN equation for the pressure drop in packed bed reactors
For the given reactor Length to dia Ratio L/D 5.000 Diameter D 1.249 m 4.095 ft Length L 6.243 m 20.476 ft Area A 1.224 m2 13.173 ft2
Volume V 7.644 m3 269.724 ft3
For Feed of R-101
Density ρ 27.340 kg/m
3 1.705 lb/ft3
Molecular Mass M 73.950
Inlet Molar Flow Rate Fo 338.320 kmol/h 93.978 mol/s
Outlet Molar Flow Rate F 338.3 kmol/h 93.972 mol/s
Pressure P 2210.000 kPa
46169.534 lbf/ft2
Temperature T 120.000 C 393.000 K
Viscosity μ 7.160E-06 lb/ft s
Compressibility Factor Z 0.839
Mass Flux G 5.676 kg/m2 s 1.161 lb/ft2
s
βo 262.053 α 0.000
dy/dw 3.44951E-06 1/y
y
0.995928192
Pressure at outlet P 2201.001304 kPa Pressure Drop ∆P
8.999
kPa
Chapter 7 Plant Design Calculations
101
7.3 DESIGNING OF NAPHTHA FEED PUMP:
A pump is one of the most important pieces of mechanical equipment that is present
in industrial processes. A pump moves liquid from one area to another by increasing
the pressure of the liquid above the amount needed to overcome the combined effects
of friction, gravity and system operating pressures.
There are two types of pump which are generally used in industrial processes: positive
displacement pump and centrifugal. It is important to choose the suitable type of
pump based on process requirement and fluid process properties.
In designing the pump, the knowledge of the effect of parameters; such as pump
capacity, NPSH, pumping maximum temperature, specific gravity, fluid viscosity,
fluid solid content, and the other process requirements are very important. All of these
parameters will affect the selection and design of the pump which will affect the
performance of the pump in the process.
NPSH as a measure to prevent liquid vaporization or called cavitation of pump. Net
Positive Suction Head (NPSH) is the total head at the suction flange of the pump less
the vapor pressure converted to fluid column height of the liquid.
Naphtha feed is coming from the atmospheric distillation column is treated with
hydrogen and brought to a pressure about 4 bar. This stream is then raised to a
pressure of 24 bar using a centrifugal compressor. The design of pump is carried out
using energy balance (extended Bernoulli‘s equation) and the power of the pump is
calculated.
Chapter 7 Plant Design Calculations
102
The stream at the inlet of the pump is at given conditions and rates specified.
Inlet pressure P1
4 bar
Outlet pressure P2
24 bar
Temperature T
35 °C
Density ρ
664.8 Kg/m3
Viscosity μ
1.037 Kg/m hr
Mass flow rate m
25000 Kg/hr
Molar flowrate F
301 Kmol/hr
Volumetric flowrate Q
37.605 m3/hr
Vapour pressure Pv
69.6 kPa
The optimum diameter of the pipe is found against given flow rate using the graph
Dopt
= 0.1061 m
The velocity of the fluid through the pump is given by
V = 4 X Q
(m/s) πD
2
V = 1.289 m/s
The work done per unit mass is given by the extended Bernoulli‘s equation.
∆W = (∆P/ ρ) + (∆PF/ ρ) + (∆V/2g) (J/kg)
∆W= (2000000/664.8) + (∆PF/664.8) + (0)
The pressure drop due to the friction is given by the Darcy‘s equation
∆PF = 8 x f x L x V2 x ρ
2 x D
For relative roughness (є) =0.046 m
Friction factor (f) = 0.002
An assumed length of 100 m from pump outlet to the inlet of the reactor
∆PF = 8670 N/m2
hence the work done per unit mass is
Chapter 7 Plant Design Calculations
103
∆W =2419.82 N/m2
The total work is given by taking efficiency of pump (η)=0.7
W = (∆W x m)/ η
W = 2419.82 x 25000/ (3600 x 0.7)
W = 24 KW or 32 hp
The Net positive suction head of the pump can be found by using the formula
NPSHavail = (P1/ρg) – (ΔPf/ρg) – (Pv/ρg)
NPSHavail = 49.37 m
Chapter 7 Plant Design Calculations
104
7.4 HEAT EXCHANGER DESIGN:
Heat exchanger E-101 is installed to recover the heat of the effluent from reactor R-
101 and heat the naphtha feed to bring it to the required temperature. The hot stream
which is coming from R-101 is at a temperature of 1750C and the cold stream is the
preheated naphtha feed coming from E-101 and is at a temperature of 78.21. The hot
stream is cooled to 1200C which is the required inlet temperature for R-102. Hence
the outlet temperature of naphtha feed can be determined.
The physical properties of both the streams are found at their mean temperatures. The
first iteration is done by assuming a constant specific heat; this is used to find the final
temperature of the naphtha stream to be 1120C.
Cold stream (Naphtha feed)
Inlet temperature (t1) = 78.21 0C
Outlet temperature (t2) = 120 0C
Molar flow rate (n) = 338.316 kmol/hr
Molecular mass (M) = 67
Specific heat (Cp) = 161.75 kJ/kg. k
Viscosity (µ) = 1.50E-5 Ns/m2
Density (ρ) = 112.36 kg/m3
Conductivity (k) = 0.091205 W/m k
Hot stream (effluent R-101)
Inlet temperature (T1) = 175 0C
Outlet temperature (T2) = 120 0C
Molar flow rate (n) = 394.58 kmol/hr
Molecular mass (M) = 74
Specific heat (Cp) = 162.4 kJ/kg. k
Viscosity (µ) = 1.01E-05 Ns/m2
Density (ρ) = 12.75 kg/m3
Conductivity (k) = 2.86E-02 W/m k
Chapter 7 Plant Design Calculations
105
Tubes of BWG 14 are selected the specifications are
Outer diameter (do) = 0.016 m
Inner diameter (di) = 0.0117836 m
Tube thickness (t) = 0.0021082 m
Tube length (L) = 5 m
The true temperature is found by
∆T = F x ∆Tm
∆Tm = (T2-t1)-(T1-t2)
Ln (T2-t1/T1-t2)
∆Tm = 51.671510020C
F can be found by using graph for two tube passes and one shell pass
F= 0.88
∆T = 0.88 x 51.671510020C
∆T = 45.47oC
The heat transfer area is given by
Q = 2.6 E+6 KJ/hr
A =
Q
U x ∆T
Assume U= 1000 KJ/m2 k
A = 52.78 m2
Number of tubes = A
π x I.D x L
Number of tubes (Nt) = 210
Number of tubes per pass (Np) = 105
Bundle diameter = do x ( Nt/k )1/n
Chapter 7 Plant Design Calculations
106
For two tube passes k= 0.249 and n=2.207
Bundle diameter (Db) = 0.3388 m
From graph at given bundle diameter clearance =0.0133 m
Shell diameter (Ds) = bundle diameter +shell clearance
Shell diameter = 0.3522 m
For tube pitches of 1.25 do
Number of baffles (b) = 5
Baffle spacing (lb) = L/number of baffles
Baffle spacing = 0.0705 m
Flow area at shell side (As) = (0.25 x di x lb x tubes at central plane)
Tubes at central plane = bundle diameter/ tube pitch
Tubes at central plane = 17
Hence,
Shell flow area = 0.00477 m2
The equivalent diameter of shell (de) = 4 x hydraulic radius
The equivalent diameter of shell = .02565 m
The tube side and shell side velocities can be found by using formula
Velocity = mass flow/ (density x area)
Us = 0.031733114 m/s
Ut = 5.707451295 m/s
Finding tube side heat transfer co=efficient
hi = (k/do)(jh x Re x Pr0.33
)
Reynolds number (Re) = (ρ x di x Ut)/ µ
Prandalt‘s number (Pr) = (Cp xµ)/k
Re = 500000
Pr=0.02664
hi = 2707.3
Chapter 7 Plant Design Calculations
107
Finding shell side heat transfer co=efficient
ho = (k/de)(jh x Re x Pr0.33
)
Re = 3700000
Pr = 0.057
ho = 2811.45
Overall heat transfer coefficient
U = (1/hi) +(1/ho) (di/do) + (t x di)/(kt x dw)
dw = (di +do)/2
kt= 15 W/m k
U = 981 KJ/m2 k
Pressure drop at tube side
Pt= Np ((8 x jf (L/d) +2.5)x(ρ x Ut))/2
Pt=1000 Pa
Shell side pressure drop
Ps= 8 x Jf x (Ds/de) x (L/lb) x (ρUs2/2)
Ps=440 Pa
Chapter 7 Plant Design Calculations
108
7.5 DESIGNING OF STABILIZER T-101:
The naphtha stabilizer column is designed as a distillation column. The feed is the
stream coming from the heat exchanger E-102. The stream temperature is 120oC and a
pressure of 18.5 bara. The feed of the column is fractionated and the product are
obtained as specified in the figure.
The method used for design is HENGTEBECK‘S METHOD, it is a modification to
the binary MC‘CABE AND THIELE method for binary distillation. The key
components selected are butane (iso and normal) and iso pentane. The heavier key is
iso-pentane and lighter key is butane stream.
KEYS
FEED FLOW
RATE
(F)
DISTILLATE
FLOW RATE
(D)
BOTTOMS
FOW RATE
(B)
Butane (LK) 12.996 12.9013 0.0946
ISO PENTANE
(HK) 94.234 0.9420 93.292
Chapter 7 Plant Design Calculations
109
COMPOSITIONS:
The molar fractions of butane and isopentane according to HENGTEBECK‘S
METHOD in the streams are given as
Feed distillate bottoms
Butane 0.12 0.9315 0.001
Iso pentane 0.88 0.0685 0.999
Using Antoine equation at column average temperature the saturation pressure of the
key components is found to be
Psatbutane= 15810 mm Hg
Psatiso pentane= 1480 mm Hg
Relative volatility of the stream with respect of the heavier key
αavg= 10.68
The expression for the vapor liquid equilibrium relation is given as
y= αx
1+(α-1)x
Using this data and developing a table for liquid vapour equilibrium curve
Liquid fraction Vapor fraction
0 0
0.1 0.546
0.2 0.7275
0.3 0.8206
0.4 0.8769
0.5 0.9143
0.6 0.9412
0.7 0.9614
0.8 0.9771
0.9 0.9897
1.0 1.0
Using MC‘CABE AND THIELE method for pseudo binary distillation for
Reflux ratio=5
Feed at bubble point=120oC feed line is vertical
Chapter 7 Plant Design Calculations
110
Intercept of top operating line= (xd)/(R+1)
Intercept of top operating line= 0.155
Number of ideal plates= 7
Feed plate= 5th
Efficiency of column
According to O‘CORNELL‘S equation, the overall efficiency of the column can be
estimated by the relation
Eo= 51-32.5log(µavgαavg )
µavg=(0.12x0.104)+(0.88x0.104)
µavg=0.104 mNs/m2
Using given equation the overall efficiency of the column is found to be EO=45%
Actual number of plates = 14
Column diameter calculations
The diameter of the column is calculated by using the formula for vapor flow through
a cylinder
Diameter of column = (4 x molar flow of vapors x mol.massavg)
1/2
(ρg x V‘x π)1/2
For bottom of the column
Mavg= 84.32
Molar flow rate = (R+1) D
Molar flow rate = 292.5 kmol/hr
ρg = 47.44kg/m3 using general gas equation
ρl = 550 kg/m3
V‘= K (ρl/ ρg -1)1/2
K can be found for 18 inches (460mm) tray spacing to be 0.135
V‘=0.437m/s
Diabottom = 0.65m (2.13 ft)
Chapter 7 Plant Design Calculations
111
For top of the column
Mavg= 76
Molar flow rate = (R+1) D
Molar flow rate = 292.5 kmol/hr
ρg = 44kg/m3 using general gas equation
ρl = 480kg/m3
V‘= K (ρl/ ρg -1)1/2
K can be found for 18 inches (460mm) tray spacing to be 0.252
V‘=0.6295m/s
Diatop = 0.0.532 m (1.74 ft)
The minimum diameter of the column must be 0.65 m
Height of the column
height of the column can be approximated as
LC =tray spacing x number of trays
LC =6.1 m appx
Pressure drop
Pressure drop across each plate is given by the relation
∆P =(9.81 X 10-3
)( ht)( ρl)
Where,
ht = hd+hw+how+hr
hd = dry pressure drop (due to friction)
hw = weir height
how = weir crest ( liquid level above weir)
hr = residual pressure drop
taking weir height hw =50 mm (2 inches)
Chapter 7 Plant Design Calculations
112
weir length = 0.7 x Dc
weir length = 0.455m
since,
hd = 51(Va/Co)2(ρg/ ρl)
Co = 0.84 (for 10% downcomer area, & hole dia/ plate thickness = 1)
hd= 119.6 mm
how =(750 Lw)/( ρlxlw)
how = 135mm
hw = 50mm
hr = (1.25 x 10-3)/ ρl
hr = 2.38 mm
ht = 307 mm
∆P =(9.81 X 10-3
)( 307)( 525)
∆P =1581 Pa (0.23psi)
Total pressure drop across column ∆Pc
∆Pc = 1581 x 14
∆Pc = 22120 Pa (3.2 psi)
Column specifications
Number of plates 14
Column diameter 0.65 m
Tray spacing 460 mm (18 inches)
Height of column 9.10 m
Weir height 50 mm (2 inches)
Pressure drop 22.12 Kpa (3.2 psi)
Downcomer area 10%
Chapter 7 Plant Design Calculations
113
Pressure At Different Stages
Q
Q
Q
7.6 DESIGNING OF HYDROGEN FEED COMPRESSOR K-101:
Chapter 7 Plant Design Calculations
114
For First Stage
γ = Cp/(Cp-R)
γ
Chapter 7 Plant Design Calculations
115
W = W/Ep
For Second Stage
γ = Cp/(Cp-R)
γ
Chapter 7 Plant Design Calculations
116
W = W/Ep
For Third Stage
γ = Cp/(Cp-R)
γ
Chapter 7 Plant Design Calculations
117
W = W/Ep
Chapter 7 Plant Design Calculations
118
For Fourth Stage
γ = Cp/(Cp-R)
γ
W = W/Ep
Chapter 7 Plant Design Calculations
118
Total Work & Power
CHAPTER 8
COST ESTIMATION
Chapter 8 Cost Estimation
119
CHAPTER # 8
COST ESTIMATION
8.1 COST ESTIMATION:
Feasibility means that the project being considered is technically possible. Economic
feasibility, in addition to acknowledging the technical possibility of a project, further
implies that it can be justified on an economic basis as well. Economic feasibility
measures the overall desirability of the project in financial terms and indicates the
superiority of a single approach over others that may be equally feasible in a technical
sense.
