Chapter No.

1
Introduction
1.1

What is crude oil?

Crude oils are complex mixtures containing many different hydrocarbon

compounds that vary in appearance and composition from one oil field to another. Crude oils
range in consistency from water to tar-like solids, and in color from clear to black. An
"average" crude oil contains about 84% carbon, 14% hydrogen, 1-3% sulfur, and less than
1% each of nitrogen, oxygen, metals, and salts. Crude oils are generally classified as
paraffinic, naphthenic or aromatic, based on the predominant proportion of similar
hydrocarbon molecules. Mixed-base crudes have varying amounts of each type of
hydrocarbon. Refinery crude base stocks usually consist of mixtures of two or more different
crude oils. [1]
Relatively simple crude oil assays are used to classify crude oils as paraffinic,
naphthenic, aromatic, or mixed. One assay method (United States Bureau of Mines) is based
on distillation, and another method (UOP "K" factor) is based on gravity and boiling points.
More comprehensive crude assays determine the value of the crude (i.e., its yield and quality
of useful products) and processing parameters. Crude oils are usually grouped according to
yield structure. [2]
Crude oils are also defined in terms of API (American Petroleum Institute) gravity.
The higher the API gravity, the lighter will be the crude. For example, light crude oils have
high API gravity and low specific gravities. Crude oils with low carbon, high hydrogen, and
high API gravity are usually rich in Paraffins and tend to yield greater proportions of gasoline
and light petroleum products; those with high carbon, low hydrogen, and low API gravities
are usually rich in aromatics.
Crude oils that contain appreciable quantities of hydrogen sulfide or other reactive
sulfur compounds are called "sour." Those with less sulfur are called "sweet." Some
exceptions to this rule are West Texas crudes, which are always considered "sour" regardless
of their H2S content, and Arabian high-sulfur crudes, which are not considered "sour"
because their sulfur compounds are not highly reactive.

Chapter 1

Introduction

Most of the world's oils are non-conventional. [3]

Composition by weight
Element

Percent range

Carbon

83 to 85%

Hydrogen

10 to 14%

Nitrogen

0.1 to 2%

Oxygen

0.05 to 1.5%

Sulfur

0.05 to 6.0%

Metals

< 0.1%

Four different types of hydrocarbon molecules appear in crude oil. The relative
percentage of each varies from oil to oil, determining the properties of oil.[3]
Composition by weight
Hydrocarbon

Average

Range

Alkanes (paraffins) 30%

15 to 60%

Naphthenes

49%

30 to 60%

Aromatics

15%

3 to 30%

Asphaltics

6%

remainder

1.2: No two crudes oils are the same:

Crude oil is not a homogeneous raw material. Each crude oil produced in the world
has a unique chemical composition, which varies according to the manner of its formation.
Currently, more than 150 crude grades are traded, and many of these are streams blended
from two or more fields.
Crude oil is a complex mixture of hydrocarbon compounds and small quantities of
materials such as oxygen, nitrogen, sulfur, salt and water. Carbon and hydrogen make up
around 98% of the content of a typical crude oil. The hydrocarbon series molecules dictate
crude oils physical and chemical properties.[1]
The gravity, sulfur contents and total acid number (TAN) are the most important
properties of crude oil.

Chapter 1

1.3

Introduction

Types of crude oil:

Crude oil is of three main classes named according to the nature of the residue left
when the more volatile components are removed by distillation.
1: Paraffin based crudes consist mainly of paraffin hydrocarbons and leave a distillation
residue of paraffin wax. They give good yields of high grade lubricating oils. These crudes
contain little or no asphaltic (naphthenic) matter.
2: Asphaltic based crudes are mainly hydrocarbons of the naphthenic series and contain little
or no paraffin mix. On distillation, they leave a residue of black, lustrous material of complex
character known as bitumen or asphalt. Asphaltic based crudes are dark, very viscous, and
difficult to separate mechanically from dirt and water and generally contain more sulfur than
paraffin based crudes.
3: Mixed based crudes contain substantial proportions of both paraffin wax and asphaltic
matter. Both paraffinic and naphthenic hydrocarbons are present over a wide range of
molecular weights together with some aromatic species. On distillation, a residue of mixed
paraffin wax and bitumen is left. The bulk of the crude oil at present produced is of this
mixed type. [4]

1.4

Composition of crude oil:

Crude oil mainly contains two types of compounds

Hydrocarbons
Non-Hydrocarbons

1.4.1

Hydrocarbons:

Crude oil is a mixture of Hydrocarbon molecules which are organic compounds of

carbon and hydrogen atom. Number of carbon atoms may range from 1 to 60 per molecule.
Properties of hydrocarbons depend on number and arrangement of carbon and hydrogen
atoms in the molecule.
Simplest hydrocarbon molecule is Methane: which has one carbon atom linked with four
hydrogen atoms. Three principal groups of hydrocarbon compounds that occur naturally in
crude oil are as follows: [5]
1.4.1.1 Paraffins:
The paraffinic series of hydrocarbon compounds is crude oil have the general
formula CnH2n+2 and can be either straight chains (Normal) or branched chains(Isomers) of
carbon atoms.
3

Chapter 1

Introduction

The lighter, straight chain paraffin molecules are found in gases, and paraffin
waxes. Examples of straight chain molecules are methane, ethane, propane and butane (gases
containing from 1-4 Carbon atoms), Pentane and Hexane (Liquids with 5-6 Carbon atoms).
The branched chain Paraffins are usually found in heavier fractions of crude oil and have
higher octane numbers than normal Paraffins.
1.4.1.2 Aromatics:
Aromatics are unsaturated ring type (cyclic) compounds which react readily
because they have carbon atoms that are deficient in hydrogen. All aromatics have at least
one benzene ring (a single ring compound characterized by three double bonds alternating
with three single bonds between six carbon atoms) as part of their molecular structure.
Naphthalenes are fused double ring aromatic compounds. The most complex aromatics, polynuclear (three or more fused aromatic rings), are found in heavier fractions of crude oil.
1.4.1.3 Naphthenes:
Naphthenes are saturated hydrocarbons grouping with the general formula CnH2n
arranged in the form of closed rings (cyclic) are found in all fractions of crude oil except the
very lightest. Single ring Naphthenes (mono-cycloparaffins) with 5 and 6 carbon atoms
predominate, with two-ring Naphthenes (Di-cycloparaffins) found in the heavier ends of
Naphtha.

1.4.2

Non-hydrocarbons

Non Hydrocarbons in crude oil may include all or the combinations of the following
types of substance; [5]
1.4.2.1 Sulfur compounds:
Sulfur may be present in crude oil as hydrogen sulfide (H2S), as compounds (e.g.,
mercaptans, sulfides, disulfides, thiophenes, etc.), or as elemental sulfur. Each crude oil has
different amounts and types of sulfur compounds but as a rule the proportion, stability and
complexity of the compounds are greater in heavier crude-oil fractions. Hydrogen sulfide is a
primary contributor to corrosion in refinery processing units. Other corrosive substances are
elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have an
obnoxious odor.
1.4.2.1.1 Impacts:
Pyrophoric iron sulfide results from the corrosive action and sulfur compounds on
the iron and steel used in refinery process equipments, piping and tanks.
The combustion of petroleum products containing sulfur compounds produces undesirables
such as sulfuric acid and sulfur dioxide.
4

Chapter 1

Introduction

1.4.2.1.2 Treatment:
Catalytic hydro treating processes such as hydrodesulphurization remove sulfur
compounds from refinery products streams. Sweetening processes either remove the
obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of
mercaptans.
1.4.2.2 Oxygen Compounds
Oxygen compounds such as phenols, ketones and carboxylic acids occur in crude
oils in varying amounts.
1.4.2.3 Nitrogen Compounds
Nitrogen is found in lighter fractions of crude oil as basic compounds, and more
often in heavier fractions of crude oil as monobasic compounds that may also include trace
metals such as copper, vanadium and/or nickel. Nitrogen oxides can form in process furnaces.
The decomposition of nitrogen compounds in catalytic cracking and hydro cracking
processes forms ammonia and cyanides that can cause corrosion.

1.4.2.4 Trace Metals

Metals including nickel, iron and vanadium are often found in crude oils in small
quantities and are removed during the refining process.
1.4.2.4.1 Impacts:
Burning heavy fuel oils in refining furnaces and boilers can leave deposits of
vanadium oxide and nickel oxide in furnace boxes, ducts and tubes. It is also desirable to
remove trace amounts of arsenic, vanadium and nickel prior to processing as they can poison
certain catalysts.

1.4.2.5 Salts
Crude oils often contain inorganic salts such as sodium chloride, magnesium
chloride and calcium chloride, in suspension or dissolved in entrained water (brine). These
salts must be removed or neutralized before processing to prevent catalyst poisoning,
equipment corrosion and fouling.
1.4.2.5.1 Impact:
Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen
chloride (HCl) and the subsequent formation of hydrochloric acid when crude is heated.
Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH4OH),
which causes fouling and corrosion.
5

Chapter 1
1.4.2.6

Introduction

Carbon Dioxide

Carbon dioxide may result from the decomposition of bicarbonates present in or

added to crude or from steam used in the distillation process.
1.4.2.7

Naphthenic Acids

Some crude oils contain naphthenic (organic) acids, which may become corrosive at
temperatures above 450 F when the acid value of the crude is above a certain level.

1.5

Crude oil refining: A historic overview

The first refineries used horizontal, elevated tanks to heat the crude oil and vaporize volatile
components. The hot vapor would rise, cool and condense in a batch operation. The process
was repeated at different temperatures to separate the various fractions. The technology was
simple, refineries was easy to set up and before long, refining capacity exceeded crude
supply. The need for improved product separation led to the use of fractionating column,
which allowed the different boiling point cuts to be separated out in a continuous process.
John D. Rockefeller sought to consolidate the US refining business and in 1870 he
established the Standard Oil Co. with his partners. By 1879, Standard Oil control 90 % of the
US refining capacity. Developments continued, but the first widely recognized continuous
distillation plants were those of M. J. Trumble (1912). [6]
The number of automobiles and the demand for gasoline greatly increased following the
advent of mass production. Distillation processes, however, could only produce a certain
amount of gasoline depending upon the composition of the crude oil and so scientist and
engineers searched for new ways to increase the yield and performance of gasoline. Thermal
cracking processes were first discovered in 1913, when heat and pressure was used to break
down, rearrange and combine hydrogen molecules.
The introduction of catalytic cracking and polymerization processes in the mid to late
1930s met the demand for higher octane gasoline. Eugene Haudry developed the first
commercial process of cracking in the presence of clay mineral catalysts which resulted in the
large hydrocarbon molecule break apart ; the product were converted to branched Paraffins,
Naphthenes and aromatics with desirable properties. Visbreaking, another form of thermal
cracking, was developed in the late 1930s to produce a more desirable and valuable product
slate. In the 1940s alkylation processes were developed to create high quality aviation fuels
for the war effects, which later were used extensively to produce gasoline blending stocks.

Chapter 1

1.6

Introduction

Refinery products

Finished refinery product may be grouped as: [7]

1.6.1

Volatile products
Liquefied gases and natural gasoline

1.6.2

Light oils
Gasoline, rocket and jet fuels, solvents, tractor fuels and kerosene

1.6.3

Distillates
Range oil, furnace distillates, diesel fuel and gas oil.

1.6.4

Lubricating oil
Motor, engine, machines, cylinder, spindle, gear, etc, oils

1.6.5

Greases and waxes

Paraffin wax, microcrystalline wax, petrolatum, salve bases and greases.

1.6.6

Residues
Fuel oil, coke, asphalt carbon black etc

1.6.7

Specialties
Medicinal products, hydrocarbons, chemicals, insecticides, etc

1.7

Gas Oil

Any oily liquid obtained in the fractional distillation of petroleum, boiling between
the kerosene lubricating oil fractions: used esp. as a diesel fuel and heating oil. Gas oil is a
heavier product than kerosene. It may be produced from atmospheric distillation units.
Atmospheric gas oil (AGO), with a boiling range of approximately190-225oC or from
vacuum distillation (VGO) having boiling point range of 299-500oC. Atmospheric gas oil has
relatively lower density and lower S content than VGO produced from same origin. The
aromatic content of gas oil ranges from about 48% for VGO. It is general rule that VGO
contain about three times as much as S as AGO.
Gas oils are used as heating oils, fuels for metallurgical other manufacturing purposes.
Gas oils containing crack products are unstable and produced more smoke and more deposit
than AGO.

Chapter 1

Introduction

Specific gravity of gas oil is usually falls within wide range of approximately 0.810.89. Substantial amounts of gas oils are used as feeds to catalytic cracking units and to steam
cracking for olefin production. Gas oils are used for ethylene production normally require a
pretreatment step to remove the sulpher compounds.
Desulphurization of heavier oil such as AGO or VGO and deasphalted oil, is widely
used in order to meet the environmental residue.

1.8

Hydrodesulphurization

Hydrodesulphurization (HDS) is a catalytic chemical process widely used to remove

sulfur (S) from natural gas and from refined petroleum products such as gasoline or petrol, jet
fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur is to reduce the
sulfur dioxide (SO2) emissions that result from using those fuels in automotive vehicles,
aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial
furnaces, and other forms of fuel combustion.
Another important reason for removing sulfur from the naphtha streams within a
petroleum refinery is that sulfur, even in extremely low concentrations, poisons the noble
metal catalysts (platinum and rhenium) in the catalytic reforming units that are subsequently
used to upgrade the octane rating of the naphtha streams.
The industrial hydrodesulphurization processes include facilities for the capture and
removal of the resulting hydrogen sulfide (H2S) gas. In petroleum refineries, the hydrogen
sulfide gas is then subsequently converted into byproduct elemental sulfur or sulfuric acid
(H2SO4). In fact, the vast majority of the 64 million metric tons of sulfur produced worldwide
in 2005 was byproduct sulfur from refineries and other hydrocarbon processing plants. [8]
An HDS unit in the petroleum refining industry is also often referred to as a hydrotreater

1.8.1

Classification of Sulfur Compounds

The petroleum feedstock contains the following sulfur compound types:

1.
2.
3.
4.
5.
6.

Mercaptans,
Sulfides,
Disulfides,
Thiophenes (T),
Benzothiophenes (BT),
Dibenzothiophenes (DBT), and their alkyl and hydrogenated derivatives.

Chapter 1

Introduction

Figure 1.1: schematic of Thiophenes (T), Benzothiophenes (BT), dibenzothiophenes

(DBT
HDS reactivity depends critically on the molecular size and structure of the sulfur
compounds. The mercaptans, sulfides and disulfides have, generally, fast kinetics compared
with the thiophenic compounds (T, BT, and DBT as shown in Figure 1). The substituent
groups adjacent to the S atom on thiophenic compounds generally retard HDS. While methyl
groups distant from the S atom generally increase HDS activity - an effect attributed to
increased electron density on the S atom - those adjacent to the S atom decrease reactivity
due to steric effect. [9]

1.8.2

History

Although some reactions involving catalytic hydrogenation of organic substances

were already known, the property of finely divided nickel to catalyze the fixation of hydrogen
on hydrocarbon (ethylene, benzene) double bonds was discovered by the French chemist Paul
Sabatier in 1897. Through this work, he found that unsaturated hydrocarbons in the vapor
phase could be converted into saturated hydrocarbons by using hydrogen and a catalytic
metal, laying the foundation of the modern catalytic hydrogenation process.
Soon after Sabatier's work, a German chemist, Wilhelm Normann, found that catalytic
hydrogenation could be used to convert unsaturated fatty acids or glycerides in the liquid
phase into saturated ones. He was awarded a patent in Germany in 1902 and in Britain in
1903, which was the beginning of what is now a worldwide industry.
In the mid-1950s, the first noble metal catalytic reforming process (the Platformer
process) was commercialized. At the same time, the catalytic hydrodesulfurization of the
naphtha feed to such reformers was also commercialized. In the decades that followed,
various proprietary catalytic hydrodesulfurization processes, such as the one depicted in the
flow diagram below, have been commercialized. Currently, virtually all of the petroleum
refineries worldwide have one or more HDS units.
By 2006, miniature microfluidic HDS units had been implemented for treating JP-8
jet fuel to produce clean feed stock for a fuel cell hydrogen reformer. By 2007, this had been
integrated into an operating 5 kW fuel cell generation system. [8]

Chapter No.2
LITERATURE REVIEW
2.1

Hydrotreatment Process

Hydrotreatment has been part of refinery processing since the 1930s (Topsoe et al.,1996).
Typical Hydrotreatment reactions refer to the catalytic hydrodesulphurization (HDS),
hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), and hydrodearomatization
(HDA) in presence of hydrogen. These reactions are typicallycarried out over a
sulfidedCoMo or NiMo catalyst at 350-450C and 35-250 atm of hydrogen partial
pressure.
A summary of the hydrotreating process conditions for different feed stocks are shown in
Table 2.1. [10]
Feedstock
Naphtha
Kerosene
Atmospheric gas oil
Vacuum gas oil
Atmospheric residue
Vacuum heavy gas oil
Vacuum residue

Temperature
(oC)
320
330
340
360
370-410
380-410
400-440

Hydrogen partial
pressure (atm)
10-20
20-30
25-40
50-90
80-130
90-140
100-150

LHSV
(h-1)
3-8
2-5
1.5-4
1-2
0.2-0.5
1-2
0.2-0.5

In the last two decades petroleum refining technology has significantly changed andthe
reactions of hydrotreatment, in particular, have risen to a level of economic
importance (Gates et al., 1979; Ma et al., 1994). Hydrotreaters now have a central
position in modern refineries as shown in Figure 2.1.

Figure 2.1 Schematic of typical hydrotreatment (HDT). (Adapted from Castaneda et al.,
1999)
10

Chapter 2

2.2

Literature Review

Hydrodesulphurization

Nearly all literature for HDS dynamic models (listed in Table 2.2) is based on validation with
pilot plant data. This approach does not transfer well to industrial applications for the
following reasons:
1. Dynamic models only run from approximately forty minutes to 3 months in length
2. Multiple variable disturbances and operator responses are not considered
3. Low conversion occurs since pilot plant reactor is 10-20 times shorter
Table 2.2: Summary on literature found and cited for modeling catalytic reactors [11]

Reference

Model
Steady
Dynamic
state

Catalyst
Deact.

Levenspiel et al
(1968)

Kodama et al (1980)

Tamm Et al (1981)

Baiker and
Bergougnan (1985)
Dhler and Rupp
(1987)
Chao et al. (1990)
Barto et al (1990)
Chao et al. (1991)
Barto et al (1991)
Miyauchi and deWind (1994)
Lucien et al (1993)
Froment et al (1994)

X
X
X
X
X

Residue
desulfurization
Industrial
Desulfurization,
metals deposition
Fixed Bed 1-d vs
2-d modeling

P/I

VGO-treatment

X
X
X

X
X

I/P

P
X

Warna and Salmi

(1996)

Trickle Bed
Fixed bed reactor
HDS
Pellet Dynamics
Residue
Hydrotreating
Shell HDS process
HDS, 1-d
heterogeneous
Four stages reactor

Kulkarni and
Dudukovic (1996)

Application
Fixed bed reactor

Borio and Schbib

(1995)
Koyama et al (1995)

Experiment
P=Pilot
I= Industrial

Vacuum Residue
HDS
Gas and solid phase
fixed bed reactor
3-phase trickle bed
reactor
hydrogenation of
toluene

11

Chapter 2

Korsten and
Hoffmann (1996)

Literature Review

Recke and
Jrgensen (1997)
Iliuta et al. (1998)

X
X

HDS, 3-phase,
Trickle Bed
Catalytic oxidation
of hydrogen to form
water
Residence time
distribution

Lababidi et al.
(1998)
Juarez et al (1999)

Kokayeff (1999)

Ho (1999)
Oballa (1999)
Julcour et al (1999)
Matos and
Guirardello (2000)

X
X

P
P

Hu et al (2001)

HDS on Industrial
data

HDS of Diesel oil

Chowdury et al
(2002)
Lababidi et al.
(2004)
Mederos et al (2006)