The cost analysis of an industrial process includes capital investment cost,
manufacturing cost and general expense such as income taxes.
8.1.1 Capital investments:
Before an industrial plant can be put into operation, large amount of money must be
supplied to purchase and install the necessary machinery and equipment, land and
service facilities must be obtained and the plant must be erected. Complete with all
pipe controls inn services. In addition it is necessary to have money available for
payment of expenses involved in the plant operation.
8.1.2 Fixed capital:
Fixed capital is that portion of the total capital that is invested in fixed assets (such as
land, buildings, vehicles, and equipment) that stay in the business almost
permanently. The capital needed to supply the necessary manufacturing and plant
facilities is called the fixed-capital investment
It includes
capital necessary for the installed process equipments
All design and construction overheads supervision
All piping, instruments and controls
insulation, foundations, and site preparation
Chapter 8 Cost Estimation
120
land, processing buildings, administrative, and other offices, warehouses,
laboratories.
Auxiliary facilities, such as utilities, land and civil engineering work
The fixed capital investment classified in to two sub divisions.
i. Direct Cost
ii. Indirect Cost
8.1.3 Working capital:
Working capital is additional investment which represents operating liquidity
available to a processing plant.
It includes the cost of
Startup
Initial catalyst charge
raw materials and supplies carried in stock
Inventories of intermediates and products
cash kept on hand for monthly payment of operating expenses, such as
salaries, wages etc.
Payable accounts and taxes.
The total capital investment is the sum of fixed and working capital. The ratio of
working capital to total capital investment varies with different companies, but most
chemical plants use an initial working capital amounting to 10 to 20 percent of the
total capital investment. This percentage may increase to as much as 50 percent or
more for companies producing products of seasonal demand because of the large
inventories which must be maintained for appreciable periods of time.
By far the most important item is the raw material expense. Labor is the component of
immediate secondary magnitude. This increased by the fact that pay role over head
Chapter 8 Cost Estimation
121
and plant overhead are always calculated fraction of labor expense and that
laboratories charges and supervision maybe estimated similarly if one chooses.
Depreciation, property taxes, insurance and sometimes maintenance and plant
supplied are estimated from the fixed capital investment. Individually there are small
in the manufacturing cost, but together they can represent a sizable total- Utilities take
collectively represent an amount of relative importance in a manufacturing cost.
Royalties on the average are small but should be carefully conceded when large.
Similarly, shipping is usually minor. Packaging expenses are usually small since the
petrochemical industry is primarily bulk supplier. However in particular face of the
industry packaging may prove to be of major importance. General expenses are a
sizable portion of total cost, can be estimated as percentage of manufacturing cost.
8.1.4 Direct cost:
Purchased Equipment Cost = E
Component Percentages of ‗Purchased Equipment
Cost‘ (E)
Purchased equipment Installation 47 %
Instrumentation (installed) 12 %
Piping (installed) 66 %
Electrical (installed) 11 %
Building (including Service) 18 %
Yard improvement 10 %
Service facilities 70 %
Total Direct Cost = D
8.1.5 Indirect cost:
Engineering and supervision 33 % E
Construction Expenses 46 % E
Total Indirect cost I
Total Direct and Indirect Cost D + I
Contractor‘s Fees 5 % (D+I) = x
Chapter 8 Cost Estimation
122
Contingency 10 % (D+I)=y
Fixed Capital investment D + I + x + y
Working Capital Investment 0.15 * (D+I+x+y)
Total Plant Cost (TPC) Fixed Capital + Working Capital
Land Cost 2 * TPC
Total Cost TPC + Land Cost
8.2 COST ESTIMATION OF OUR PLANT:
Cost of Equipment:
Cost of 2012 = cost of 2007 × (Index 2012/ Index 2007)
Cost Index of year 2007 = 525.4
Cost Index of year 2012 = 593.8
Equipment Purchased Cost (E):
Equipment 2007 Cost (US $) 2012 Cost (US $)
Drier
12600 14240.35021
Mixer 7800 8815.454892
Compressor 128400 145115.9498
pump 7900 8928.473544
Exchanger E-101 183500 207389.2273
Exchanger E-102 183500 207389.2273
Exchanger E-103 183500 207389.2273
Reactor R-101 31100 35148.80091
Reactor R-102 56300 63629.50133
Distillation Column 53300 60238.94176
Scrubber 4200 4746.783403
Total 852100 963031.9376
8.2.1 Direct cost estimation:
Purchased equipment installation 452625.0107 $
Instrumentation installation 115563.8325 $
Piping installed 636501.0788 $
Chapter 8 Cost Estimation
123
Electrical installed 105933.5131 $
Building including services 173345.7488 $
Yard improvement 96303.19376 $
Service facilities 674122.3563 $
Total direct cost 2253494.734 $
8.2.2 Indirect cost estimation:
Engineering and supervision 317800.5394 $
Construction expenses 394843.0944 $
Total direct and indirect cost 2966138.368 $
Miscellaneous,
Contractors fee 148306.9184 $
Contingency 2966138.8368 $
Total plant cost 3922717.991 $
Land cost 7845345.983 $
Total cost 11768153.97 $
Including present worth of catalyst for 4 years life, and given plant life of 16 years at
rate of $ 196/kg.
Present worth of catalyst 1611366 $
Miscellaneous 4541961.6 $
Annual revenues
For 24500 kg/hr and a production capacity of 24 hours a day and 300 days a year
Inflows 37849680 $
Annual expenses
Electricity 651183.16 $
Salaries and wages 65684.211 $
Income tax (40%) 15139872 $
Chapter 8 Cost Estimation
124
Sales tax (16%) 6055948.8 $
Net annual revenues = inflows – outflows
Net annual revenues = 12152024 $
8.2.3 Payback period:
Calculating discounted payback period at a MARR of 25%.
End of year 1 = -3657901 $
End of year 2 = 4119394.4 $
Hence 2nd
year is the payback period.
8.3 ECONOMICS OF PLANT LOCATION:
The final choice of the plant site usually involves a presentation of the economic
factors for several equally attractive sites. The exact type of economic study of plant
locations will vary with each company making a study. It should include the
following:
8.3.1 Investment:
Plant
New Money
Existing facilities
Working capital
Annual sales
Cost
Manufacturing
Distributing
Selling
Research
Annual Earnings
Operative
Net after taxes
Net annual return on total investment
Chapter 8 Cost Estimation
125
The limitations of preliminary plant location cost studies should be recognized
pointed out a management. No matter how carefully a survey is prepared, future
trends such as population and marketing shifts, development of competitive processes
and the advent of new industries. Services and transportation facilities cannot be
reliably predicated.
8.4 PLANT LOCATION AND SITE SELECTION:
The location of plant has a crucial effect on the profitability of project and the scope
for future expansion. Many factors are considered when selecting a suitable site. A
brief explanation of each factor is given below:
8.4.1 Raw Materials Supply:
Probably the location of the raw materials of an industry contributes more towards
the choice of a plant site than any other factor. This is especially noticeable in
those industries in which the raw material is inexpensive and bulky and is made
more compact and obtains a high bulk value during the process of manufacturing.
8.4.2 Marketing Area:
For materials that are produced in bulk quantities, such as cement, minerals acids
and fertilizers, where the cost of e product per ton is relatively low and cost of
transportation has a significant fraction of the sale price. The plant should be
located closed to the primary market. This consideration will be less important for
low volume production, high price product such as pharmaceuticals.
8.4.3 Transportation Facilities:
The Transport of material and products to and from the plant will be overriding
consideration in site selection. If practicable, a site should be selected that is
closed to at least two major forms of transport, road, rail, water way (canal or
river) or a sea port. Road transport is being increasingly used and is suitable for
local distribution from a central ware house. Rail transportation will be cheaper
for long distance transport of bulk chemicals. Air transport is convenient and
efficient for the movement of personnel and essential equipment and supplies and
the proximity of the site to a major airport should be considered.
Chapter 8 Cost Estimation
126
8.4.4 Sources of Power:
Power for chemical industry is primarily from coal, water and oil; these fuels
supply (he most flexible and economical sources, in as much as they provide for
generation of steam both for processing and for electricity production power can
be economically developed as a by-product in the most chemical plants. If the
needs are great enough, since the process requirements generally call for low-
pressure steam. The turbines of engines used to generate electricity can be
operated non-condensing and supply exhaust steam for processing purposes.
8.4.5 Availability of Labor:
Labor will be needed for construction of the plant and its operation. Skilled
construction workers will usually be brought in from outside the site area, but here
should be an adequate pool of unskilled labor available locally; and lab our
suitable for training to operate plant. Skilled tradesmen will be needed for plant
maintenance. Local trade union customs and restrictive practices will have to be
considered when assessing the availability and suitability of the local labor for
recruitment and training.
8.4.6 Water Supply:
Water for industrial purpose can be obtained from one of two general sources: the
plant's own source or municipal supply. If the demand for water is larger, it is
more economical for the industry to supply its own water. Such a supply may be
obtained from drilled wells, rivers, lakes, dammed streams or other impounded
supplies. Before a company enters upon any project, it must ensure itself of a
sufficient supply of water for all industrial, sanitary and fire demands, both
present and future.
8.4.7 Effluent Disposal:
All industrial process produce waste products and full consideration must be given
to the difficulties and cost of their disposal. The disposal of toxic and harmful
effluents will be covered by local regulations and appropriate authorities must be
consulted during the initial site survey to determine the standards that must be
met.
Chapter 8 Cost Estimation
127
8.4.8 Local Community Considerations:
The proposed plant must fit in with and be acceptable to the local community. Full
consideration must be given to the safe location of the plant so that it dies not
impose a significant additional risk to the community. On a new site, the local
community must be able to provide adequate facilities for, the plant personnel:
school, banks, housing and recreational and cultural facilities.
8.4.9 Land Considerations:
Sufficient suitable land must be available for the proposed pant and for future
expansion. The land should ideally be flat, well drained and have suitable load
bearing characteristics. A full site evaluation should be made to determine the
need for piling or other special foundation.
8.4.10 Climate:
Adverse climatic conditions at a site will increase costs. Abnormally low
temperature will require the provision of additional insulation and special heating
for equipment and pipe runs. Stronger structures will be need at locations
subjected to strong winds (cyclone hurricane areas) or earthquakes.
8.4.11 Political and Strategic Considerations:
Capital grants, tax concessions, and other inducements are often given by
government's direct new investment to preferred locations such as areas of high
unemployment. The availability of such grants can be over-riding consideration
site selection.
CHAPTER 9
ENVIRONMENT AND SAFETY
Chapter 9 Environment And Safety
129
CHAPTER # 9
ENVIRONMENT AND SAFETY
Petroleum refining is one of the largest industries and a vital part of the national
economy. However, potential environmental hazards associated with refineries have
caused increased concern for communities in close proximity to them. This update
provides a general overview of the processes involved and some of the potential
environmental hazards associated with petroleum refineries.
9.1 DEFINITION OF A PETROLEUM REFINERY:
Petroleum refineries separate crude oil into a wide array of petroleum products
through a series of physical and chemical separation techniques. These techniques
include fractionation, cracking, hydro treating, combination/blending processes, and
manufacturing and transport. The refining industry supplies several widely used
everyday products including petroleum gas, kerosene, diesel fuel, motor oil, asphalt,
and waxes.
9.2 BACKGROUND:
A refinery is an industrial plant for purifying a crude substance. The refining sector
investment in Pakistan has been almost nonexistent since the 1960s.In the late 90s,
Pakistan‘s refining capacity was less than 150k bbl. /day. Pakistan imported over 60%
of its total POL product consumption. At present, Pakistan‘s refining
capacity stands slightly below 300Kbb/day. This was mainly due to the
commencement of PARCO in the late 2000.Almost the refineries work at around 80%
capacity except Byco, which just utilized 45% of its capacity. NRL and PPl operate at
full capacity. Inspite of current condition there is a general lack of refineries; where
Pakistan is facing a deficit 100,000 to 150,000 barrels a day in refining fuel oil and
diesel. There are certain standards that are followed internationally known as EURO 2
and EURO 4 that relate to environmental cleanliness. Neither of these is followed in
Pakistan. The major players or the 5 refineries under OCAC (Oil Companies
Advisory Committee) are:
1. Pak Arab Refinery Complex
2. National Refinery Limited
Chapter 9 Environment And Safety
130
3. Pakistan Refinery Limited
4. Attock Refinery Limited
5. Byco Refinery Limited
Two refineries that have been introduced and don‘t come under OCAC. Enar
Petrotech Services Limited and Dohaka Refinery Limited.