X
X

Desulfurization

X
X

H2S impact on HDS

HDS Aromatic
Saturation
HDS kinetics
Hydrocracking
3-phase fixed bed
HDS + HDM

P
P

Advanced control
HDS, Trickle Bed

All the dynamic models developed are run over such a short time, that the accuracy of any
catalyst deactivation factors, if included, cannot be ascertained. In addition, the robustness of
these models cannot be verified since the interaction of various variables (crude, temperature
and hydrogen changes) is not demonstrated. Finally, non-validated correlations have been
developed to factor in the incomplete catalyst wetting through contacting effectiveness that
creates lower sulfur conversion in pilot plants. As a result, there is little or no confidence in
scaling up a pilot plant validated dynamic model to industrial scale conditions. Any one of
these factors show that there is a need to create a VGO HDS dynamically based model that is
valid over an entire run length (at least 1.5 years).
There are a few papers (Table 3.2) that try to show compatibility with industrial data by
adding 1 or 2 commercial reactor data points from other literature to show how well the
model could be applied to industry. Any model can match up with one or two data points.
Also, they exhibit one of the three noted deficiencies when trying to extend applicability to
actual industrial conditions.
The literature review of dynamic modelling is still important for this body of work, since
there are definitely valuable findings from pilot-plant validated dynamic model development

12

Chapter 2

Literature Review

that can be used for creating a novel industrial validated dynamically based Vacuum gas-oil
hydro-treater model.
2.2.1 Thermodynamics
The HDS of sulfur compounds is exothermic and fundamentally irreversible under the
reaction conditions employed industrially (Gates et al., 1979; Speight, 1981; Vrinat,1983).
Actually, there is very little thermodynamics data available for sulfur compounds present in
high boiling fractions. Vrinat (1983) shows data for dibenzothiophene HDS. According to
these results the conversion of dibenzothiophene into biphenyl is favoredat
temperatures of industrial practice and is exothermic (Ho = -11 kcal/mol). Those
results also suggest that the HDS of higher molecular weight sulfur compounds (e.g.,
benzo naphtha thiophenes) are also favored.
Sulfur removal occurs along two parallel pathways, hydrogenolysis and hydrogenation
(Froment, 2004). Since hydrogenation of the rings of sulfur compounds is equilibriumlimited at industrial HDS temperatures, the pathways concerning previous
hydrogenation of the ring can be affected by thermodynamics (Girgis and Gates,
1991). Vrinat (1983) found that the equilibrium constant for hydrogenation of
thiophene into tetra hydrothiophene is less than unity at temperatures above 350C.
Thus, sulfur-removal pathways via hydrogenated sulfur intermediates may be inhibited at
low pressures and high temperatures because of the low equilibrium concentrations of
the latter species.
2.2.2 first-order Kinetics
The most important hydroprocessing application in a refinery is hydrodesulphurization
(HDS), which comprises reactions leading to removal of sulfur from petroleum
fractions by their conversion into hydrocarbon products and hydrogen sulfide (H2S).
The literature on hydrodesulphurization of oil fractions and sulfurcontaining model
compounds has been reviewed by Gates et al. (1979), Vrinat (1983), Vanrysselberghe
and Froment (2003) and Froment (2004) The kinetics for the decomposition of substituted
benzothiophene and dibenzothiophenes in complex mixtures has been published by Kabe
et al. (1992) in the study of hydrodesulphurization of a light oil on a CoMo/Al2O3
catalyst, and Ma et al. (1994) in the study on hydrodesulphurization in a diesel fuel, a gas
oil, and a vacuum gas oil, on CoMo/Al2O3
The numbering of the carbon atoms in benzothiophene and dibenzothiophene is as follows:

13

Chapter 2

Literature Review

First-order kinetics for the removal of substituted benzothiophene and

dibenzothiophenes in complex mixtures prevail in the literature. Studies of
hydrodesulphurization of a light oil (245-374C) on a CoMo/Al2O3 catalyst found that
benzothiophene with substituents in positions 2, 3, and/or 7 were less reactive than BT (Kabe
et al., 1992). The most refractive methyl substituted-BT was 2,3,7-trimethyl-BT (2,3,7TriMeBT). Dibenzothiophenes with substituents in positions 4 and/or 6 were less reactive
than other substituted dibenzothiophenes. Similar results were obtained by Ma et al.
(1994, 1995a, 1996) in the HDS of substituted BTs and dibenzothiophenes in oil fractions
such as diesel fuel, gasoil, and vacuum gasoil, on CoMo/Al2O3and NiMo/Al2O3
catalysts. In addition, methyl substituents in positions 2, 3, and/or 7 reduce the
hydrodesulphurization rate (Kilanowski et al., 1978). The reactivates of a set of sulfur
compounds, reported as the pseudo-first-order rate constants at 300C and 71 atm, are
shown in Table 2.3.
Table 2.3 Reactivates of Several Sulfur Compounds. (Adapted from Nag et al., 1979)

Reactant

Structure

Pseudo first order rate

constant
L/gcat.s

Thiophene (T)

1.38 x 10-3

Benzothiophene (BT)

8.11 x 10-4

Dibenzothiophene (DBT)

6.11 x 10-5

Benzo[b]naphtho-[2,3-d]
thiophene

1.61 x 10-4

7,8,9,10-Tetrahydrobenzo[b]naphtho-[2,3-d]
thiophene

7.78 x 10-4

The operating conditions of data presented in Table 2.3 can be considered as

representative of industrial conditions. From this Table it can be inferred that DBT is one of
the most representative sulfur compounds comprised in higher boiling fractions of oil.
Because DBT is readily available commercially, it has been used as model compound
orparent molecule for investigating the HDS of organic sulfur compounds.

14

Chapter 2

Literature Review

The hydrogenation rate of 2-methyl-, 3-methyl-, and 2,3-dimethylbenzothiophenewas

less than benzothiophene (Geneste et al. (1980) and Levache et al (1981))
Hydrogenolysis reactions were not considered by these researchers.
Vanrysselberghe&Froment (1998b) obtained similar results in a study of
hydrodesulphurization of Light Cycle Oil (LCO). Benzothiophene with substituents in
positions 2, 3, and/or 7 were less reactive than benzothiophene. Dibenzothiophenes with
substituents in positions 4 and/or 6 were even less reactive. Methyl groups in other
positions led to hydrodesulphurization rates higher than that of dibenzothiophene.
Opposite to this, Kabe et al. (1992, 1997) and Ma et al. (1994, 1995a, 1996) found that
methyl groups in positions 1, 2, and/or 3 had no influence on the
hydrodesulphurization rate. Houalla et al. (1980) established that the first-order rate
coefficient for the HDS of DBT is almost identical with that of 2,8-DiMeDBT (dimethyl
dibenzothiophene) and is about 2 times larger than that of 3,7-DiMeDBT. The HDS of
the reactants shown in Table 2.4 is described by pseudo-first order kinetics as determined by
this investigator.
Table 2.4 Hydrogenolysis Rate Coefficients of Selected Methyl-Substituted
Dibenzothiophenes (a). (Adapted from Houalla, 1980)
Reactant

Structure

Pseudo first order rate

constant
m3/gcat.s

Dibenzothiophene (DBT)

6.11 x 10-5

2,8-dimethyldibenzothiophene
(2,8-DMDBT)

6.72 x 10-5

3,7-dimethyldibenzothiophene
(3,7-DMDBT)

3.53 x 10-5

4-methyldibenzothiophene
(4-MDBT)

6.64 x 10-6

4,6-dimethyldibenzothiophene
(4,6-DMDBT)

4.92 x 10-6

15

Chapter No 3
Process of hydrodesulphurization
3.1

Processing considerations

The operating conditions in the distillate hydrodesulphurization are dependent on the stock to
be charged as well as the desired desulphurization or quality improvement. Kerosene and
light gas oils are generally processed at mild severity and high throughput.
The principal variables affecting the required severity in the distillate desulphurizer are:
i.
ii.
iii.
iv.
i.

Hydrogen partial pressure

Space velocity
Reaction temperature
Feed properties

Hydrogen partial pressure

The important effect of hydrogen partial pressure is the minimization of coking reactions. If
hydrogen pressure is too low for the required duty at any position within the reaction system,
premature aging of the remaining portion of the catalyst will be encountered. The effect of
hydrogen partial pressure on desulphurization varies with feed boiling range. For a given feed
there exists a threshold level above with hydrogen pressure is beneficial to the desired
desulphurization reaction. Below this level desulphurization drops off rapidly as hydrogen
pressure is reduced.

ii.

Space velocity

As space velocity is increased, desulphurization is decreased. However, increasing hydrogen

partial pressure and/ or reactor temperature can offset the detrimental effect of increasing
space velocity.

iii.

Reaction temperature

Higher temperature increases the rate of desulphurization. The start-of -run temperature is set
by the design desulphurization level, space velocity and hydrogen partial pressure. Capability
to increase temperature as catalyst deactivates is built into the unit design. Temperature of
780 oF and above will result in excessive coking reaction and higher than normal catalyst
aging rates. Therefore units are designed to avoid use of such temperatures for any significant
part of the cycle life.

iv.

Feed stock properties

The feed boiling range has the greatest effect on the ultimate design of the unit. The reaction
rate constant in the kinetic relationships decreases rapidly with the increasing average boiling
16

Chapter 3

Process of hydrodesulphurization

point in the kerosene and light gas oil range but much more slowly in the heavy oil range.
This is attributed to the difficulty in removing sulphur from ripping present in the entire
heavy gas oil boiling range. [1]

3.2

Process description

Hydro processing has largely replaced acid base sweetening processes. Modern reactors
generally use sulfide CoMo4 catalyst. Careful control of operating conditions results in
conversion of mercaptans, alkyl sulfides and thiophenes to hydrogen sulfide without
significant Hydro cracking or hydrogenation of aromatics. Olefins, however, are converted to
paraffin. Hydrogen sulfide is scrubbed out of the gas stream with an alkaline or amine
absorbent and is eventually recovered as sulfuric acid, or with the Claus process, as elemental
sulfur.
Modified process is becoming popular for the heavier feed stocks. Its used for catalytic
reforming and hydro cracking feeds is widespread. A development effort has been under the
way for many years on residuum HDS. It is difficult task because of sulfur content, 2 to 5
wt% and the high level of, V and Ni which deposit in the catalyst pores, reducing catalyst
activity.
Table 3.1 Distillate feed stock for hydrodesulphurization
Petroleum feed stock
Light
Light gasoline
Naphtha (Reformer feed)
Kerosene (Jet fuel)
Gas oil (Diesel and heating oil)
Heavy
Residual oil (fuel oil)

Approximate B.P range oC

<80
80-160
150-230
170-370
<350

3.2.1 Process Flow Sheet

Figure 3.1 show the schematic diagram of shell HDS process, which is typical of Hydro
treating processes. The feed stock is mixed with Hydrogen from reforming (or other source)
and hydrogen rich recycle gas which has been recovered from the desulphurized product.
This mixture is heated in a furnace to a temperature 750 oF and then passed downward
through a concurrent fixed bed reactor charged with palletized catalyst. Reactor pressure is
held between 900-1200 psia.
The reactor effluent, consisting of desulphurized oil, hydrogen and hydrogen sulfide, is
cooled and products are separated in high pressure knock out. The hydrogen rich gas from
which hydrogen sulfide is removed is recycled to the feed inlet and the liquid products passes
to the stripping column where dissolved hydrogen sulfide and high hydrocarbons are
17

Chapter 3

Process of hydrodesulphurization

18

Chapter 3

Process of hydrodesulphurization

removed. With feed stock low in metals, catalyst deactivation occurs primarily through coke
deposition and catalyst life without regeneration may be a year or more.
The catalyst may be regenerated when necessary, without removing it from the reactor, by
passing over it a mixture of steam and air to burn out the coke deposits. The trickle bed is
flexible and can be used for treating a variety of refinery streams.
Operating practice calls for gradually increasing the temperature of feed to the reactor to
compensate for coking of the catalyst. Periodically, the reactor is shut down and the
accumulated coke is burnt off as mentioned above. A catalyst charge may endure several of
these run-regeneration cycles and remain in the reactor for as long as 10 years. Catalyst life is
reduced sharply with heavier feeds, reflecting their higher metal content and propensity to
form coke.
Table 3.2 hydrodesulphurization operating conditions as function of feed stock
Processing conditioning
Temperature oC
Pressure range (atm)
LHSV ( vol., fed/vol.,
catalyst/hr)
H2 recycle rate (std.
ft3/bbls)
Catalyst life (years)

Light petroleum (Feedstock)

300-400
35-70

Heavy petroleum
(Feedstock)
340-425
55-170

2-10

0.2-1

300-2000

2000-10,000

10

-1

A possible alternative to trickle beds for residuum, bitumen and coal processing is a three
phase fluidized or emulating bed Reactor. Catalyst particles are held in suspension by the
upward velocity of the liquid reactants, through which hydrogen flows concurrently.
There are several advantages to this Reactor design:
I.
II.

III.

The deactivating catalyst can be removed and replaced continuously (as in catalytic
cracking).
Small catalyst particles can be used, and they are more effective than larger particles
because intra particles mass-transport interface is insignificant (particles with
dimensions less than few mm are avoided in fixed bed because the pressure drop is
unacceptably high), and
The fluidized bed Reactor contents are expected to be very well mixed, which
suggests that uniform temperatures can be maintained.

19

Chapter 3

3.3

Process of hydrodesulphurization

Hydrodesulphurization catalysis

Catalyst developed for hydrotreating includes cobalt and molybdenum oxides on alumina,
nickel oxide, nickel thiolybdate, tungsten and nickel sulphides, and vanadium (II) oxide. The
cobalt and molybdenum oxides on alumina catalysts are in most general use today because
they have proven to be highly selective at the same operating conditions, easy to regenerate
and resistant to poisons. They must be activated by converted the hydrogenation metals from
the oxides to the sulphide form.
Cobalt-molybdenum catalysts are selective for sulphur removal and nickel molybdenum
catalysts are selective for nitrogen removal although both catalysts have a higher
hydrogenation activity than Cobalt-molybdenum catalyst which results, at the same operating
conditions, in a greater saturation of aromatic rings. Simply stated if sulphur reduction is
primary objective, then a Cobalt-molybdenum catalyst will rescue the sulphur a given amount
at less severe operating conditions with low hydrogen consumption than nickel-molybdenum
catalyst. If nitrogen reduction or aromatic ring saturation is desired, nickel-molybdenum
catalyst is the preferred catalyst.
Catalysts commonly used for distillates are alumina-supported mixed oxide of Co and Mo
whose surfaces are usually sulphides before use. Industrial catalyst may contain as high as 10
to 20 percent Co and Mo. Molybdates predominates in the mixture and usually the Mo/Co
ratio is much greater than one. One widely used catalyst contains 3 weight% CoO and 12
weight% MoO. A number of related compositions have also been employed as HDS
catalysts, for example, Ni and W instead of Co and Mo. In contrast to the supported Pt and Pt
alloy catalyst used in reforming, HDS catalyst have hydrogenation activity in the presence of
high concentration of sulphur compounds; their activities, however, are characteristically less
than Pt by several orders of magnitude.
Catalyst structure and details of the desulphurization mechanism are still far from understood.
Sulphiding clearly converts the surface layers to the metal sulphide (MoO3+MoS2:
CoO+Co9S8). The sulphide ion S-2 is much larger than O-2 so Sulphiding disrupts the surface
structure. Since MoS2 is much more active than Co9S8, but quite a bit less active then mixture
of sulphides, and intercalculation explanation for the activity had been proposed. Al2O3 is
used exclusively as a support apparently because the surface structure inhibits then formation
CoMoO4. On sulphiding, CoMoO4 forms a sulphide which is catalytically inactive. Schultz
and Gates have purposed a radix mechanism for the sulphides catalysts involving electron
transfer from MO+3 to the sulphur containing hydrocarbon for form Co and Mo+4. HDS
catalyst is furnished as porous particles or extradites with diameter of 1.5 to 3mm. The
particles size and pore geometry significantly influence catalyst performance, especially for
the heaviest feeds.

20

Chapter 3
3.4

Process of hydrodesulphurization

Hydrodesulphurization Reactions

Petroleum crudes contain many different sulphur compounds. More are created in cracking
operations which may precede HDS units. Figure 2 identifies a few of these compounds and
illustrates their structure. Note the first four members of the list represent different kinds of
C-S bonding. The list is ordered to show reactivity of each class in hydrodesulphurization.
The thiols are very reactive, while S bond into an aromatic ring is refractory. Reactions which
take place are cleavage of the C-S and S-S bonds;

Thiols:

RSH + H2

Disulphides:

RSSR + 3H2

Sulphides:

RSR + 2H2

RH + H2S
RH + RH + 2H2S

RS + RH + H2S

Where R & R are usually paraffin groups. Hydrogenolysis of thiophenessulphur is typified

by:

But there are variations:

All of the above reactions are essential irreversible at 350-450 oC and 100-200 atm H2
pressure, although at very low sulphur levels the equilibrium system must be considered.

+ 2

The hydrogenolysis of the sulphur containing compounds is accompanied by some rupture of

C-C bonds.

21

Chapter 3

Process of hydrodesulphurization

And splitting of nitrogen compound to form ammonia

Reaction of this type may be beneficial. Removing nitrogen from feed stocks is often
necessary before refining by hydro cracking, since basic nitrogen containing compounds are
poisons for the acidic sites of bifunctional hydro cracking catalysts.
Hydrogenation of unsaturated compounds also occurs during HDS and reaction rates are
significant compared with those of hydrodesulphurization. For example, naphthalenes
hydrogenated readily:

The last three classes of reactions take on economic importance in the processes by
consuming expensive hydrogen without removing sulphur.
HDS reactions are exothermic with heats of reaction of the order of 10 to 20 Kcal/mole of
hydrogen consumed or roughly 50 to 100 Btu/standard cubic foot of hydrogen consumed.

Compounds Class

Structure

Thiols (Mercaptans)
Disulphides
Sulphides

RSH
RSSR
RSR

Thiophenes
Benzothiophenes

Dibenzothiophenes

Benzonaphthothiophenes

BenzoDibenzothiophenes
Figure 3.2: Classes of sulphur containing compounds in petroleum

22

Chapter 3

3.5

Process of hydrodesulphurization

Hydrodesulphurization Kinetics

A thiophenes compound are the least reactive sulphur compounds in petroleum, is the
simplest compound in this class. Thiophenes have frequently been chosen for the study as a
model reactant. Thiophenes hydrodesulphurization is examined in series kinetics. The
catalysts are a commercial Co-Mo/Al2O3 (1.3 percent Co and 6.1 percent Mo), Chromia, and
several molybdenum disulphides. Hydrodesulphurization apparently proceeds through
rupture of the -S- bonds to form butadiene.

Figure 3.3: Thiophenes Hydrogenation Network

A reaction scheme is shown in figure 3.3.
H2S inhibits thiophenes hydrogenation and the -S- cleavage and butane hydrogenation occurs
on different catalytic sites. Take this inhibition into account when they analyzed their data for
thiophenes hydrodesulphurization over a 3 wt% CoO-7 wt% MoO3 / y-alumina catalyst. In
the temperature range 235 to 265oC, their data for the rates of thiophenes disappearance
(hydrogenation) where represents by Landmuir-Hinshelwood rate equation as follows:
rHDS = kPtPH2 / (1 + KTPT + KH25 PH25)2 ----------------------- I
rhyd = KP8PH2 / (1K8P8 + KH25 PH25) ------------------------- II

23

Chapter 3

Process of hydrodesulphurization

Value of the rate-equation parameters are summarized in Table 3. Although the

appropriateness of these models for petroleum fractions is not firmly established, the models
do agree with the observation that:
1. H2S inhibits both Hydrogenolysis and hydrogenation and
2. Significant amounts of thiophenes and butane are adsorbed on the catalyst surface in
competition with H2S. The separate models suggest the hydrogenolysis and HDS
proceed on different catalytic sites.
TABLE 3.3: Thiophenes Hydrodesulphurization Kinetics: Parameters values for
Equation 1 & 2
KH2
S/atm-

Temperature

Kr/

KH2S/

KB/

(oC)

(mole/gatm.sec)

atm-1

atm-1

mole/gtam.sec

atm-1

235

1.5 x 10-5

43

31

2.0 x 10-8

980

91

251

1.6 x 10-5

23

13

12.2 x 10-8

120

19

265

1.8 x 10-5

25

56

--------------

-------

13

3.6

Discussion about Reactor

3.6.1

Introduction

A trickle-bed reactor (TBR) is a chemical reactor that uses the downward movement of a
liquid and gas over a packed bed of catalyst particles. It is considered to be the simplest
reactor type for performing catalytic reactions where a gas and liquid (normally both
reagents) are present in the reactor and accordingly it is extensively used in processing plants.
Typical examples are liquid phase hydrogenation in refineries (three phase hydro treater) and
oxidation of harmful chemical compounds in wastewater streams. [12]
At high liquid and/or gas flow rates, TBRs are operated in the pulsating flow regime, where
the gas/liquids distributions vary and liquid rich pulses move down the bed. The conductance
method had been used extensively to characterize this liquid pulses [13] with two or more
pairs of conductance rings place at different heights down the bed. Each pairs measures the
electrical impedance of the liquid, hence the liquid holdup, in the bed cross section between
the ring electrodes at a sampling rate of up to thousands of Hz. This technique is in situ and
very robust for studying transient behavior in TBRs. However, an intrinsic drawback is that
all measurements made are averaged between pairs of conductance rings and no spatial
information is given.
24