9.3 PROCESSES INVOLVED IN REFINING CRUDE OIL:
The process of oil refining involves a series of steps that includes separation and
blending of petroleum products. The five major processes are briefly described below:
9.3.1 Separation Processes:
These processes involve separating the different fractions/ hydrocarbon compounds
that make up crude oil based on their boiling point differences. Crude oil generally is
composed of the entire range of components that make up gasoline, diesel, oils and
waxes. Separation is commonly achieved by using atmospheric and vacuum
distillation. Additional processing of these fractions is usually needed to produce final
products to be sold within the market.
9.3.2 Conversion Processes:
Cracking, reforming, coking, and visbreaking are conversion processes used to break
down large longer chain molecules into smaller ones by heating or using catalysts.
These processes allow refineries to break down the heavier oil fractions into other
light fractions to increase the fraction of higher demand components such as gasoline,
diesel fuels or whatever may be more useful at the time.
9.3.3 Treating:
Petroleum-treating processes are used to separate the undesirable components and
impurities such as sulfur, nitrogen and heavy metals from the products. This involves
processes such as hydro treating, deasphalting, acid gas removal, desalting,
hydrodesulphurization, and sweetening.
Chapter 9 Environment And Safety
131
9.3.4 Blending/Combination Processes:
Refineries use blending/combination processes to create mixtures with the various
petroleum fractions to produce a desired final product. An example of this step would
be to combine different mixtures of hydrocarbon chains to produce lubricating oils,
asphalt, or gasoline with different octane ratings.
9.3.5 Auxiliary Processes:
Refineries also have other processes and units that are vital to operations by providing
power, waste treatment and other utility services. Products from these facilities are
usually recycled and used in other processes within the refinery and are also important
in regards to minimizing water and air pollution. A few of these units are boilers,
wastewater treatment, and cooling towers.
9.4 ENVIRONMENTAL HAZARDS OF PETROLEUM REFINERIES:
Refineries are generally considered a major source of pollutants in areas where they
are located and are regulated by a number of environmental laws related to air, land
and water. Some of the regulations that affect the refining industry include the
following Laws, Rules and Regulations have been issued under the Pakistan
Environmental Protection Act, 1997.
9.4.1 Rules:
National Environmental Quality Standards (self-monitoring and Reporting by
Industries) Rules, 2001
Provincial Sustainable Development Fund (Procedure) Rules, 2001
Pakistan Sustainable Development Fund (Utilization) Rules, 2001
Provincial Sustainable Development Fund (Utilization) Rules, 2003
Pollution Charge for Industry (Calculation and Collection) Rules, 2001
Environmental Tribunal Rules, 1999
Environmental Tribunal Procedures and Qualifications Rules, 2000
Environmental Samples Rules, 2001
Chapter 9 Environment And Safety
132
Hazardous Substances Rules, 2000
Hazardous Substances Rules, 2003
9.4.2 Regulations :
Review of IEE/EIA Regulations, 2000 Pakistan Environmental Protection
Agency (Review of IEE1EIA) Regulations, 2000
National Environmental Quality Standards (Environmental Laboratories
Certification) Regulations, 2000
National Environmental Quality Standards
Draft Hospital waste Management Rules
Draft Composition of Offences and Payment of Administrative Penalty Rules,
1999
9.4.3 Policies &Strategies:
National Environment Policy
National Resettlement Policy March, 2002 (Draft)
National Drinking water Policy (Draft)
National Drinking water Policy
Clean Development Mechanism (CDM)
National Operational Strategy
Here is a breakdown of the air, water, and soil hazards posed by refineries:
9.4.4 Air Pollution Hazards:
Petroleum refineries are a major source of hazardous and toxic air pollutants such as
BTEX compounds (benzene, toluene, ethyl benzene, and xylem). They are also a
major source of criteria air pollutants: particulate matter (PM), nitrogen oxides (Knox),
carbon monoxide (CO), hydrogen sulfide (H2S), and sulfur dioxide (SO2). Refineries
also release less toxic hydrocarbons such as natural gas (methane) and other light
volatile fuels and oils. Some of the chemicals released are known or suspected cancer-
causing agents, responsible for developmental and reproductive problems. They may
Chapter 9 Environment And Safety
133
also aggravate certain respiratory conditions such as childhood asthma. Along with
the possible health effects from exposure to these chemicals, these chemicals may
cause worry and fear among residents of surrounding communities. Air emissions can
come from a number of sources within a petroleum refinery including: equipment
leaks (from valves or other devices); high-temperature combustion processes in the
actual burning of fuels for electricity generation; the heating of steam and process
fluids; and the transfer of products. Many thousands of pounds of these pollutants are
typically emitted into the environment over the course of a year through normal
emissions, fugitive releases, accidental releases, or plant upsets. The combination of
volatile hydrocarbons and oxides of nitrogen also contribute to ozone formation, one
of the most important air pollution problems in the United States.
9.4.5 Water Pollution Hazards:
Refineries are also potential major contributors to ground water and surface water
contamination. Some refineries use deep-injection wells to dispose of wastewater
generated inside the plants, and some of these wastes end up in aquifers and
groundwater. These wastes are then regulated under the Safe Drinking Water Act
(SDWA). Wastewater in refineries may be highly contaminated given the number of
sources it can come into contact with during the refinery process (such as equipment
leaks and spills and the desalting of crude oil). This contaminated water may be
process wastewaters from desalting, water from cooling towers, storm water,
distillation, or cracking. It may contain oil residuals and many other hazardous
wastes. This water is recycled through many stages during the refining process and
goes through several treatment processes, including a wastewater treatment plant,
before being released into surface waters. The wastes discharged into surface waters
are subject to state discharge regulations and are regulated under the Clean Water Act
(CWA). These discharge guidelines limit the amounts of sulfides, ammonia,
suspended solids and other compounds that may be present in the wastewater.
Although these guidelines are in place, sometimes significant contamination from past
discharges may remain in surface water bodies.
9.4.6 Soil Pollution Hazards:
Contamination of soils from the refining processes is generally a less significant
problem when compared to contamination of air and water. Past production practices
Chapter 9 Environment And Safety
134
may have led to spills on the refinery property that now need to be cleaned up.
Natural bacteria that may use the petroleum products as food are often effective at
cleaning up petroleum spills and leaks compared to many other pollutants. Many
residuals are produced during the refining processes, and some of them are recycled
through other stages in the process. Other residuals are collected and disposed of in
landfills, or they may be recovered by other facilities. Soil contamination including
some hazardous wastes, spent catalysts or coke dust, tank bottoms, and sludge from
the treatment processes can occur from leaks as well as accidents or spills on or off
site during the transport process.
9.5 MATERIAL SAFETY DATA SHEET:
Material name: Light Straight Run Naphtha
Synonym(s): LSR; LSR Gasoline; Light Straight Run; Light Straight Run
Gasoline; Gasoline - Straight-Run, Topping-Plant
Physical State Liquid.
Appearance Colorless to light yellow liquid.
9.5.1 Emergency Overview DANGER!
Extremely flammable liquid and vapor - vapor may cause flash fire. Will be easily
ignited by heat spark or flames. Heat may cause the containers to explode. Harmful if
inhaled, absorbed through skin, or swallowed. Aspiration may cause lung damage.
Irritating to eyes, respiratory system and skin. In high concentrations, vapors and
spray mists are narcotic and may cause headache, fatigue, dizziness and nausea.
Contains benzene, Cancer hazard, Mutagen, may cause heritable genetic damage.
May cause adverse reproductive effects -such as birth defects, miscarriages, or
infertility. Hydrogen sulfide, a highly toxic gas, may be present or released. Signs and
symptoms of overexposure to hydrogen sulfide include respiratory and eye irritation,
dizziness, nausea, coughing, a sensation of dryness and pain in the nose, and loss of
consciousness. Odor does not provide a reliable indicator of the presence of hazardous
levels in the atmosphere. Prolonged exposure may cause chronic effects. Toxic to
aquatic Organisms. May cause long-term adverse effects in the aquatic environment.
Chapter 9 Environment And Safety
135
9.5.2 OSHA Regulatory Status:
This product is considered hazardous under 29 CFR 1910.1200 (Hazard
Communication).
9.5.3 Potential Health Effects:
9.5.3.1 Eyes: Contact may irritate or burn eyes. Eye contact may result in corneal
injury.
9.5.3.2 Skin: Harmful if absorbed through skin. Irritating to skin. Frequent or
prolonged contact may defat and dry the skin, leading to discomfort and dermatitis.
9.5.3.3 Inhalation: Harmful if inhaled. Irritating to respiratory system. In high
concentrations, vapors and spray mists are narcotic and may cause headache, fatigue,
dizziness and nausea. May cause breathing disorders and lung damage. May cause
cancer by inhalation. Prolonged inhalation may be harmful.
9.5.3.4 Ingestion: Harmful if swallowed. Ingestion may result in vomiting; aspiration
(breathing) of vomiting into lungs must be avoided as even small quantities may
result in aspiration pneumonitis. Irritating to mouth, throat, and stomach.
9.5.3.5 Target organs: Blood. Eyes. Liver, Respiratory system, Skin, Kidneys,
Central nervous system.
9.5.3.6 Chronic effects: Cancer hazard. Contains material which may have
reproductive toxicity, teratogenetic or Mutagenic effects. Liver injury may occur.
Kidney injury may occur. May cause central nervous system disorder (e.g., narcosis
involving a loss of coordination, weakness, fatigue, mental confusion and blurred
vision) and/or damage. Frequent or prolonged contact may defat and dry the skin,
leading to discomfort and dermatitis.
9.5.3.7 Signs and symptoms: Irritation of nose and throat. Irritation of eyes and
mucous membranes. Skin irritation, Unconsciousness, Corneal damage, Narcosis,
Chapter 9 Environment And Safety
136
Cyanosis (blue tissue condition, nails, lips, and/or skin). Decrease in motor functions.
Behavioral changes, Edema, Liver enlargement. Jaundice, Conjunctivitis. Proteinuria,
Defatting of the skin rash.
9.5.3.8 Potential environmental effects: Toxic to aquatic organisms. May cause long-
term adverse effects in the aquatic environment.
9.5.4 Composition:
component percentage
Gasoline, straight-run, topping-plant 0 - 100
Pentane 0 - 35
Hexane (Other Isomers) 0 - 25
Pentane Isomers Mixture 0 - 25
n-Hexane 0 - 20
Benzene 0 - 5
Cyclohexane 0 - 5
Cyclopentane 0 - 5
Methyl cyclohexane 0 - 5
n- Heptanes 0 - 5
n-Butane 0 - 4
Hydrogen sulfide < 1
9.5.5 First Aid Measures:
9.5.5.1 Eye Contact :
Immediately flush eyes with plenty of water for at least 15 minutes. Remove contact
lenses, if present and easy to do. Continue rinsing. Get medical attention.
9.5.5.2 Skin Contact :
Remove contaminated clothing and shoes. Wash off immediately with soap and
plenty of water. Get medical attention if irritation develops or persists. Wash clothing
separately before reuse. Destroy or thoroughly clean contaminated shoes. If high
pressure injection under the skin occurs, always seek medical attention.
9.5.5.3 Inhalation:
Chapter 9 Environment And Safety
137
Move to fresh air. If breathing is difficult, give oxygen. If not breathing, give artificial
respiration. Get medical attention.
9.5.5.4 Ingestion:
Rinse mouth thoroughly. Do not induce vomiting without advice from poison control
center. Do not give mouth-to-mouth resuscitation. If vomiting occurs, keep head low
so that stomach content does not get into the lungs. Get medical attention
immediately.
9.5.5.5 Notes To Physician:
In case of shortness of breath, give oxygen. Keep victim warm. Keep victim under
observation. Symptoms may be delayed.
9.5.5.6 General Advice:
If exposed or concerned: get medical attention/advice. Ensure that medical personnel
are aware of the material(s) involved, and take precautions to protect themselves.
Show this safety data sheet to the doctor in attendance. Wash contaminated clothing
before re-use.
9.5.6 Fire Fighting Measures:
9.5.6.1 Extinguishing Media:
Suitable Extinguishing Media: Foam, CO2 or dry powder.
For Large Fire Use: Water.
Unsuitable Extinguishing Media: Do not use water jet.
9.5.6.2 Special Hazards Arising From The Substance Or Mixture:
Vapor may create explosive atmosphere. The vapor is heavier than air; beware of pits
and confined spaces. May give off toxic fumes in a fire. Carbon monoxide, Carbon
dioxide and various hydrocarbons.
Chapter 9 Environment And Safety
138
9.5.6.3 Advice For Fire-Fighters:
A self-contained breathing apparatus and suitable protective clothing should be worn
in fire conditions. Keep fire exposed containers cool by spraying with water.