Chapter 3
3.6.2

Process of hydrodesulphurization

Trickle Bed Reactor Operation

Summary of the typical H2 and oil phase mass flow rates for HDS are reproduced. Bearing in
mind that the transition between trickling and pulsing is downward concurrent operation is
2<L<10kg/m2/s and 0.1<G<1.0kg/m2/s, pilot plant HDS beds operate in the trickling regime,
while full scale units may sometimes function in the pulsating regime.
The gas and liquid loading in HDS trickle beds make it unlikely that mass transfer from the
liquid phase to the catalyst particles is rate controlling. On the other hand, transport within
the catalyst reduces the apparent HDS activity. Effectiveness factors, are about 0.4 to 5mm
diameter CoMoO4/Al2O3 extradites (55 atm, 370oC), whereas they are about 0.6 for 3.2mm
particles at 34 atm and 416oC. Internal diffusion may not be the only source of the particle
size dependence.
Advantages of a trickle bed are ease of installation, low liquid holdup(and therefore less
undesirable homogeneous reactions), minimal catalyst handling issues, low catalyst attrition,
and catalyst life of 1 to 4 years.
The liquid and gas flow in trickle beds approaches plug flow (leading to higher conversion
than slurry reactors for the same reactor volume).
Downsides of trickle beds include flow maldistribution (bypassing),sensitivity to packing
uniformity and prewetting (leading to hot spots),incomplete contacting/wetting, intra particle
diffusion resistance, potential for fouling and bed plugging due to particulate matter in the
feed, and high pressure drop. A significant fraction of the flow is gas that has to be
compressed and recycled (i.e., increased compressor costs).
3.6.3

Trickle Bed Reactor Design

Figure shows a vertical cross section of a trickle bed designed to hydro treat 25,000 bbl/day
of gas oil. Nominal feed rates of the 30oAPI oil and gas (75%H2) are 323,078 lb/hr and
weight hourly space velocity for this reactor is about 3.5. Oil and hydrogen are mixed prior to
the fired heater. They enter the reactor at about 700-800oF and 800-1000 psi. Somewhat over
the half i=oil is vaporized in the heater.
The liquid phase entering the top of the reactor drops into a perforated catch plate which
distributes the phase across the upper catalyst bed. Gas enter the bed through the chimneys a
six inch deep layer of inert ball protect the catalysts and probably further distributed the
liquid and gas phase, depending on the bed depth. Primarily, flow distributer will be used as
may be seen in PFD. Their design is much like the top distributor. Gas descends to the lower
bed in chimneys and most of the liquid phase is redistributed by the catch plane. The design
shows also permits a gas quench for temperature controls. [14]

25

Chapter 3

Process of hydrodesulphurization

A bed of coarse, inert spheres supports the catalyst (beds are connected through the
chimneys), while a bed of finer spheres prevents catalyst from mixing with the supports. A
nozzle in the bottom of head may be opened to withdraw spent catalyst. Fresh catalyst would
be loaded from the top of the reactor.

Figure 3.4: Trickle bed Reactor

Hydrodesulphurization of petroleum oils was the first large-scale application of trickle bed
reactors commercialized in 1955. In this application, organo sulfur species contained in
refinery feeds are removed in the presence of hydrogen and a catalyst and released as
hydrogen sulfide. Conditions depend on the quality and boiling range of the oil. The reactor
pressure is optimized to increase the solubility of the hydrogen and minimize catalyst
deactivation due to coking. Over the life of the catalyst, the temperature is increased to
maintain a constant conversion. Temperatures are in the range of 345 to 425C (653 to
797F) with pressures of 34 to 102 atm (500 to 1500 psi). A large commercial reactor may
have 20 to 25 m (66 to 82 ft) of total depth of catalyst, and may be up to 3-m (9.8-ft) diameter
or above in several beds of 3- to 6-m (9.8- to 19.7-ft) depth. Bed depth is often limited by
pressure drop, the catalyst crush strength, and the maximum adiabatic temperature increase
for stable operation. [15]
26

Chapter 3

Process of hydrodesulphurization

The need to limit pressure drop is driven by the capital and operating costs associated with
the hydrogen recycle compressor. Catalyst granules are 1.5 to 3.0 mm (0.06 to 0.12 in),
sometimes a little more. Catalysts are 10 to 20 percent Co and Mo (or Ni and W) on alumina.
The adiabatic temperature rise in each bed usually is limited to 30C (86F) by injection of
cold hydrogen between beds. Since the liquid trickles over the catalyst, the wetting efficiency
of the catalyst is important in determining the volumetric reaction rate. As expected, wetting
efficiency increases with increasing liquid rate. Catalyst effectiveness of particles 3 to 5 mm
(0.12 to 0.20 in) in diameter has been found to be about 40 to 60 percent. [15]

27

Chapter No. 4
PLANT LOCATION & LAYOUT
4.1

Plant Location

The geographical location of the final plant can have strong influence on the success of an
industrial venture. Considerable care must be exercised in selecting the plant site, and many
different factors must be considered. Primarily, the plant should be located where the
minimum cost of production and distribution can be obtained, but other factors, such as room
for expansion and safe living conditions for plant operation as well as the surrounding
community, are also important.
A general consensus as to the plant location should be obtained before a design project
reaches the detailed estimate stage, and a firm location should be established upon
completion of the detailed-estimate design. The choice of the final site should first be based
on a complete survey of the advantages and disadvantages of various geographical areas and,
ultimately, on the advantages and disadvantages of available real estate. The following
factors should be considered in selecting a plant site:
1. Raw materials availability
2. Markets
3. Energy availability
4. Climate
5. Transportation facilities
6. Water supply
7. Waste disposal
8. Labor supply
9. Taxation and legal restrictions
10. Site characteristics
11. Flood and fire protection
12. Community factors
The factors that must be evaluated in a plant-location study indicate the need for a vast
amount of information, both quantitative (statistical) and qualitative. Fortunately, a large
number of agencies, public and private, publish useful information of this type greatly
reducing the actual original gathering of the data. [16]

4.1.1

Raw materials availability

The source of raw materials is one of the most important factors influencing the selection of a
plant site. This is particularly true if large volumes of raw materials are consumed, because
location near the raw-materials source permits considerable reduction in transportation and
storage charges. Attention should be given to the purchased price of the raw materials,
distance from the source of supply, freight or transportation expenses, availability and
reliability of supply, purity of the raw materials, and storage requirements.
28

Chapter 4

4.1.2

Plant Location & Layout

Markets

The location of markets or intermediate distribution centers affects the cost of product
distribution and the time required for shipping. Proximity to the major markets is an
important consideration in the selection of a plant site, because the buyer usually finds it
advantageous to purchase from nearby sources. It should be noted that markets are needed for
by-products as well as for major final products.

4.1.3

Energy availability

Power and steam requirements are high in most industrial plants, and fuel is ordinarily
required to supply these utilities. Consequently, power and fuel can be combined as one
major factor in the choice of a plant site. Electrolytic processes require a cheap source of
electricity, and plants using electrolytic processes are often located near large hydroelectric
installations. If the plant requires large quantities of coal or oil, location near a source of fuel
supply may be essential for economic operation. The local cost of power can help determine
whether power should be purchased or self-generated.

4.1.4

Climate

If the plant is located in a cold climate, costs may be increased by the necessity for
construction of protective shelters around the process equipment, and special cooling towers
or air-conditioning equipment may be required if the prevailing temperatures are high.
Excessive humidity or extremes of hot or cold weather can have a serious effect on the
economic operation of a plant, and these factors should be examined when selecting a plant
site.

4.1.5

Transportation facilities

Water, railroads, and highways are the common means of transportation used by major
industrial concerns. The kind and amount of products and raw materials determine the most
suitable type of transportation facilities. In any case, careful attention should be given to local
freight rates and existing railroad lines. The proximity to railroad centers and the possibility
of canal, river, lake, or ocean transport must be considered: Motor trucking facilities are
widely used and can serve as a useful supplement to rail and water facilities. If possible, the
plant site should have access to all three types of transportation, and, certainly, at least two
types should be available. There is usually need for convenient air and rail transportation
facilities between the plant and the main company headquarters, and effective transportation
facilities for the plant personnel are necessary.

4.1.6

Water supply

The process industries use large quantities of water for cooling, washing, steam generation,
and as a raw material. The plant, therefore, must be located where a dependable supply of
29

Chapter 4

Plant Location & Layout

water is available. A large river or lake is preferable, although deep wells or artesian wells
may be satisfactory if the amount of water required is not too great. The level of the existing
water table can be checked by consulting the state geological survey, and information on the
constancy of the water table and the year-round capacity of local rivers or lakes should be
obtained. If the water supply shows seasonal fluctuations, it may be desirable to construct a
reservoir or to drill several standby wells. The temperature, mineral content, silt or sand
content, bacteriological content, and cost for supply and purification treatment must also be
considered when choosing a water supply.

4.1.7

Waste disposal

In recent years, many legal restrictions have been placed on the methods for disposing of
waste materials from the process industries. The site selected for a plant should have
adequate capacity and facilities for correct waste disposal. Even though a given area has
minimal restrictions on pollution, it should not be assumed that this condition will continue to
exist. In choosing a plant site, the permissible tolerance levels for various methods of waste
disposal should be considered carefully, and attention should be given to potential
requirements for additional waste-treatment facilities.

4.1.8

Labor supply

The type and supply of labor available in the vicinity of a proposed plant site must be
examined. Consideration should be given to prevailing pay scales, restrictions on number of
hours worked per week, competing industries that can cause dissatisfaction or high turnover
rates among the workers, and variations in the skill and productivity of the workers.

4.1.9

Taxation and legal restrictions

State and local tax rates on property income, unemployment insurance and similar items vary
from one location to another. Similarly, local regulations on zoning, building codes, nuisance
aspects, and transportation facilities can have a major influence on the final choice of a plant
site. In fact, zoning difficulties and obtaining the many required permits can often be much
more important in terms of cost and time delays than many of the factors discussed in the
preceding sections.