Flash Point (°C): < 0
Flammable Limits (Lower) (%v/v): 1
Flammable Limits (Upper) (%v/v): 10
Auto Ignition Temperature (°C): > 250
9.5.7 Accidental Release Measures:
9.5.7.1 Personal Precautions:
Keep unnecessary personnel away. Local authorities should be advised if significant
spills cannot be contained. Keep upwind. Keep out of low areas. Ventilate closed
spaces before entering. Do not touch damaged containers or spilled material unless
wearing appropriate protective clothing. See Section 8 of the MSDS for Personal
Protective Equipment.
9.5.7.2 Environmental Precautions:
Gasoline may contain oxygenated blend products (Ethanol, etc.) that are soluble in
water and therefore precautions should be taken to protect surface and groundwater
sources from contamination. If facility or operation has an "oil or hazardous substance
contingency plan", activate its procedures. Stay upwind and away from spill. Wear
appropriate protective equipment including respiratory protection as conditions
warrant. Do not enter or stay in area unless monitoring indicates that it is safe to do
so. Isolate hazard area and restrict entry to emergency crew. Extremely flammable.
Review Fire Fighting Measures, Section 5, before proceeding with lean up. Keep all
sources of ignition (flames, smoking, flares, etc.) and hot surfaces away from release.
Contain spill in smallest possible area. Recover as much product as possible (e.g. by
vacuuming). Stop leak if it can be done without risk. Use water spray to disperse
vapors. Use compatible foam to minimize vapor generation as needed. Spilled
material may be absorbed by an appropriate absorbent, and then handled in
accordance with environmental regulations. Prevent spilled material from entering
sewers, storm drains, other unauthorized treatment or drainage systems and natural
waterways. Contact fire authorities and appropriate federal, state and local agencies. If
Chapter 9 Environment And Safety
139
spill of any amount is made into or upon navigable waters, the contiguous zones, or
adjoining shorelines, contact the National Response Center
9.5.7.3 Methods For Containment:
Eliminate all ignition sources (no smoking, flares, sparks, or flames in immediate
area). Stop leak if you can do so without risk. This material is a water pollutant and
should be prevented from contaminating soil or from entering sewage and drainage
systems and bodies of water. Dike the spilled material, where this is possible. Prevent
entry into waterways, sewers, basements or confined areas.
9.5.7.4 Methods For Cleaning Up:
Use non-sparking tools and explosion-proof equipment. Small Spills: Absorb spill
with vermiculite or other inert material, then place in a container for chemical waste.
Clean surface thoroughly to remove residual contamination. This material and its
container must be disposed of as hazardous waste. Large Spills: Use a non-
combustible material like vermiculite, sand or earth to soak up the product and place
into a container for later disposal. Prevent product from entering drains. Do not allow
material to contaminate ground water system. Should not be released into the
environment.
9.5.7.5 Other Information:
Clean up in accordance with all applicable regulations.
9.5.8 Handling And Storage:
9.5.8.1 Handling:
Wear personal protective equipment. Do not breathe dust/fume/gas/mist/vapors/spray.
Avoid contact with eyes, skin, and clothing. Do not taste or swallow. Avoid
prolonged exposure. Use only with adequate ventilation. Wash thoroughly after
handling. The product is extremely flammable, and explosive vapor/air mixtures may
be formed even at normal room temperatures. DO NOT handle, store or open near an
open flame, sources of heat or sources of ignition. Protect material from direct
sunlight. Take precautionary measures against static discharges. All equipment used
when handling the product must be grounded. Use non-sparking tools and explosion-
Chapter 9 Environment And Safety
140
proof equipment. When using, do not eat, drink or smoke. Avoid release to the
environment.
9.5.8.2 Storage :
Flammable liquid storage. Do not handle or store near an open flame, heat or other
sources of ignition. This material can accumulate static charge which may cause spark
and become an ignition source. The pressure in sealed containers can increase under
the influence of heat. Keep container tightly closed in a cool, well-ventilated place.
9.5.9 Exposure Controls/Personal Protection:
9.5.9.1 Appropriate Engineering Controls:
Provide adequate ventilation, including appropriate local extraction, to ensure that the
occupational exposure limit is not exceeded occupational Exposure Limit assigned.
9.5.9.1.2 Personal Protection
9.5.9.1.2.1 Eye/face protection: Goggles giving complete protection to eyes
9.5.9.1.2.2 Skin protection: Protective gloves
9.5.9.1.2.3 Respiratory protection: In case of insufficient ventilation, wear suitable
respiratory equipment
Chapter 9 Environment And Safety
141
9.5.10 Physical And Chemical Properties
Information on basic physical and chemical properties
Appearance: Liquid.
Color: Pale yellow.
Odour: Hydrocarbon.
Boiling Point (°C): < 35
Flash Point (°C):<0
Flammable Limits (Lower) (%v/v) : 1
Flammable Limits (Upper) (%v/v): 10
Vapor Pressure (mm Hg): 200 (@ 20°C)
Specific Gravity: 0.70-0.80
Solubility (Water): Negligible.
Partition Coefficient:
(n-Octane/water) 1.0-8.0
Auto Ignition Temperature (°C): >250
Viscosity: 1 mm2/s (@ 20°C)
Explosive Properties: Vapor may create explosive
atmosphere.
Oxidizing Properties: Not oxidizing.
Vapor Density (Air=1):>2
Other information
Conductivity: 15-35
9.5.11 Stability And Reactivity:
Reactivity Reacts with Strong oxidizing agents.
Chemical stability Stable under normal
conditions.
Possibility of hazardous reactions No information available.
Conditions to avoid Keep away from heat, sources of
Chapter 9 Environment And Safety
142
ignition and direct sunlight.
Incompatible materials Oxidizing agents.
Hazardous Decomposition Product(s) May give off toxic fumes in a
fire. Carbon monoxide, Carbon
dioxide and various hydrocarbons
9.5.12 Toxicological Information:
Ingestion LD50 (oral/rat):>5000 mg/kg
Inhalation LC50 (inhalation/rat):>5.2 mg/l/4
h
Skin Contact LD50 (dermal/rabbit):>2000
mg/kg
Eye Contact No information available.
Skin corrosion/irritation Irritating to skin.
Serious eye damage/irritation May cause eye irritation.
Respiratory or skin sensitization Negative.
Mutagenicity May cause heritable genetic
damage.
Carcinogenicity May cause cancer.
Reproductive toxicity Suspected of damaging
fertility.
Suspected of damaging the unborn
child.
STOT-single exposure Vapors may cause drowsiness and
dizziness.
STOT-repeated exposure Negative.
Aspiration hazard Risk of aspiration .Aspiration of
Liquid may cause pulmonary
edema.
CHAPTER 10
INSTRUMENTATION AND
CONTROL
Chapter 10 Instrumentation and Control
143
CHAPTER # 10
INSTRUMENTATION AND CONTROL
The important feature common to all process is that a process in never in a state of
static equilibrium except for a very short period of time and process is a dynamic
entity subject to continual upset or disturbance which' tend to drive it away from the
desired state of equilibrium the process must then be manipulated upon or
corrected to derive some disturbance bring about only transient effect in the process
behavior. These passes away and the never occur again. Others may apply periodic or
cycle forces which may make the process respond in a cyclic or periodic fashion.
Most disturbances are completely random with respect to time a show no repetitive
pattern. Thus their occurrence may be expected hut cannot be predicated at any
particular time. If a process is to operate efficiently, disturbances in the process must
be controlled.
A process is designed for a particular objective or output and is then found.
Sometimes by trial and error and sometimes by referring from the previous,
experience that control of a particular variable associated with some stages of the
process is necessary to achieve the desired efficiency.
Each process will have associated with it number of variables which are independent
of the process and/ or its operation and which are likely to change at random. Each
such change will lead to changes in the dependent variables of the process one of
which is selected as bring indicative of successfully operation. One of the input
variable will be manipulated to cause further changes in the output variable will be
manipulated to cause further changes in the output variable the original
conditions, Process may controlled more precisely to give more uniform and
higher quality products by the application of automatic control, often leading to
higher profits additionally, process which response too rapidly to be controlled by
human operators can be controlled automatically. Automatic control is also
beneficial in certain remote, hazardous or routine operations. After a period of
experimentation, computers are now being used to operate automatic ally control
Chapter 10 Instrumentation and Control
144
processing systems, which may too large and too complex for effective direct
human control.
Since process profit is usually the most important benefit to obtained by
applying automatic control. The quality of control and its cost should be
compared with the economic return expected and the process technical
objective. The economic return includes reduced operating costs, maintenance and of
the specification product along with improved process operability and increased
throughout.
10.1 COMPONENTS OF THE CONTROL SYSTEM:
10.1.1 Process:
Any operation of series of operations that produce a desired final result is a process.
In this discussion the process is the purification of natural
10.1.2 Measuring Means:
As all the parts of the control system, measuring element, is perhaps the most
important. If the measurements are not made properly the remainder of the system
cannot operate satisfactorily. The measured variable is chosen to represent the desired
condition in the process.
10.2 ANALYSIS OF MEASUREMENT:
10.2.1 Variables to be Measured:
a. Pressure Measurement
b. Temperature Measurement
c. Flow Rate Measurement
d. Level Measurement
10.2.2 Variables to be Recorded:
Indicated temperature, composition, pressure etc.
Chapter 10 Instrumentation and Control
145
10.3 CONTROLLER:
The controller is the mechanism that responds to any error indicated by the
error detecting mechanism. The output of the controller is some predetermined
function of the error. There are three types of controllers.
1. Proportion action which moves the control valve indirect proportion to
the magnitude of the error.
2. Integral action (reset) which moves the control valve based on the time
integral of the error and the purpose of integral actions is to drive the process
back to .its set point when it has been disturbed.
3. Ideal derivative action and its purpose are to anticipate where the process
is heading by cooking at the time a rate of change of error. The final
control element receives the signal from the controller and by some
predetermined relationship changes the energy input to the process.
10.4 CHARACTERISTICS OF CONTROLLER:
In general the process controllers can be classified as
a. Pneumatic controllers
b. Electronic controllers
c. Hydraulic controllers
While dealing with the gases, the controller and the final control element may
be pneumatically operated due to the following reasons.
i. The pneumatic controller is very rugged and almost free of maintenance.
The maintenance men have not had sufficient training and background in
electronics, so pneumatic equipment is simple.
ii. Pneumatic controller appears to be safer in a potentially explosive
atmosphere which is often present in the industry.
iii. Transmissions distances are short pneumatic and electronic transmissions
system are generally equal up to about 200 to 300 feet. Above this distance
electronic system beings to offer savings.
Chapter 10 Instrumentation and Control
146
10.5 MODES OF CONTROL:
The various types of control are called modes, and they determine type of
response obtained. In other words these describe the action of controller that is the
relationship of output of output signal to the input or error signal. It must be noted
that is error that achieve the controller. The four basic mode of control are:
1. On-off control
2. Integral control
3. Proportional control
4. Rate or derivative control
In industry purely integral, proportional or derivative modes seldom occur alone in
the control system. The on-off controller is the controller with very high gain. In this
case the error signal at once off the valve or any other parameter upon which it sites
or completely sets system.
10.6 ALARMS AND SAFETY TRIPS:
Alarms are used to alert operators of serious and potentially hazardous,
deviations in process conditions, key instruments are fitted with switches and relays
to operate audible and visual alarms on the control panels.
The basic components of an automatic trip system are
1. A sensor to monitor the control variable and provide and output signal when a
preset value is exceeded (the instrument).
2. A link to transfer the signal to the activator, usually consisting of a
system of pneumatic or electric relays.
3. An activator to carry out the required action close or open a valve, switch off a
motor.
10.7 CONTROL LOOPS:
For instrumentation and control of different sections and equipments of plants,
following control loops are most often used.
1. Feed backward control loop
Chapter 10 Instrumentation and Control
147
2. Feed forward control loop
3. Ratio control loop
4. Auctioneering control loop
5. Split range control loop
6. Cascade control loop
Here is given a short outline of these control schemes, so that to justify our selection
of a control loop for specified equipment.
10.8 FEED BACK CONTROL LOOP:
A method of control in which a measured value of a process variable is compared
with the desired value of the process variable and any necessary action is taken.
Feedback control is considered as the basic control loops system. Its disadvantage
lies in its operational procedure. For example if a certain quantity is entering in a
process, then a monitor will be there at the process to note its value. Any changes
from the set point will be sent to the final control element through the controller so
that to adjust the incoming quantity according to desired value (set point). But in fact
change has already occurred and only corrective action can be taken while using
feedback-control system.
10.9 FEED FORWARD CONTROL LOOP:
A method of control in which the value of a disturbance is measured, and action is
taken to prevent the disturbance by changing the value of a process variable. This is a
control method designed to prevent errors from occurring in a process variable.
This control system is better than feedback control because it anticipates the change in
the process variable before it enters the process takes the preventive action. While in
feedback enter system action is taken after the change has occurred.
10.10 RATIO CONTROL:
A control loop in which, the controlling element maintains a predetermined ratio of
one variable to another. Usually this control loop is attached to such a system
where two different streams enter a vessel for reaction that may be of any kind.
To maintain the stoichiometric quantities of different streams this loop is used
so that to ensure proper process going on in the process vessel.