4.1.10

Site characteristics

The characteristics of the land at a proposed plant site should be examined carefully. The
topography of the tract of land and the soil structure must be considered, since either or both
may have a pronounced effect on construction costs. The cost of the land is important, as well
as local building costs and living conditions. Future changes may make it desirable or
necessary to expand the plant facilities. Therefore, even though no immediate expansion is
planned, a new plant should be constructed at a location where additional space is available.
30

Chapter 4

4.1.11

Plant Location & Layout

Flood and fire protection

Many industrial plants are located along rivers or near large bodies of water, and there are
risks of flood or hurricane damage. Before selecting a plant site, the regional history of
natural events of this type should be examined and the consequences of such occurrences
considered. Protection from losses by fire is another important factor in selecting a plant
location. In case of a major fire, assistance from outside fire departments should be available.
Fire hazards in the immediate area surrounding the plant site must not be overlooked.

4.1.12

Community factors

The character and facilities of a community can have quite an effect on the location of the
plant. If a certain minimum number of facilities for satisfactory living of plant personnel do
not exist, it often becomes a burden for the plant to subsidize such facilities. Cultural
facilities of the community are important to sound growth. Churches, libraries, schools, civic
theaters, concert associations, and other similar groups, if active and dynamic, do much to
make a community progressive. The problem of recreation deserves special consideration.
The efficiency, character, and history of both state and local government should be evaluated.
The existence of low taxes is not in itself a favorable situation unless the community is
already well developed and relatively free of debt.

4.2

Selection of the Plant Site

The major factors in the selection of most plant sites are (1) raw materials, (2) markets, (3)
energy supply, (4) climate, (5) transportation facilities, and (6) water supply. For a
preliminary survey, the first four factors should be considered. Thus, on the basis of raw
materials, markets, energy supply, and climate, acceptable locations can usually be reduced to
one or two general geographical regions. For example, a preliminary survey might indicate
that the best location for a particular plant would be in the south-central or south-eastern part
of the United States. In the next step, the effects of transportation facilities and water supply
are taken into account. This permits reduction of the possible plant location to several general
target areas. These areas can then be reduced further by considering all the factors that have
an influence on plant location.
As a final step, a detailed analysis of the remaining sites can be made. Exact data on items
such as freight rates, labor conditions, tax rates, price of land, and general local conditions
can be obtained. The various sites can be inspected and appraised on the basis of all the
factors influencing the final decision. Many times, the advantages of locating a new plant on
land or near other facilities already owned by the concern that is building the new plant
outweigh the disadvantages of the particular location. In any case, however, the final decision
on selecting the plant site should take into consideration all the factors that can affect the
ultimate success of the overall operation.

31

Chapter 4

Plant Location & Layout

We have selected our site near pak-arab refinery limited (PARCO) Qasba Gujrat District
Muzaffargarh Pakistan.

4.3

Plant Layout

After the process flow diagrams are completed and before detailed piping, structural, and
electrical design can begin, the layout of process units in a plant and the equipment within
these process units must be planned. This layout can play an important part in determining
construction and manufacturing costs, and thus must be planned carefully with attention
being given to future problems that may arise. Since each plant differs in many ways and no
two plant sites are exactly alike, there is no one ideal plant layout. However, proper layout in
each case will include arrangement of processing areas, storage areas, and handling areas in
efficient coordination and with regard to such factors as: [16]
1. New site development or addition to previously developed site
2. Type and quantity of products to be produced
3. Type of process and product control
4. Operational convenience and accessibility
5. Economic distribution of utilities and services
6. Type of buildings and building-code requirements
7. Health and safety considerations
8. Waste-disposal requirements
9. Auxiliary equipment
10. Space available and space required
11. Roads and railroads
12. Possible future expansion

32

Chapter No. 5
Material Balance
5.1

Material balance

Material balance is defined as the mass conserved; the mass entering in a process is equal to
mass exiting from the process. It is based on the law of conservation of mass which states that
mass is neither be created nor be destroyed.
5.1.1

Law conservation of mass

It states that:
[Rate of mass going into the system]-[Rate of mass going out of the system] +[Rate of mass
generation within the system]-[Rate of mass consumption within the
system]=[Rate of mass accumulation in the system]
5.2

Gas oil specifications

Specific gravity of oil

0.8767 [18]

APIo

30

Sulphur content in feed

1.81% (wt)

Amount of gas oil to be desulphurized

25,000bbl/day

Sulphur content in product

0.05%

Hydrodesulphurization of gas oil is carried out by shell process.

33

Chapter 5

5.3

Material Balance

Gas Oil
We want to know the mass of gas oil used.
=

.. 1

water
=

1kg/litre
.

= 0.8767 * 1
=0.8767 kg/litre
(as 1kg = 2.2lbm)

= 0.8767

= 1.9287

2.2
1

Quantity of oil

25,000 bbl/day

(as 1bbl = 42 gallons and 1 gallon = 3.7853 litre)

Volume of oil (V oil)

25,000

V oil

3974565 litre/day

3.7853

Putting values in equation 1

34

Chapter 5

Material Balance

Mass of oil (M oil)

1.9287

3974565 litre/day

M oil

7665744 lbm/day

319406 lbm/hr

(as one day = 24 hr)

M oil

5.4

Hydrogen gas

Mass of hydrogen gas used is given by

Mass of H2

H2 * VH2

H2

0.0056 lbm/ft3

1 bbl of oil require H2 (for hydrodesulphurization) = 325 ft3 [19]

1 bbl of oil require H2 (when conversion is 97%)

= 315 ft3

25,000 bbl of oil Required H2 (for hydrodesulphurization) = 315 * 25,000

= 78,75,000 ft3/day
Putting values in equation 2
M hydrogen

0.0055954

M hydrogen

44064 lbm/day

M hydrogen

1836 lbm/hr

7875000

35

Chapter 5

Material Balance

If 100% excess H2 is used, then

M hydrogen

1836*2

M hydrogen

3672 lbm/hr

5.5

Material balance across Reactor

M hydrogen

3672 lbm/hr

Trickle Bed Reactor

Mass
M oil

= 319406 lbm/hr

Oil = ?

= 1.81% of oil

H2= ?

= 5781.25 lbm/hr

H2S = ?

Reaction occurring is
+
Theoretical H2 required

H2S produced

5781.25*2/32

361.33 lbm of H2

5781.25*34/32

6142.58 lbm of H2S

36

Chapter 5

Material Balance

Gas oil contains different sulphur compounds such as sulphides, cyclic sulphide,
Benzothiophenes,

Dibenzothiophenes, and each compound will take different quantity of

H2. But here we are taking a model compound of thiophenes.

+ 3

.. (A)

Above equation shows that

1 mole of H2S

1 mole of C4H4S

34 lbm of H2S

84 lbm of C4H4S

6142.58 lbm of H2S

84/34*6142.58

15175.8 lbm of C4H4S

15175.8 5781.25

9394.55 lbm of C4H4

Total C4H4

From the equation A it is clearly indicate that 1 mole of H2 react with C4H4S to form one
mole of H2S and two moles of H2 reacts with C4H4 to form C4H8.
1 mole of C4H4 require

2 moles of H2

52 lbm of C4H4 require

4 lbm of H2

9394.55 lbm of C4H4 require

4/52*9394.55

722.66 lbm of H2

total H2 - H2 for sulphur - H2 for C4H4

Unreacted H2

37

Chapter 5

Material Balance

Unreacted H2

3672 361.33 722.66

2588 lbm of H2 (unreacted)

Thus total mass balance around reactor

M 1 + M2

M3

MH2 + Moil

oil + H2 + H2S

3672 + 319406

oil + 2588 + 6142.58

Oil = 314347.42 lbm/hr

M hydrogen

3672 lbm/hr

M1
Trickle Bed Reactor
M2

M3

M oil

= 319406 lbm/hr

Oil = 314347.42 lbm/hr

= 1.81% of oil

H2= 2588 lbm/hr

= 5781.25 lbm/hr

H2S = 6142.58 lbm/hr

38

Chapter 5

5.6

Material Balance

Material balance across Separator

H2= 2588 lbm/hr
H2S = 6142.58 lbm/hr

Separator

Oil = 314347.42 lbm/hr

H2= 2588 lbm/hr

Oil = 314347.42 lbm/hr

H2S = 6142.58 lbm/hr

5.7

Material balance across Scrubber

Lean DEA
M2
M1

M3

Scrubber

H2= 2588 lbm/hr

H2= 2588 lbm/hr

H2S = 6142.58 lbm/hr

M4
Rich DEA

If 25% solution of diethanol amine is used then

1.3 mol of DEA

1 mol of H2S [20, pg-52]

Moles of H2S

6142.58

180.66 lbmol/hr

39

Chapter 5

Material Balance

Moles of DEA required For H2S

1 mol of H2S

1.3 mol of DEA

180.66 lbmol of H2S

180.66*1.3

234.66 lbmol/hr of DEA

Weight of DEA required

Moles

weight/ mol. wt

Weight

moles * mol.wt

Weight of DEA required

234.66 * (105*.25)

6165.1 lbm/hr

M3

M4

(6142.58 + 2588) + 6165.1

2588

M4

M4

12307.68 lbm/hr

Total balance
M1

M2

weight of rich DEA

Lean DEA = 6165.1 lbm/hr

M2
M1

Scrubber

H2= 2588 lbm/hr

H2S = 6142.58 lbm/hr

M3
H2= 2588 lbm/hr

M4
Rich DEA = 12307.68 lbm/hr
40

Chapter 5

Material Balance

5.8 Material balance across Stripper

Fuel gas = ?

Stripper
Oil = = 314347.42 lbm/hr
Gas oil = ?
(Desulphurized)
From the reactor mass balance
+2

9394.55 lbm of C4H4 require

722.66 lbm of H2

So, Total C4H8

9394.55 + 722.66

10117.21 lbm/hr

Total oil

314347.42 lbm/hr

Fuel gas (C4H8)

10117.21 lbm/hr

Gas oil

Total oil - Fuel gas (C4H8)

Gas oil

314347.21 10117.21

304230.21 lbm/hr

41

Chapter 5

Material Balance
Fuel gas = 10117.21 lbm/hr

Stripper
Oil = = 314347.42 lbm/hr
Gas oil = 304230.21 lbm/hr
(Desulphurized)

42

Chapter 5

Material Balance

43

Chapter No. 6
Energy Balance
6.1.