Chapter 10 Instrumentation and Control
148
10.11 AUCTIONEERING CONTROL LOOP:
This type of control loop is normally used for a huge vessel where, readings of a
single variable may be different at different locations. This type of control loop
ensures safe operation because it employs all the readings of different locations
simultaneously, and compares them with the set point, if any of those readings is
deviating from the set point then the controller sends appropriate signal to final
control element.
10.12 SPLIT RANGE LOOP:
In this loop controller is per set with different values corresponding to different action
to be taken at different conditions. The advantage of this loop is to maintain the
proper conditions and avoid abnormalities at very differential levels.
10.13 CASCADE CONTROL LOOP:
This is a control in which two or more control loops are arranged so that the output of,
one controlling element adjusts the set point of another controlling element. This
control loop is used where proper and quick control is difficult by simple feed forward
or feed backward control. Normally first loop is a feedback control loop. We have
selected a cascade control loop for our heat exchanger in order to get quick on proper
control.
10.14 INTERLOCKS:
Where it is necessary to follow a fixed sequence of operations for example, during a
plant start-up and shut-down, or in batch operations. Interlocks are includes to prevent
operators departing from the required sequence. They may be incorporated in the
control system design, as pneumatic or electric relays or may be mechanical
interlocks.
10.15 CONTROL OF HEAT EXCHANGER:
10.15.1 The Normal Way:
The normal method of controlling a heat exchanger is to measure exit
temperature of process fluid and adjust input of heating or cooling medium to
hold the desired temperature.
Chapter 10 Instrumentation and Control
149
To stabilize this feedback control, in almost all cases the control must have a
wide proportional band (i.e., wide range of exit temperature change operates the
control valve through full stroke). The proportional band is determined by gain of
other components in the control loop by process considerations.
Since heat-exchanger control require a wide proportional band for stabilization,
reset response (rate of change of heating medium How proportional to exit
temperature.
deviation from controller set point is normally required to correct for offset in
the controlled variable (temperature). It there are process load change and reset
response can be eliminated in cases where disturbance such as heating fluid header
pressure, product flow rate or inlet temperature changes have small effects relative to
desired tolerance on the controlled variable.
When throughout to a heat exchanger is changed rapidly a short-term error in control
temperature results. The magnitude and duration of this error can normally be reduced
by a factor of two by adding derivative response to the control mechanism and
adjusting it properly. In derivative responses, heating fluid flow rate is proportional to
rate or change of temperature derivation from the set point.
10.15.2 A Pressure Cascade Control:
A pressure cascade control system cascades output of a standard three action
temperature controller into the set point of a pressure controller. It achieves a more
rapid recovery to process load disturbances in a shell-and-tube exchanger than can be
obtained without the pressure controller. Heating fluid to the heater is regulated
by the pressure controller which is normally provided with proportional and reset
responses. Load change is rapidly sensed by a change is shell pressure which is
compensated for by the pressure controller. The temperature control system senses the
residual error and resets the pressure control set point.
10.15.3 Bypass Improves Control of Slow-Response Exchanger:
In certain cascade, the time response characteristic of heat exchanger is too slow to
hold temperature deviations resulting from load changes within desired tolerances. In
Chapter 10 Instrumentation and Control
150
some of these cases, the transient characteristic of the heat exchanger can be
circumvented by by- passing the heater with a parallel line and bleeding cold process
fluid with hot fluid from the heater. In the by-pass system care must be taken in sizing
valves to obtain the-desired flow sprit with adequate flow versus steam travel
characteristics. Thermal elements response time is particularly important since this tie
constant is a major factor influencing performance of the system.
10.15.4 Flow Controllers:
These are used to control tin-feed rate into a process unit Orifice plates are by far the
most type of How-rate sensor. Normally orifice plates arc designed to give pressure
drops in the range of 20 to 200 inch of water Venture tubes amend turbine meter are
also used.
10.15.5 Temperature controller:
Thermocouples are the most commonly used temperature sensing device. The two
dissimilar wires produce a millivolt emf that varies with the ―hot- functions‖
temperature. Iron constant to thermocouples are commonly used over the 0 to 1300 F.
temperature range.
10.15.6 Pressure Controller:
Bourdon tubes, bellows and diaphragms are used to sense pressure and differential
pressure. For example, in mechanical system the process pressure force is balanced by
the movement of a spring. The spring positing can be related to process pressure.
10.15.7 Level Indicator:
Liquid levels are detected in a variety of ways. The three common are
1. The following the position of a float that is lighter than the fluid.
2. Measuring one apparent-weight of a heavy cylinder as it is buoyed up more or
less by the liquid (they are called displacement meters).
3. Measuring the difference in static pressure between two fixed elevations, one
in the vapour above the liquid and the other under the liquid surface.
The differential pressure between the two level taps is directly related to the
liquid level in the vessel.
Chapter 10 Instrumentation and Control
151
10.15.8 Transmitter:
The transmitter is the interface between the process and its control system. The Job of
the transmitter is to convert the sensor signal (millivolts, mechanical movement,
pressure difference etc.) into a control signal 3 to 15 psig air pressure signal, 1 to 5 10
to 50 milli ampere electrical signal etc.
10.15.9 Control Valves:
The interface with the process at the other end of the control loop is made by the final
control element in an automatic control valves control the flow of heating fluid the
open or close and orifice opening as the system is raised or lowered.
152
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2. J.H Gray, Petroleum Refining Technology and Economics, 4th
edition, Marcel
Dekker 2001
3. Serge Raseev, Thermal and Catalytic Processes in Petroleum Refining, Marcel
Dekker 2003
4. Ludwig, E.E, ‖ Applied process design‖ , 3rd
ed, vol. 2, Gulf
Professional Publishers, 2002.
5. Ludwig, E.E, ―Applied Process Design, 3rd ed, vol. 3, Gulf
Professional Publishers, 2002.
6. McKetta, J.J., ―Encyclopedia of chemical Processing and Design‖, Executive
ed, vol. 1, Marcel Dekker Inc, New York, 1976.
7. Levenspiel, O., ―Chemical Reaction Engineering:, 3rd ed ,John Wily and
Sons Inc., 1999.
8. Peters, M.S. and Timmerhaus ,K.D., ―Plant Design and Economics for
Chemical Engineering ―, 5th ed, McGraw Hill, 1991.
9. Rase, H.F., ―Fixed Bed Reactor Design and Diagnostics, Butterworth
Publishers, 1990.
10. Frank L., Evans Jr. ―Equipment Design Hand Book For Refineries &
Chemical Plants‖ Vol 2, 2nd Ed., 1980,
11. Peacock, D.G.,‖ Coulson & Richardson‘s Chemical engineering‖,
3rded,vol,Butterworth Heinenann, 1994.
12. Kern D.Q., ―Process Heat Transfer‖, McGraw H ill Inc.,2000.
13. Mcabe, W.L, ―Unit Operations of Chemical Engineering ―,5th
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Hill, Inc,1993.
14. Perry, R.H and D.W. Green (eds): Perry‘s Chemical Engineering Hand Book,
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16. Rohsenow,Hartnett,Ganic ―Hand Book of Heat Transfer Application‖ 2nd
edition.
17. Fogler H.S. ―Elements of Chemical Reaction Engineering‖ 2nd Edition.
18. W.L.Nelson. ―Petroleum Refinery Engineering‖4th
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21. Kirk: ―Encyclopedia of Chemical Technology ― John Willey and Sons, New
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23. Warren M. Rohenson: ―Hand book of Heat Transfer ―, McGrawHill, New York
154
APPENDICES
A Components Properties
B Thermodynamic Properties
C Equilibrium Constants
D Graphs used in the designing of Compressor, pump,
heat exchanger and Distillation column
155
Components
Boiling
Temperature C
Mol Wt
Critical
Pressure Kpa
Critical Temp
C
APPENDIX A
Hydrogen -252.595 2.016 1315.5 -239.71 Methane -161.525 16.0429 4640.68 -82.451 Ethane -88.6 30.0699 4883.85 32.278 Propane -42.102 44.097 4256.66 96.748 n-Butane -0.50199 58.124 3796.62 152.049 n-Pentane 36.059 72.151 3375.12 196.45 n-Hexane 68.73 86.1779 3031.62 234.748 n-Heptane 98.429 100.205 2736.78 267.008 i-Butane -11.73 58.124 3647.62 134.946 i-Pentane 27.878 72.151 3333.59 187.248 2-Mpentane 60.261 86.1779 3010.36 224.347 3-Mpentane 63.27 86.1779 3123.84 231.299 22-Mbutane 49.731 86.1779 3880.62 231.299 23-Mbutane 57.977 86.1779 3126.87 226.83 2-Mhexane 90.049 100.205 2733.62 257.219 3-Mhexane 91.847 100.205 2813.79 262.1 22-Mpentane 79.191 100.205 2773.26 247.35 23-Mpentane 89.778 100.205 2908.02 264.198 24-Mpentane 80.493 100.205 2736.78 246.639 33-Mpentane 86.059 100.205 2945.51 263.248 3-Epentane 93.472 100.205 2890.8 267.49 Benzene 80.089 78.11 4924.39 288.948 Toluene 110.649 92.1408 4100.04 318.649 Cyclopentane 49.248 70.135 4508.95 238.45 Mcyclopentan 71.809 84.1619 3789.55 259.55 Cyclohexane 80.73 84.16 4053 280.05 Ecyclopentan 103.467 98.189 3397.62 296.37 Mcyclohexane 100.929 98.189 3475.37 298.948 223-Mbutane 80.876 100.205 2953.62 258.019
H2O 99.998 18.0151 22120 374.149
CCl4 76.748 153.822 4559.99 283.25
156
Heat of
Combustion
kJ/Kmol
Heat of
Formation
kJ/Kmol
MON
RON
Flash point
Freez point
-241942 0 130 -259.25