Energy balance

Energy balance is defined as the energy conserved; the energy entering in a process is equal
to energy exiting from the process. It is based on the law of conservation of energy that
energy is neither being created nor be destroyed but it changes from one form to another.
6.1.1

Law of conservation of energy:

It states that
[Rate of energy going into the system]- [Rate of energy going out of the system] +[Rate of
energy generation within the system]-[Rate of energy consumption within the system]=[Rate
of energy accumulation in the system]
6.1.2

Reference conditions

Conditions for the calculations in energy balance are:

Temperature = 273 K
Pressure

6.2.

= 101.325 kPa

Energy balance across a reactor

=

78,75,000 ft3/day

7875000

Hydrogen consumed

328125 ft3/hr

1 ft3 of H2 produces energy

50 BTU [21]

328125 ft3 of H2 produces energy

50*328125

16406250 BTU/hr

Hydrogen consumed
(1day = 24hr)

44

Chapter 6

Energy Balance

Heat produced, Q

1.641*107 BTU/hr

M oil

319406 lbm/hr

Cp at 750 oF

0.82 BTU/ lbm-oF [22]

MoilCpT

1.641*107

319406 * 0.82 (T2 7500F)

T2

813 0F

Thus heat produced in the reactor, Q

1.641*107 BTU/hr

Outlet temperature of stream from the reactor, T2

813 0F

6.3.

Energy balance across Heat exchanger

Hot Stream T1=8130F

Cold stream

Heat Exchanger

t1 = 77 0F

t2 = 250 0F

T2= ?

For Cold Stream

Moil

319406 lbm/hr

Average temperature

(t1 + t2)/2

(77 + 250)/2

163.5 0F

45

Chapter 6

Energy Balance

Cp at 163.5 oF

0.5 BTU/ lbm-oF [22]

Qcold Stream

MoilCp(t2 - t1)

319406 * 0.5 * (250-77)

27628619 BTU/hr

Qcold Stream

For Hot Stream

Mass of Oil from Reactor, moil = 314347.42 lbm/hr
In the reactor there is no gain or loss in mass of oil.
Qhot stream

moil Cp(T2 T1)

Cp at 813 oF

0.845 BTU/ lbm-oF [22]

Qhot stream

moil Cp(T2 T1)

27628619

314347.42*0.845*(T2 813)

T2

729 0F

Temperature of outlet Hot stream, T2 =

729 0F

Heat utilize in the heat exchanger, Q =

27628619 BTU/hr

46

Chapter 6

6.4.

Energy Balance

Energy balance across Cooler

Cooler

T1 = 7290F

t1 = 77 0F

T2 = 100 0F

t2 = 130 0F

Heat in cooler
Qin

MCpT1

Cp at 729 0F

0.81 BTU/ lbm-oF [22]

Qin

314347.42*0.81*729

185619008.0358 BTU/hr

T2

100 0F

Cp at 100 0F

0.465 BTU/ lbm-oF [22]

Qout

MCpT2

314347.42*0.465*100

14617155.03 BTU/hr

Qin - Qout

Heat out from cooler

Heat removed in cooler

47

Chapter 6
Heat removed in cooler

Energy Balance
=

185619008.0358 BTU/hr - 14617155.03 BTU/hr

171001853 BTU/hr

Coolant required (Water)

Mass of coolant, m

t1

77 0F

t2

130 0F

t2 - t1

130 77

53 0F

(t2 + t1)/2

(130 + 77) / 2

103.5 0F

Cp of water at Tavg

1 BTU/ lbm-oF [22]

mCpt

Q/Cpt

171001853/(1*53)

3226450.06 lbm/hr

Tavg

Mass of coolant, m

Volume of water required, V =

?
48

Chapter 6

Energy Balance

m/

Density of water at STP,

62.4 lbm/ft3

6.5.

.
.

51705.93 ft3/hr

Energy balance across Heater

6.5.1 Heat in
For oil
M oil

319406 lbm/hr

250 0F

Cp at 100 0F

0.55 BTU/ lbm-oF [22]

Qoil

MoilCp T

319406 * 0.55 * 250

43918325 BTU/hr

M hydrogen

3672 lbm/hr

77 0F

Cp of Hydrogen at 77 0F

3.5 BTU/ lbm-oF [22]

Qoil
For Hydrogen

49

Chapter 6
Qhydrogen

Qhydrogen

Energy Balance
=

MhydrogenCp T

3672 * 3.5 * 77

989604 BTU/hr

Total heat in in the heater-1 =

(MoilCp T) + (MhydrogenCp T)

Qin

43918325 BTU/hr + 989604 BTU/hr

Qin

44907929 BTU/hr

After mixing temperature

Reference temperature, TR

32 0F

MoilCp (T TR) + MhydrogenCp (T TR) =

(Moil * Cpoil + MH2 * CpH2) * (T- TR)

{319406 * 0.55 * (250 32)} + {3672 * 3.5 * (77 32)} = {(319406 * 0.55) + (3672 * 3.5)}
* {T 32}
38296779.4 + 578340 = (175673.3 + 12852) * (T 32)
38875119.4 = 188525.3 T - 6032809.6
=

238.2 0F

After mixing temperature, T =

238.2 0F

6.5.2 Heat out

For oil
T

750 0F
50

Chapter 6

Energy Balance

Cp at 750 oF

0.82 BTU/ lbm-oF [22]

M oil

319406 lbm/hr

Qoil

MoilCp T

319406 * 0.82 * 750

196434690 BTU/hr

750 0F

Cp at 750 oF

3.5 BTU/ lbm-oF [22]

M hydrogen

3672 lbm/hr

Qhydrogen

MhydrogenCp T

3672 * 3.5 * 750

Qhydrogen

9639000 BTU/hr

Total Heat out

Qoil + Qhydrogen

196434690 + 9639000

Qout

206073690 BTU/hr

Heat given by heater

Qout Qin

206073690 44907929

161165761 BTU/hr

For Hydrogen

51

Chapter 6

Energy Balance

6.5.3 Source of Heating

Refinery gas (dry) is used for heating purpose.
(Characteristics of refinery gas are taken form. [7, pg-417]
M.wt of dry refinery gas

28 lbm/lbmol

Gross Heating Value

1540 BTU/ft3

Net Heating value

1407 BTU/ft3

So, 1407 BTU needed gas

1 ft3

1 BTU needed gas

1/1407

161165761 BTU needed gas

1/1407 * 161165761

114545.67 ft3

Air needed
1 ft3 of fuel (Refinery gas) needed air

15.7 ft3{zero % excess air}[7]

114545.67 ft3 of fuel needed air

15.7 * 114545.67

1798367.019 ft3/hr

1.35 * 1798367.019

2427795.5 ft3/hr

Normally 35% excess air is used. [7]

Excess air

52

Chapter 6

6.6.

Energy Balance

Energy balance across Heater-2

Feed of heater-2 is oil coming from separator is 314347.42 lbm/hr.

M

314347.42 lbm/hr

100 0F

Cp of oil at 100 0F

0.465 BTU/lbm-0F [22]

M Cp T

314347.42 * 0.465 * 100

14617155 BTU/hr

300 0F (Assume)

Cp at 300 0F

0.575 BTU/lbm-0F [22]

Qout

M Cp T

314347.42 * 0.575 * 300

54224930 BTU/hr

Heat in
Qin

Heat out

Heat provided by heater =

=

Qout Qin
54224930 14617155

53

Chapter 6

Energy Balance

Heat provided by heater =

39607775BTU/hr

Source of heating
Steam enter at 214.7 Psia or 200 Psig
T

388 0F

Latent heat,

837 BTU/lbm (From steam table)

m*

Q/

39607775/837

47321 lbm/hr

Mass of Steam, M

Thus, 47321 lbm/hr of steam is required for heating.

54

Chapter 6

Energy Balance

55

Chapter No. 7
Equipment Design
7.1

Design of furnace
The furnace is designed to heat the feed form 238.2 0F to 750 0F.
The fuel used in heater is the refinery gas. Furnace is handling the flow rate of feed

323078 lbm/hr of feed.

Entering temperature of feed

238.2 0F

Exiting temperature of feed

750 0F

(750 238.2)

511.8 0F

(T1 + T2)/2

(238.2 + 750)/2

494.10F

Cp at Tavg

0.685 BTU/lbm-0F [22]

Mass flow rate of feed

323078 lbm/hr

Heat absorbed

mCpT

323078 * .685 * 511.8

113265654.5 BTU/hr

Tavg

56

Chapter 7

Equipment Design

Heat transfer film coefficient for Gas oil

hi

180 BTU/hr-ft2-0F [7,p-562]

Fouling factor for hydrogen rich gas oil

Ro

0.004

1/ (1/hi + Ro)

1/ (1/180 + 0.004)

104.65 BTU/hr-ft2-0F

UAT

Q/UT

113265654.5/ (104.65 * 511.8)

2114.75 ft2

Taking nominal pipe size IPS

2 inch

Outer diameter, O.D

2.38 [22, p-844]

Surface area per linear ft

0.622 ft2/ft

0.622 ft2 require length

1 ft

1 ft2 require length

1/0.622

2114.75 ft2 require length

1/0.622 * 2114.75

Overall heat transfer coefficient is

U

57

Chapter 7

Equipment Design
=

3399.92 ft

3399.92/30

113.33 say 114

So, number of 30 ft pipes

114 pipes

Material of construction of tubes

Stainless steel

Number of 30 ft pipes

58

Chapter 7

Equipment Design

Table 7.1: Specification sheet for heater

Description

Units

Duty

Charge Oil flow rate

BPD

25,000

Flow rate

lbm/hr

323078

Gravity

API

30

Inlet Temperature

238.2

Outlet Temperature

750

Heat Absorb. Normal

106 BTU/hr

113.27

Heat transfer coefficient

BTU/hr-ft2-0F

180

Fouling factor

hr-ft2-0F/BTU

0.004

Area

ft2

2114.75

Pipe size

Inch

Linear Length required

ft

3399.92

No. of pipes

114

Material of construction

Stainless steel

59

Chapter 7

7.2

Equipment Design

Reactor Design
The function of reactor is to react 319406 lbm/hr of gas oil containing 1.81% (wt) of

sulphur with 3672 lbm/hr of Hydrogen. Feed passed through fixed bed reactor and sulphur is
converted into H2S in the presence of catalyst. We are using Trickle bed reactor. In this
reactor flow rate of liquid is very slow as compared to gas flow rate. Thats why the process
of Trickling occurs.