-802703 -74900 120 -182.75
-1.43E+06 -84738 100.789 111.378 -182.75
-2.04E+06 -103890 97.1 112.135 -187.65
-2.66E+06 -126190 89.6 93.8 -138.15
-3.27E+06 -146490 62.6 61.7 -40.15 -130.15
-3.89E+06 -167290 26 24.8 -21.15 -95.15
-4.50E+06 -187890 0 0 -4.15 -90.15
-2.65E+06 -134590 97.6 101.426 -159.15
-3.27E+06 -154590 90.3 92.3 -56.15 -160.15
-3.85E+06 -174390 73.5 73.4 -35.15 -153.15
-3.88E+06 -171690 74.3 74.5 -32.15 -163.15
-3.87E+06 -185690 93.4 91.8 -48.15 -99.15
-3.88E+06 -177890 94.3 100 -29.15 -128.15
-4.50E+06 -195090 46.4 42.4 -23.15 -118.15
-4.50E+06 -192390 55.8 52 -4.15 -119.15
-4.49E+06 -206290 95.6 92.8 -15.15 -124.15
-4.49E+06 -199390 88.5 91.1 -15.15 -4.49E+06 -202090 83.8 83.1 -12.15 -119.15
-4.49E+06 -201690 86.6 80.8 -19.15 -134.15
-4.50E+06 -189790 69.3 65 -12.15 -118.15
-3.17E+06 82977 101 106 -11.15 5.85
-3.77E+06 50029 103.524 120.083 3.85 -95.15
-3.10E+06 -77288 84.9 101.426 -40.15 -94.15
-3.71E+06 -106790 80 91.3 -27.15 -142.15
-3.69E+06 -123190 77.2 83 -20.15 6.85
-4.32E+06 -127190 61.2 67.2 -4.15 -138.15
-4.29E+06 -154890 71.1 74.8 -6.15 -126.15
-4.49E+06 -204890 101 100 -24.15 -24.15
- -241814
-258069 -100488
157
13 32 101.3 9.183 -107.9 0 0.1641 6.02E-04 2 91 190.4 101.3 31.35 -1308 0 -3.261 2.94E-05 2
133 305.4 101.3 44.01 -2569 0 -4.976 1.46E-05 2 145 369.8 101.3 52.38 -3491 0 -6.109 1.12E-05 2 170 425.2 101.3 66.94 -4604 0 -8.255 1.16E-05 2 165 408.1 101.3 58.78 -4137 0 -7.017 1.04E-05 2 195 469.6 101.3 63.33 -5118 0 -7.483 7.77E-06 2 220 460.4 101.3 66.76 -5059 0 -8.089 9.25E-06 2 260 433.8 101.3 69.98 -4845 0 -8.701 1.11E-05 2 220 507.5 101.3 70.43 -6056 0 -8.379 6.62E-06 2 230 497.5 101.3 72.46 -5929 0 -8.765 7.62E-06 2 235 504.4 101.3 70.35 -5909 0 -8.419 7.06E-06 2 225 488.8 101.3 56.69 -5087 0 -6.384 5.41E-06 2 235 500 101.3 67.02 -5625 0 -7.959 6.96E-06 2 230 540.2 101.3 78.33 -6947 0 -9.449 6.48E-06 2 230 530.4 101.3 75.79 -6688 0 -9.1 6.44E-06 2 235 535.3 101.3 74.79 -6650 0 -8.95 6.30E-06 2 225 520.5 101.3 70.43 -6198 0 -8.363 6.29E-06 2 230 537.3 101.3 70.99 -6430 0 -8.391 5.88E-06 2 225 519.8 101.3 71.35 -6255 0 -8.497 6.39E-06 2 225 536.4 101.3 77.56 -6450 0 -9.517 7.89E-06 2 265 540.6 101.3 78.75 -6816 0 -9.568 6.93E-06 2 250 531.2 101.3 69.23 -6100 0 -8.213 6.30E-06 2 213 552 101.3 169.7 -1.03E+04 0 -23.59 2.09E-05 2
178.2 591.8 101.3 76.45 -6995 0 -9.164 6.23E-06 2 288 511.6 101.3 51.84 -4915 0 -5.623 4.80E-06 2 288 532.7 101.3 71.34 -6030 0 -8.572 7.17E-06 2 293 553.2 101.3 70.98 -6187 0 -8.465 6.45E-06 2
376.6 569.5 101.3 98.91 -7885 0 -12.58 8.90E-06 2 298 572.1 101.3 72.24 -6555 0 -8.597 5.97E-06 2 275 647.3 101.3 65.93 -7228 0 -7.177 4.03E-06 2 250 556.4 101.3 74.22 -6240 0 -8.987 7.19E-06 2
APPENDIX B
Antoine Equation ln(P) = a + b/(T + c) + d*ln(T) + e*T^f
Tmin Tmax Default Q a b c d e f
Hydrogen Methane Ethane
Propane n-Butane i-Butane
n-Pentane i-Pentane
22-Mpropane n-Hexane
2-Mpentane 3-Mpentane 22-Mbutane 23-Mbutane n-Heptane 2-Mhexane 3-Mhexane
22-Mpentane 23-Mpentane 24-Mpentane 33-Mpentane 3-Epentane
223-Mbutane Benzene Toluene
Cyclopentane Mcyclopentan Cyclohexane Cyclopentane
Mcyclohexane H2O CCl4
158
0 0 0 0 0 -7.72E+04 87.74 8.60E-03 0 0 -8.58E+04 168.6 2.69E-02 0 0 -1.06E+05 264.8 3.25E-02 0 0 -1.28E+05 360.5 3.83E-02 0 0 -1.37E+05 376.4 3.75E-02 0 0 -1.49E+05 457.5 4.44E-02 0 0 -1.57E+05 464 4.34E-02 0 0 -1.69E+05 502.8 3.96E-02 0 0 -1.71E+05 554.2 5.03E-02 0 0 -1.78E+05 563 4.83E-02 0 0 -1.75E+05 562.7 5.04E-02 0 0 -1.89E+05 586.5 4.76E-02 0 0 -1.81E+05 577.8 4.97E-02 0 0 -1.92E+05 650.5 5.64E-02 0 0 -1.99E+05 658.4 5.65E-02 0 0 -1.96E+05 654.3 5.65E-02 0 0 -2.10E+05 685.6 5.64E-02 0 0 -2.03E+05 664.6 5.63E-02 0 0 -2.06E+05 681.9 5.63E-02 0 0 -2.05E+05 678.9 5.63E-02 0 0 -1.93E+05 666.9 5.65E-02 0 0 -2.09E+05 698.1 5.26E-02 0 0 8.15E+04 152.8 2.65E-02 0 0 4.78E+04 238.3 3.19E-02 0 0
-8.05E+04 384.5 4.52E-02 0 0 -1.10E+05 474 4.91E-02 0 0 -1.28E+05 520.3 4.47E-02 0 0 -1.31E+05 571.4 5.48E-02 0 0 -1.60E+05 612.5 4.63E-02 0 0 -2.41E+05 43.41 4.96E-03 0 0 -1.01E+05 145.6 -8.68E-03 0 0
Gibbs Free Energy G = a + b*T + c*T^2 + d*T^3 + e*T^4
a b c d e
Hydrogen Methane Ethane
Propane n-Butane i-Butane
n-Pentane i-Pentane
22-Mpropane n-Hexane
2-Mpentane 3-Mpentane 22-Mbutane 23-Mbutane n-Heptane 2-Mhexane 3-Mhexane
22-Mpentane 23-Mpentane 24-Mpentane 33-Mpentane 3-Epentane
223-Mbutane Benzene Toluene
Cyclopentane Cyclopentane Cyclohexane Ecyclopentane
Mcyclohexane H2O CCl4
159
-49.68 13.84 3.00E-04 3.46E-07 -9.71E-11
-12.98 2.365 -2.13E-03 5.66E-06 -3.73E-09
-1.768 1.143 -3.24E-04 4.24E-06 -3.39E-09
39.49 0.395 2.11E-03 3.97E-07 -6.67E-10
67.72 8.54E-03 3.28E-03 -1.11E-06 1.77E-10
30.9 0.1533 2.64E-03 7.27E-08 -7.28E-10
63.2 -1.17E-02 3.32E-03 -1.17E-06 2.00E-10
64.25 -0.1318 3.54E-03 -1.33E-06 2.51E-10
0 -2.20E-02 3.29E-03 -8.71E-07 -9.07E-11
74.51 -9.67E-02 3.48E-03 -1.32E-06 2.52E-10
111.5 -0.6057 4.92E-03 -3.02E-06 1.07E-09
83.82 -0.1695 3.68E-03 -1.56E-06 3.54E-10
0 -0.193 3.65E-03 -2.42E-06 6.44E-10
0 -0.1695 3.57E-03 -2.35E-06 6.41E-10
71.41 -9.69E-02 3.47E-03 -1.33E-06 2.56E-10
47.74 -0.125 3.60E-03 -1.28E-06 9.86E-11
1.96E-08 -5.61E-02 3.38E-03 -1.21E-06 1.85E-10
77.69 0.2155 2.82E-03 -6.68E-07 0
80.01 0.158 2.83E-03 -6.76E-07 0
75.92 0.2227 2.82E-03 -6.68E-07 0
82.69 0.1556 2.83E-03 -6.75E-07 0
78.61 0.1546 2.83E-03 -6.77E-07 0
86.02 0.1548 2.83E-03 -6.74E-07 0
84.47 -0.5133 3.25E-03 -1.54E-06 3.65E-10
74.16 -0.4231 3.18E-03 -1.44E-06 3.27E-10
1.56E-08 -0.7645 3.87E-03 -1.44E-06 2.31E-10
127.2 -0.6841 4.01E-03 -1.68E-06 3.58E-10
4.56E-09 -0.6481 3.63E-03 -9.99E-07 3.92E-11
64.92 -0.677 4.22E-03 -2.12E-06 7.00E-10
107.6 -0.7046 4.10E-03 -1.53E-06 1.83E-10
-5.73 1.915 -3.96E-04 8.76E-07 -4.95E-10
0 0.2649 6.67E-04 -4.92E-07 1.44E-10
Enthalpy H = a + b*T + c*T^2 + d*T^3 + e*T^4
a b c d e
Hydrogen
Methane
Ethane
Propane
n-Butane
i-Butane
n-Pentane
i-Pentane
22-Mpropane
n-Hexane
2-Mpentane
3-Mpentane
22-Mbutane
23-Mbutane
n-Heptane
2-Mhexane
3-Mhexane
22-Mpentane
23-Mpentane
24-Mpentane
33-Mpentane
3-Epentane
223-Mbutane
Benzene
Toluene
Cyclopentane
Mcyclopentane Cyclohexane
Ecyclopentane
Mcyclohexane
H2O
160
27.143 9.27E-03 -1.38E-05 7.65E-09
19.251 5.21E-02 1.20E-05 -1.13E-08
5.409 1.78E-01 -6.94E-05 8.71E-09
-4.224 3.06E-01 -1.59E-04 3.21E-08
9.487 3.31E-01 -1.11E-04 -2.82E-09
-3.626 4.87E-01 -2.58E-04 5.30E-08
-4.413 5.82E-01 -3.119E-04 6.49E-08
-5.146 6.76E-01 -3.65E-04 7.66E-08
-1.39 3.85E-01 -1.85E-04 2.90E-08
-9.525 5.07E-01 -2.73E-04 5.72E-08
-10.57 6.18E-01 -3.57E-04 8.08E-08
-2.386 5.69E-01 -2.87E-04 5.03E-08
-16.634 6.29E-01 -3.48E-04 6.85E-08
-14.608 6.15E-01 -3.38E-04 6.82E-08
-39.389 8.64E-01 -6.29E-04 1.84E-07
-7.046 6.84E-01 -3.73E-04 7.83E-08
-50.099 8.96E-01 -6.36E-04 1.74E-07
-7.046 7.05E-02 -3.73E-04 7.83E-08
-7.046 6.84E-01 -3.73E-04 7.83E-08
-7.046 6.84E-01 -3.73E-04 7.83E-08
-7.046 6.84E-01 -3.73E-04 7.83E-08
-33.917 4.74E-01 -3.02E-04 7.13E-08
-24.355 5.12E-01 -2.77E-04 4.91E-08
-53.625 5.43E-01 -3.03E-04 6.49E-08
-50.108 6.38E-01 -3.64E-04 8.01E-08
-54.541 6.11E-01 -2.52E-04 1.32E-08
-61.919 7.84E-01 -4.44E-04 9.37E-08
-55.312 7.51E-01 -4.40E-04 1.00E-07
-22.944 7.52E-01 -4.42E-04 1.00E-07
Heat Capacity (Gas) CpG
CpG = a + b*T + c*T^2 + d*T^3
a b c d
Hydrogen
Methane
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
i-Butane
i-Pentane
2-Mpentane
3-Mpentane
22-Mbutane
23-Mbutane
2-Mhexane
3-Mhexane
22-Mpentane
23-Mpentane
24-Mpentane
33-Mpentane
3-Epentane
Benzene
Toluene
Cyclopentane
Mcyclopentane
Cyclohexane
Ecyclopentane
Mcyclohexane
223-Mbutane
161
15.84 -0.8189 4.87E-02 0 0
370.4 -11.3 0.1483 -8.55E-04 1.86E-06
143.4 -2.118 2.15E-02 -9.35E-05 1.52E-07
124.03 -1.0717 1.01E-02 -3.84E-05 5.57E-08
319.19 -3.5845 2.26E-02 -6.07E-05 6.28E-08
164.2199 -0.3209 1.11E-03
198.2 -0.3866 1.26E-03
218.5 -0.2968 1.06E-03
172.37 -1.7839 1.48E-02 -4.79E-05 5.81E-08
108.3 0.146 -2.92E-04 1.51E-06
142.22 -4.78E-02 7.39E-04
140.49 -3.48E-02 6.81E-04
125.45 3.54E-02 5.96E-04
129.45 1.85E-02 6.08E-04
174.01 -0.10578 9.05E-04
157.94 -4.40E-03 7.10E-04
133.57 0.1093999 6.19E-04
146.42 5.92E-02 6.04E-04
133.5 0.1278 5.92E-04
156.03 -5.28E-02 8.34E-04
148.02 6.39E-02 5.91E-04 -2.72E-17 3.61E-20
129.44 -0.1695 6.48E-04
140.1399 -0.1523 6.95E-04 3.98E-20 -3.47E-23
122.53 -0.4038 1.73E-03 -1.10E-06
155.92 -0.4899999 2.14E-03 -1.56E-06
-220.6 3.1183 -9.42E-03 1.07E-05 9.34E-22
178.52 -0.51835 2.33E-03 -1.68E-06 1.17E-22
131.34 -6.31E-02 8.13E-04
88.446 0.40272 5.62E-05
276.37 -2.0901 8.13E-03 -1.41E-05 9.37E-09
Heat Capacity (Liquid) CpL
CpL = a + b*T + c*T^2 + d*T^3 +e*T^4
a b c d e
Hydrogen
Methane
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
i-Butane
i-Pentane
2-Mpentane
3-Mpentane
22-Mbutane
23-Mbutane
2-Mhexane
3-Mhexane
22-Mpentane
23-Mpentane
24-Mpentane
33-Mpentane
3-Epentane
Benzene
Toluene
Cyclopentane
Mcyclopentane
Cyclohexane
Ecyclopentane
Mcyclohexane
223-Mbutane
H2O
162
Tem
era
ture
C
Tem
era
ture
Ka
bc
G n
C4
a b
cG
iC4
∆G
ln K
KX
X %
100
373
-1.2
8E+0
53.
60E+
023.
83E-
021.
14E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
8.82
E+03
-2.5
9E+0
30.
8351
442.
3051
450.
6974
4169
.744
14
110
383
-1.2
8E+0
53.
60E+
023.
83E-
021.
53E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
1.29
E+04
-2.4
4E+0
30.
7650
842.
1491
760.
6824
5768
.245
66
120
393
-1.2
8E+0
53.
60E+
023.
83E-
021.
92E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
1.69
E+04
-2.2
8E+0
30.
6986
372.
0110
10.
6678
8666
.788
55
130
403
-1.2
8E+0
53.
60E+
023.
83E-
022.
31E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
2.10
E+04
-2.1
3E+0
30.
6355
331.
8880
270.
6537
4365
.374
29
140
413
-1.2
8E+0
53.
60E+
023.
83E-
022.
70E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
2.51
E+04
-1.9
8E+0
30.
5755
281.
7780
70.
6400
3864
.003
78
150
423
-1.2
8E+0
53.
60E+
023.
83E-
023.
10E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
2.91
E+04
-1.8
2E+0
30.
5184
041.
6793
460.
6267
7562
.677
45
160
433
-1.2
8E+0
53.
60E+
023.
83E-
023.
49E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
3.32
E+04
-1.6
7E+0
30.
4639
611.
5903
610.
6139
5361
.395
34
170
443
-1.2
8E+0
53.
60E+
023.
83E-
023.
88E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
3.73
E+04
-1.5
2E+0
30.
4120
171.
5098
60.
6015
7160
.157
13
180
453
-1.2
8E+0
53.
60E+
023.
83E-
024.
28E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
4.14
E+04
-1.3
6E+0
30.
3624
061.
4367
820.
5896
2358
.962
28
190
463
-1.2
8E+0
53.
60E+
023.
83E-
024.
67E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
4.55
E+04
-1.2
1E+0
30.
3149
781.
3702
290.
5781
57.8
0999
200
473
-1.2
8E+0
53.
60E+
023.
83E-
025.
07E+
04-1
.37E
+05
3.76
E+02
3.75
E-02
4.96
E+04
-1.0
6E+0
30.
2695
941.
3094
330.
5669
9356
.699
32
iC4/
nC
4
APPENDIX C
163
iC5/nC5
Temperature C
Temperature
K
a
b
c
G nC5
a
b
c
G iC5
∆G
ln K
K
X
X %
100 373 -1.49E+05 4.57E+02 4.44E-02 2.77E+04 -1.57E+05 4.64E+02 4.34E-02 2.17E+04 -6.01E+03 1.938594 6.948976 0.874198 87.41976 110 383 -1.49E+05 4.57E+02 4.44E-02 3.26E+04 -1.57E+05 4.64E+02 4.34E-02 2.66E+04 -5.95E+03 1.869926 6.487819 0.86645 86.64498 120 393 -1.49E+05 4.57E+02 4.44E-02 3.75E+04 -1.57E+05 4.64E+02 4.34E-02 3.16E+04 -5.90E+03 1.804815 6.078845 0.858734 85.8734 130 403 -1.49E+05 4.57E+02 4.44E-02 4.24E+04 -1.57E+05 4.64E+02 4.34E-02 3.66E+04 -5.84E+03 1.742994 5.714428 0.851067 85.1067 140 413 -1.49E+05 4.57E+02 4.44E-02 4.74E+04 -1.57E+05 4.64E+02 4.34E-02 4.16E+04 -5.78E+03 1.684226 5.38828 0.843463 84.34633 150 423 -1.49E+05 4.57E+02 4.44E-02 5.23E+04 -1.57E+05 4.64E+02 4.34E-02 4.66E+04 -5.73E+03 1.628294 5.095175 0.835936 83.59358 160 433 -1.49E+05 4.57E+02 4.44E-02 5.73E+04 -1.57E+05 4.64E+02 4.34E-02 5.16E+04 -5.67E+03 1.575001 4.830747 0.828495 82.84954 170 443 -1.49E+05 4.57E+02 4.44E-02 6.22E+04 -1.57E+05 4.64E+02 4.34E-02 5.66E+04 -5.61E+03 1.524169 4.591326 0.821152 82.11515 180 453 -1.49E+05 4.57E+02 4.44E-02 6.72E+04 -1.57E+05 4.64E+02 4.34E-02 6.17E+04 -5.56E+03 1.475634 4.373809 0.813912 81.39123 190 463 -1.49E+05 4.57E+02 4.44E-02 7.22E+04 -1.57E+05 4.64E+02 4.34E-02 6.67E+04 -5.50E+03 1.429249 4.17556 0.806784 80.67842 200 473 -1.49E+05 4.57E+02 4.44E-02 7.72E+04 -1.57E+05 4.64E+02 4.34E-02 7.17E+04 -5.45E+03 1.384875 3.994328 0.799773 79.97728
164
2MP/nC6 Temperature
C
Temperature K
a
b
c
G nC6
a
b
c
G 2MP
∆G
ln K
K
X
X %
100 373 -1.70E+05 5.54E+02 5.30E-02 4.36E+04 -1.78E+05 5.63E+02 4.83E-02 3.91E+04 -4.57E+03 1.473963 4.366507 0.813659 81.36591 110 383 -1.70E+05 5.54E+02 5.30E-02 4.96E+04 -1.78E+05 5.63E+02 4.83E-02 4.51E+04 -4.52E+03 1.418852 4.132373 0.805158 80.51583 120 393 -1.70E+05 5.54E+02 5.30E-02 5.55E+04 -1.78E+05 5.63E+02 4.83E-02 5.11E+04 -4.47E+03 1.366833 3.922909 0.796868 79.68681 130 403 -1.70E+05 5.54E+02 5.30E-02 6.15E+04 -1.78E+05 5.63E+02 4.83E-02 5.71E+04 -4.42E+03 1.317678 3.73474 0.788795 78.87952 140 413 -1.70E+05 5.54E+02 5.30E-02 6.75E+04 -1.78E+05 5.63E+02 4.83E-02 6.31E+04 -4.37E+03 1.271178 3.565051 0.780944 78.09444 150 423 -1.70E+05 5.54E+02 5.30E-02 7.35E+04 -1.78E+05 5.63E+02 4.83E-02 6.91E+04 -4.32E+03 1.227145 3.411476 0.773319 77.33185 160 433 -1.70E+05 5.54E+02 5.30E-02 7.94E+04 -1.78E+05 5.63E+02 4.83E-02 7.52E+04 -4.27E+03 1.185408 3.272021 0.765919 76.59188 170 443 -1.70E+05 5.54E+02 5.30E-02 8.55E+04 -1.78E+05 5.63E+02 4.83E-02 8.12E+04 -4.22E+03 1.145811 3.144991 0.758745 75.8745 180 453 -1.70E+05 5.54E+02 5.30E-02 9.15E+04 -1.78E+05 5.63E+02 4.83E-02 8.73E+04 -4.17E+03 1.108213 3.028941 0.751796 75.17958 190 463 -1.70E+05 5.54E+02 5.30E-02 9.75E+04 -1.78E+05 5.63E+02 4.83E-02 9.34E+04 -4.13E+03 1.072484 2.922631 0.745069 74.5069 200 473 -1.70E+05 5.54E+02 5.30E-02 1.04E+05 -1.78E+05 5.63E+02 4.83E-02 9.95E+04 -4.08E+03 1.038506 2.824993 0.738562 73.85616
3MP/nC6 Temperature
C
Temperature K
a
b
c
G nC6
a
b
c
G 3MP
∆G
ln K
K
X
X %
100 373 -1.70E+05 5.54E+02 5.30E-02 4.36E+04 -1.75E+05 5.63E+02 4.83E-02 4.18E+04 -1.87E+03 0.603146 1.827861 0.646376 64.63758 110 383 -1.70E+05 5.54E+02 5.30E-02 4.96E+04 -1.75E+05 5.63E+02 4.83E-02 4.78E+04 -1.82E+03 0.571776 1.771411 0.639173 63.91729 120 393 -1.70E+05 5.54E+02 5.30E-02 5.55E+04 -1.75E+05 5.63E+02 4.83E-02 5.38E+04 -1.77E+03 0.542291 1.719943 0.632345 63.23453 130 403 -1.70E+05 5.54E+02 5.30E-02 6.15E+04 -1.75E+05 5.63E+02 4.83E-02 5.98E+04 -1.72E+03 0.514551 1.672888 0.625873 62.58728 140 413 -1.70E+05 5.54E+02 5.30E-02 6.75E+04 -1.75E+05 5.63E+02 4.83E-02 6.58E+04 -1.68E+03 0.488429 1.629755 0.619736 61.97364 150 423 -1.70E+05 5.54E+02 5.30E-02 7.35E+04 -1.75E+05 5.63E+02 4.83E-02 7.18E+04 -1.63E+03 0.463811 1.590122 0.613918 61.39178 160 433 -1.70E+05 5.54E+02 5.30E-02 7.94E+04 -1.75E+05 5.63E+02 4.83E-02 7.79E+04 -1.59E+03 0.440591 1.553626 0.6084 60.84 170 443 -1.70E+05 5.54E+02 5.30E-02 8.55E+04 -1.75E+05 5.63E+02 4.83E-02 8.39E+04 -1.54E+03 0.418676 1.519949 0.603167 60.31665 180 453 -1.70E+05 5.54E+02 5.30E-02 9.15E+04 -1.75E+05 5.63E+02 4.83E-02 9.00E+04 -1.50E+03 0.39798 1.488814 0.598202 59.82021 190 463 -1.70E+05 5.54E+02 5.30E-02 9.75E+04 -1.75E+05 5.63E+02 4.83E-02 9.60E+04 -1.46E+03 0.378422 1.459979 0.593492 59.34924 200 473 -1.70E+05 5.54E+02 5.30E-02 1.04E+05 -1.75E+05 5.63E+02 4.83E-02 1.02E+05 -1.42E+03 0.359931 1.43323 0.589024 58.90237
165
22DMB/nC6 Temperature
C
Temperature K
a
b
c
G nC6
a
b
c
G 22DMB
∆G
ln K
K
X
X %
100 373 -1.70E+05 5.54E+02 5.30E-02 4.36E+04 -1.89E+05 5.86E+02 4.76E-02 3.62E+04 -7.47E+03 2.407693 11.10831 0.917412 91.74121 110 383 -1.70E+05 5.54E+02 5.30E-02 4.96E+04 -1.89E+05 5.86E+02 4.76E-02 4.24E+04 -7.18E+03 2.256172 9.546472 0.905182 90.51816 120 393 -1.70E+05 5.54E+02 5.30E-02 5.55E+04 -1.89E+05 5.86E+02 4.76E-02 4.86E+04 -6.90E+03 2.112692 8.270474 0.892131 89.21307 130 403 -1.70E+05 5.54E+02 5.30E-02 6.15E+04 -1.89E+05 5.86E+02 4.76E-02 5.49E+04 -6.62E+03 1.976655 7.218559 0.878324 87.83242 140 413 -1.70E+05 5.54E+02 5.30E-02 6.75E+04 -1.89E+05 5.86E+02 4.76E-02 6.11E+04 -6.34E+03 1.847522 6.344076 0.863836 86.38358 150 423 -1.70E+05 5.54E+02 5.30E-02 7.35E+04 -1.89E+05 5.86E+02 4.76E-02 6.74E+04 -6.07E+03 1.724801 5.611403 0.848746 84.87462 160 433 -1.70E+05 5.54E+02 5.30E-02 7.94E+04 -1.89E+05 5.86E+02 4.76E-02 7.37E+04 -5.79E+03 1.608049 4.993059 0.83314 83.31403 170 443 -1.70E+05 5.54E+02 5.30E-02 8.55E+04 -1.89E+05 5.86E+02 4.76E-02 7.99E+04 -5.51E+03 1.496861 4.467645 0.817106 81.71059 180 453 -1.70E+05 5.54E+02 5.30E-02 9.15E+04 -1.89E+05 5.86E+02 4.76E-02 8.62E+04 -5.24E+03 1.39087 4.018345 0.800731 80.07311 190 463 -1.70E+05 5.54E+02 5.30E-02 9.75E+04 -1.89E+05 5.86E+02 4.76E-02 9.25E+04 -4.96E+03 1.289738 3.631835 0.784103 78.41028 200 473 -1.70E+05 5.54E+02 5.30E-02 1.04E+05 -1.89E+05 5.86E+02 4.76E-02 9.88E+04 -4.69E+03 1.193157 3.297476 0.767305 76.73053
23DMB/nC6 Temperature
C
Temperature K
a
b
c
G nC6
a
b
c
G 23DMB
∆G
ln K
K
X
X %
100 373 -1.70E+05 5.54E+02 5.30E-02 4.36E+04 -1.81E+05 5.78E+02 4.97E-02 4.11E+04 -2.48E+03 0.801183 2.228175 0.690227 69.02275 110 383 -1.70E+05 5.54E+02 5.30E-02 4.96E+04 -1.81E+05 5.78E+02 4.97E-02 4.73E+04 -2.27E+03 0.713815 2.041766 0.671244 67.12436 120 393 -1.70E+05 5.54E+02 5.30E-02 5.55E+04 -1.81E+05 5.78E+02 4.97E-02 5.35E+04 -2.06E+03 0.631096 1.87967 0.652738 65.2738 130 403 -1.70E+05 5.54E+02 5.30E-02 6.15E+04 -1.81E+05 5.78E+02 4.97E-02 5.96E+04 -1.85E+03 0.55268 1.737904 0.634757 63.47571 140 413 -1.70E+05 5.54E+02 5.30E-02 6.75E+04 -1.81E+05 5.78E+02 4.97E-02 6.58E+04 -1.64E+03 0.478253 1.613254 0.617335 61.73354 150 423 -1.70E+05 5.54E+02 5.30E-02 7.35E+04 -1.81E+05 5.78E+02 4.97E-02 7.20E+04 -1.43E+03 0.407534 1.503107 0.600496 60.04965 160 433 -1.70E+05 5.54E+02 5.30E-02 7.94E+04 -1.81E+05 5.78E+02 4.97E-02 7.82E+04 -1.23E+03 0.340265 1.40532 0.584255 58.42549 170 443 -1.70E+05 5.54E+02 5.30E-02 8.55E+04 -1.81E+05 5.78E+02 4.97E-02 8.44E+04 -1.02E+03 0.276213 1.318128 0.568617 56.86175 180 453 -1.70E+05 5.54E+02 5.30E-02 9.15E+04 -1.81E+05 5.78E+02 4.97E-02 9.07E+04 -8.10E+02 0.215164 1.240065 0.553584 55.35844 190 463 -1.70E+05 5.54E+02 5.30E-02 9.75E+04 -1.81E+05 5.78E+02 4.97E-02 9.69E+04 -6.04E+02 0.156924 1.169907 0.539151 53.91507 200 473 -1.70E+05 5.54E+02 5.30E-02 1.04E+05 -1.81E+05 5.78E+02 4.97E-02 1.03E+05 -3.98E+02 0.101315 1.106625 0.525307 52.53071
166
2MH/nC7
Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 2MH
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -1.99E+05 6.58E+02 5.65E-02 5.48E+04 -4.19E+03 1.350422 3.859053 0.794199 79.41986 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -1.99E+05 6.58E+02 5.65E-02 6.18E+04 -4.11E+03 1.290441 3.634389 0.784222 78.42218 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -1.99E+05 6.58E+02 5.65E-02 6.88E+04 -4.03E+03 1.233511 3.433263 0.774433 77.44325 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -1.99E+05 6.58E+02 5.65E-02 7.59E+04 -3.95E+03 1.179405 3.252437 0.764841 76.48407 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -1.99E+05 6.58E+02 5.65E-02 8.29E+04 -3.87E+03 1.127916 3.089213 0.755454 75.54542 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -1.99E+05 6.58E+02 5.65E-02 9.00E+04 -3.79E+03 1.078861 2.941327 0.746278 74.62783 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -1.99E+05 6.58E+02 5.65E-02 9.70E+04 -3.72E+03 1.032069 2.806869 0.737317 73.73169 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -1.99E+05 6.58E+02 5.65E-02 1.04E+05 -3.64E+03 0.987389 2.684216 0.728572 72.85719 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -1.99E+05 6.58E+02 5.65E-02 1.11E+05 -3.56E+03 0.944679 2.571988 0.720044 72.00439 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -1.99E+05 6.58E+02 5.65E-02 1.18E+05 -3.48E+03 0.903813 2.469 0.711732 71.17325 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -1.99E+05 6.58E+02 5.65E-02 1.25E+05 -3.40E+03 0.864673 2.37423 0.703636 70.36361
3MH/nC7 Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 3MH
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -1.96E+05 6.54E+02 5.65E-02 5.59E+04 -3.08E+03 0.993105 2.699603 0.729701 72.97007 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -1.96E+05 6.54E+02 5.65E-02 6.29E+04 -3.04E+03 0.955376 2.599647 0.722195 72.2195 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -1.96E+05 6.54E+02 5.65E-02 6.98E+04 -3.00E+03 0.919566 2.508202 0.714954 71.49537 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -1.96E+05 6.54E+02 5.65E-02 7.68E+04 -2.97E+03 0.885533 2.424276 0.707967 70.79675 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -1.96E+05 6.54E+02 5.65E-02 8.38E+04 -2.93E+03 0.853148 2.347023 0.701227 70.1227 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -1.96E+05 6.54E+02 5.65E-02 9.09E+04 -2.89E+03 0.822293 2.275712 0.694723 69.47228 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -1.96E+05 6.54E+02 5.65E-02 9.79E+04 -2.85E+03 0.792863 2.209713 0.688446 68.84457 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -1.96E+05 6.54E+02 5.65E-02 1.05E+05 -2.82E+03 0.764761 2.14848 0.682386 68.23864 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -1.96E+05 6.54E+02 5.65E-02 1.12E+05 -2.78E+03 0.737899 2.091536 0.676536 67.65362 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -1.96E+05 6.54E+02 5.65E-02 1.19E+05 -2.74E+03 0.712197 2.038464 0.670886 67.08864 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -1.96E+05 6.54E+02 5.65E-02 1.26E+05 -2.70E+03 0.687581 1.988899 0.665429 66.54286
167
22DMP/nC7 Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 22DMP
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -2.10E+05 6.86E+02 5.64E-02 5.37E+04 -5.29E+03 1.704711 5.499794 0.846149 84.6149 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -2.10E+05 6.86E+02 5.64E-02 6.10E+04 -4.94E+03 1.550164 4.712242 0.824937 82.49374 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -2.10E+05 6.86E+02 5.64E-02 6.83E+04 -4.59E+03 1.403488 4.069368 0.802737 80.27368 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -2.10E+05 6.86E+02 5.64E-02 7.56E+04 -4.24E+03 1.264096 3.539892 0.77973 77.97305 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -2.10E+05 6.86E+02 5.64E-02 8.29E+04 -3.89E+03 1.13146 3.100181 0.756108 75.61083 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -2.10E+05 6.86E+02 5.64E-02 9.02E+04 -3.53E+03 1.005101 2.732183 0.73206 73.20603 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -2.10E+05 6.86E+02 5.64E-02 9.76E+04 -3.18E+03 0.884583 2.421975 0.707771 70.77711 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -2.10E+05 6.86E+02 5.64E-02 1.05E+05 -2.83E+03 0.769511 2.158711 0.683415 68.34152 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -2.10E+05 6.86E+02 5.64E-02 1.12E+05 -2.48E+03 0.659525 1.933873 0.659154 65.91536 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -2.10E+05 6.86E+02 5.64E-02 1.20E+05 -2.13E+03 0.554294 1.740712 0.635131 63.51313 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -2.10E+05 6.86E+02 5.64E-02 1.27E+05 -1.78E+03 0.453517 1.573838 0.611475 61.14752
23DMP/nC7 Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 23DMP
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -2.03E+05 6.65E+02 5.63E-02 5.27E+04 -6.28E+03 2.023518 7.564889 0.883244 88.32443 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -2.03E+05 6.65E+02 5.63E-02 5.98E+04 -6.14E+03 1.926974 6.868691 0.872914 87.29141 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -2.03E+05 6.65E+02 5.63E-02 6.69E+04 -6.00E+03 1.835352 6.267342 0.862398 86.23981 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -2.03E+05 6.65E+02 5.63E-02 7.39E+04 -5.86E+03 1.748287 5.744756 0.851737 85.17367 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -2.03E+05 6.65E+02 5.63E-02 8.11E+04 -5.72E+03 1.665448 5.288042 0.840968 84.0968 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -2.03E+05 6.65E+02 5.63E-02 8.82E+04 -5.58E+03 1.586534 4.886784 0.830128 83.0128 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -2.03E+05 6.65E+02 5.63E-02 9.53E+04 -5.44E+03 1.511274 4.532504 0.81925 81.925 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -2.03E+05 6.65E+02 5.63E-02 1.02E+05 -5.30E+03 1.439421 4.218252 0.808365 80.8365 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -2.03E+05 6.65E+02 5.63E-02 1.10E+05 -5.16E+03 1.370748 3.938296 0.797501 79.7501 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -2.03E+05 6.65E+02 5.63E-02 1.17E+05 -5.02E+03 1.30505 3.687873 0.786684 78.66837 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -2.03E+05 6.65E+02 5.63E-02 1.24E+05 -4.88E+03 1.242138 3.463009 0.775936 77.59359
168
24DMP/nC7 Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 24DMP
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -2.06E+05 6.82E+02 5.63E-02 5.64E+04 -2.54E+03 0.820507 2.271651 0.694344 69.43439 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -2.06E+05 6.82E+02 5.63E-02 6.37E+04 -2.23E+03 0.700839 2.015443 0.668374 66.83738 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -2.06E+05 6.82E+02 5.63E-02 7.09E+04 -1.92E+03 0.587269 1.799068 0.642738 64.27382 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -2.06E+05 6.82E+02 5.63E-02 7.82E+04 -1.61E+03 0.479341 1.615009 0.617592 61.75922 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -2.06E+05 6.82E+02 5.63E-02 8.55E+04 -1.29E+03 0.376646 1.457388 0.593064 59.30639 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -2.06E+05 6.82E+02 5.63E-02 9.28E+04 -9.81E+02 0.278813 1.321561 0.569255 56.92553 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -2.06E+05 6.82E+02 5.63E-02 1.00E+05 -6.68E+02 0.185506 1.203827 0.546244 54.62438 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -2.06E+05 6.82E+02 5.63E-02 1.07E+05 -3.55E+02 0.096416 1.101218 0.524085 52.40855 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -2.06E+05 6.82E+02 5.63E-02 1.15E+05 -4.24E+01 0.011267 1.01133 0.502817 50.28166 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -2.06E+05 6.82E+02 5.63E-02 1.22E+05 2.70E+02 -0.0702 0.932208 0.482457 48.24574 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -2.06E+05 6.82E+02 5.63E-02 1.29E+05 5.83E+02 -0.14821 0.862246 0.463014 46.3014
33DMP/nC7 Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 33DMP
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -2.05E+05 6.79E+02 5.63E-02 5.57E+04 -3.25E+03 1.048635 2.853753 0.740513 74.05127 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -2.05E+05 6.79E+02 5.63E-02 6.29E+04 -2.97E+03 0.932509 2.540876 0.717584 71.7584 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -2.05E+05 6.79E+02 5.63E-02 7.02E+04 -2.69E+03 0.8223 2.275728 0.694724 69.47243 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -2.05E+05 6.79E+02 5.63E-02 7.74E+04 -2.40E+03 0.717567 2.049441 0.672071 67.20711 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -2.05E+05 6.79E+02 5.63E-02 8.47E+04 -2.12E+03 0.617913 1.855053 0.649744 64.97438 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -2.05E+05 6.79E+02 5.63E-02 9.19E+04 -1.84E+03 0.522978 1.687044 0.627844 62.78438 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -2.05E+05 6.79E+02 5.63E-02 9.92E+04 -1.56E+03 0.432434 1.541003 0.606455 60.64546 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -2.05E+05 6.79E+02 5.63E-02 1.06E+05 -1.27E+03 0.345984 1.413379 0.585643 58.56433 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -2.05E+05 6.79E+02 5.63E-02 1.14E+05 -9.92E+02 0.263357 1.301291 0.565461 56.54612 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -2.05E+05 6.79E+02 5.63E-02 1.21E+05 -7.09E+02 0.184305 1.202382 0.545946 54.59462 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -2.05E+05 6.79E+02 5.63E-02 1.28E+05 -4.27E+02 0.108602 1.114718 0.527124 52.71238
169
2EP/nC7 Temperature
e C
Temperature
K
a
b
c
G nC7
a
b
c
G 2EP
∆G
ln K
K
X
X %
100 373 -1.92E+05 6.51E+02 5.64E-02 5.90E+04 -1.93E+05 6.67E+02 5.64E-02 6.32E+04 4.25E+03 -1.37008 0.254086 0.202606 20.26065 110 383 -1.92E+05 6.51E+02 5.64E-02 6.59E+04 -1.93E+05 6.67E+02 5.64E-02 7.03E+04 4.41E+03 -1.38566 0.250157 0.200101 20.01007 120 393 -1.92E+05 6.51E+02 5.64E-02 7.29E+04 -1.93E+05 6.67E+02 5.64E-02 7.74E+04 4.58E+03 -1.40045 0.246485 0.197744 19.7744 130 403 -1.92E+05 6.51E+02 5.64E-02 7.98E+04 -1.93E+05 6.67E+02 5.64E-02 8.45E+04 4.74E+03 -1.41451 0.243045 0.195524 19.55236 140 413 -1.92E+05 6.51E+02 5.64E-02 8.68E+04 -1.93E+05 6.67E+02 5.64E-02 9.17E+04 4.90E+03 -1.42789 0.239815 0.193428 19.34282 150 423 -1.92E+05 6.51E+02 5.64E-02 9.37E+04 -1.93E+05 6.67E+02 5.64E-02 9.88E+04 5.07E+03 -1.44063 0.236779 0.191448 19.14478 160 433 -1.92E+05 6.51E+02 5.64E-02 1.01E+05 -1.93E+05 6.67E+02 5.64E-02 1.06E+05 5.23E+03 -1.45279 0.233918 0.189573 18.95733 170 443 -1.92E+05 6.51E+02 5.64E-02 1.08E+05 -1.93E+05 6.67E+02 5.64E-02 1.13E+05 5.39E+03 -1.46439 0.231219 0.187796 18.77965 180 453 -1.92E+05 6.51E+02 5.64E-02 1.15E+05 -1.93E+05 6.67E+02 5.64E-02 1.20E+05 5.56E+03 -1.47549 0.228667 0.18611 18.61101 190 463 -1.92E+05 6.51E+02 5.64E-02 1.22E+05 -1.93E+05 6.67E+02 5.64E-02 1.27E+05 5.72E+03 -1.4861 0.226253 0.184507 18.45074 200 473 -1.92E+05 6.51E+02 5.64E-02 1.29E+05 -1.93E+05 6.67E+02 5.64E-02 1.35E+05 5.88E+03 -1.49627 0.223964 0.182983 18.29825
170
Figure 3.1 C5 paraffin equilibrium plot
Equilibrium Curve
171
Iso-pentane equilibrium curve
2-2Dimethyl butane Equilibrium curve
172
APPENDIX D
Typical Baffles clearances and Tolerances
Shell Bundle Clearance
173
Tube side heat transfer Factor
174
Tube side friction factor
175
Shell side heat transfer factor, for segmental baffles
176
Shell side friction Factor, for segmental baffles
177
Temperature Correction factor: Two shell passes, four or multiple of four tube passes
Temperature Correction factor: One shell passes, two or even tube passes
178
Typical Overall Coefficients
179
Designing Algorithm for Heat Exchanger
180
Discharge Coefficient sieve plate
181
Pump selection guide
182
Pipe Friction verse Reynolds number and relative roughness
183
184
Compressor operating range