Calculations
Inlet temperature of the stream

750 0F

Outlet temperature of the stream

813 0F

Pressure in the reactor

1200 psia

LHSV (Liquid hour space velocity)

3.5 hr-1

Space velocity, S

3.5 hr-1

Space Time, T

1/S

1/3.5

0.29 hr

V/Vo

Volume of reactor

Space Time, T
We know the equation
T
Where,
V

60

Chapter 7

Equipment Design

Vo

Volumetric flow rate

Mass flow rate of oil

319406 lbm/hr

Mass flow rate of H2

3672 lbm/hr

Total mass flow rate

323078 lbm/hr

Specific gravity of oil, S.G

0.8767

water

62.4 lbm/ft3

oil

0.8767 * 62.4

oil

54.71 lbm/ft3

hydrogen

0.0056 lbm/ft3

Volumetric flow rate of feed, Vo

323078/54.71

Vo

5905.3 ft3/hr

T * Vo

0.29 * 5905.3

1712.5 ft3

Since reactor is packed with catalyst. So, we will have to consider fraction voids
which is . suppose
61

Chapter 7

Equipment Design
=

0.4

V/

Vf

Volume of reactor + Catalyst

Vf

1712.5/0.4

Vf

4281.3 ft3

We have formula
Vf
Where,

Suppose 30% space is provided at top and bottom of reactor. i.e.

Vf

4281.3 * 1.3

Vf

5565.69 ft3

Assume dia of reactor

15 ft

Vf

A*L

A*L

5565.69 ft3

/4 * d2 * L

5565.69 ft3

5565.69 ft3 * 4/3.142 *1/152

31.5 ft

So, volume occupied by catalyst

4281.3 ft3 1712.5 ft3

2568.8 ft3
62

Chapter 7
Empty Space

Equipment Design
=

5565.69 - 2568.8 1712.5

1275.39 ft3

Empty space at top

Empty space at bottom

So, Empty space at top

637.695 ft3

and, Empty space at bottom

637.695 ft3

Material of construction of tubes

Stainless steel

63

Chapter 7

Equipment Design

Table 7.2: Specification sheet for Reactor

Description

Units

Duty

Flow rate

lbm/hr

323078

Pressure range

Psia

900-1200

Inlet Temperature

750

Outlet Temperature

813

LHSV

hr-1

3.5

Volume of reactor

ft3

5565.69

Fraction Voids

0.4

Additional Space proviede

%age

30

Dia of reactor

ft

15

Length of reactor

ft

31.5

Volume occupied by catalyst

ft3

2568.8

Material of construction

Stainless steel

64

Chapter 7

7.3

Equipment Design

Design of Heat Exchanger

Heat exchanger is installed for two processes. First, we want to heat the feed steam so

that on the load on the furnace can be reduced by preheating second. We want to lower down
the temp. of stream from the reactor. Feed stream is heated from 77F to 250F while
temperature of stream from the reactor is lower down from 813F to 729F.
Hot Stream T1=8130F

Cold stream

Heat Exchanger

t1 = 77 0F

t2 = 250 0F

T2= ?

For Cold Stream

Moil

319406 lbm/hr

Average temperature

(t1 + t2)/2

(77 + 250)/2

163.5

Cp at t Avg

0.5 Btu/lbm- oF [22]

MoilCp (t2-t1)

319406*0.5*(250-77)

27628619 Btu / hr

For Hot Stream

Mass of Oil from Reactor, moil = 314347.42 lbm/hr

65

Chapter 7

Equipment Design

In the reactor there is no gain or loss in mass of oil.

Qhot stream

moil Cp(T2 T1)

Cp at 813 oF

0.845 BTU/ lbm-oF [22]

Qhot stream

moil Cp(T2 T1)

27628619

314347.42*0.845*(T2 813)

T2

729 0F

Temperature of outlet Hot stream, T2 =

729 0F

Calculation of LMTD
Flow is countercurrent. So,
1

lm

T1 t2

813 250

563 0F

T2 t1

729 -77

652 0F

(2 -1) / ln(2 /1)

(652-563) /ln(652/563)

606.41 0F
66

Chapter 7

Equipment Design

Ud is given in literature =

(10-40) Btu / hr ft2-0F [22, P-840]

So, Ud

38 Btu / hr ft2-0F

Ud A lm

Q/ Udlm

27628619/ (38*606.41)

1199ft3

3.14DoNtL

Now, A

We should have to select shell dia, no. of tubes length heat exchange and dia of tube
Let,
Outer dia of tubes, Do

1.5 in [22]

Square pitch

1.875 in

Shell ID

31 in

No. of tubes, Nt

151

20ft

3.14 DoNtL

1185.35 ft2

Q/ A lm

27628619/ (1185.35*606.41)

67

Chapter 7
U

Equipment Design
=

38.44 Btu / hr ft2-0F

Calculation of Caloric Temp Difference

T

T1 T2

813-729

84 0F

Kc

0.3 [22, P-827]

t2 t1

250-77

173 0F

T1 t2

729-77

652 0F

T1 t2

813- 250

563 0F

652/563

1.16

0.3

tc

th

tc/th

As Kc

and

tc/th

= 1.16
68

Chapter 7

Equipment Design

Fc

0.48 [22]

Tc

T2+Fc (T1 T2)

729 +0.48(813-729)

769.32 0F

770 0F

tc

t1 + Fc(t2 t1)

tc

77 +0.48(250-77)

160 0F

Allocation of Fluids
Hot oil passes through tube side while cold oil will flow through shell side
Properties of Oil
Properties of cold Fluid (shell side)
Tc

160Fo

0.0743 Btu / hr ft2- 0F

Cp

0.5 Btu / lb-0F [22]

4.5 c.p.

4.5*2.42

10.9 lb / hr ft

69

Chapter 7
S.G

Equipment Design
=

0.84

As

I D * C B / 144 pt

Pt

1.875 in [22]

Dia of tubes

1.5 in

pt - Do

0875-1.5

0.345 in

ID

31 in

31 in

As

(31*0.375*31) /(144*1.875)

As

1.335 ft3

Moil/As

319406/1.335

239255 lb/hr ft2

Flow Area

Mass Velocity
Gs

70

Chapter 7

Equipment Design

Reynolds number Calculation

Res

DeGs/

De

1.48 in [22]

De

1.48/12

0.123 ft

(0.123)*(239255)/10.9

2700

28 [22]

(Cp/K)1/3

(0.5*10.9/0.0743)1/3

4.13

ho

Jh(k/De)(Cp/k)0.33s

ho/ s

28*(0.0743/0.123)*4.13

ho/ s

69.85 Btu / hr ft2-0F

Res

JhFactor
Jh
Prandtl no.
Pt

71

Chapter 7

Equipment Design

Properties of Hot Oil (Tube Side)

Tc

770 0F

0.06 Btu / hr ft2- 0F

Cp

0.85 Btu / lb-0F

0.53 c.p.

0.53*2.42

1.283 lb / hr ft

0.615

For tube side dia

1.5 in & 10 BWG

ID

1.23 in or 0.1025 ft

3.14*(ID)2/4

1.19 in2

A*Nt/(144*n)

1.19*15.1/(144*1)

1.25ft2

Area of tube

Area Calculations

At

Where,
A

72

Chapter 7
At

Equipment Design
=

Total area of all tubes

Moil/At

319406/1.25

255525 lb/ (hr-ft2)

Ret

IDtGt/

Ret

(0.123)*(255525)/1.283

244970

20/0.1025

195

520 [22]

(Cp/K)1/3

(0.85*1.283)/(0.06)1/3

2.627

Mass Velocity
Gt

Reynolds no. Calculation

JhFACTOR
L/D

Jh
Prandtl no.
Pt

73

Chapter 7

Equipment Design

hi/t

hi

Jh(k/De)(Cp/k)1/3t

hi/t

520*(0.06/0.1025)*2.627

hi/t

800 Btu / hr ft2-0F

hio/t

(hi/t)(I D / OD)

800*(1.23/1.5)

656 Btu / (hr ft2-0F)

hio/t

Calculation of wall temperature

tw

tc + [(ho/s)/(hio/ t + ho/ s)](Tc-tc)

160 + {69.85/ (656+69.85)}*(770-160)

218.7 0F

219 0F

tw

219 0F

2.5 cp

2.5*2.42

6.05lb / (ft-hr)

(/w) 0.14

(10.9/6.05)

1.082

tw
TUBE SIDE

74

Chapter 7

Equipment Design

ho/ s

69.85 Btu / hr ft2-0F

ho

69.85*1.082

ho

75.6 Btu / hr ft2-0F

hio/t

656 Btu / (hr ft2-0F)

hio

656 * 1.082

hio

709.8 Btu / hr ft2-0F

(hio*ho)/(hio+ho)

(709.8*75.6)/ (709.8+75.6)

68.32 Btu / (hr-ft2-0F)

(1/UC) +RD

1/(68.32)+0.003

56.7 Btu / (hr-ft2-0F)

and

Calculation of UC
UC

UC
Calculation of UD
1/UD

UD

Calculation of Pressure Drop

Tube side
Ret

244970
75

Chapter 7

Equipment Design

0.00012 ft2/in2

Pt

(fG2tLn)/(5.22*1010*D*S* t)

=
Pt

{0.00012*(255525)2*20*1}/ (5.22*1010*0.1025*0.8767*0.805)
=

0.041 psi

Gt

255525 lb / (hr-ft2)

V2/2g

0.0084 [22, fig-27]

Pr

(4n/S)(v2/2g)

(4*1/0.8767*0.0084)

0.038 psi

Pt+Pr

0.041+0.038

0.079 psi

10psi

2700

0.0027 ft2/in2

12*L/B

When

Pt

Allowable PT
SHELL SIDE
Res

No. of crosses (N+1)

[22, fig-29]

76

Chapter 7

Equipment Design

N+1

Ps
=

12*20/31

7.74

{f*Gs2*D*(N+1)}/(5.22*1010*Ds*S*s)

{0.0027*(239255)2*(31/12)*7.74}/(5.22*1010*0.123*0.8767*1.086)
=

0.5 psi

Allowable Ps

10 psi

Material of construction

stainless steel

77

Chapter 7

Equipment Design

Table 7.3: Specification Sheet for Heat Exchanger

Description

Units

ALLOCATION OF FLUID

Shell side
in

Shell side
out

COLD GAS OIL

TOTAL FLUID QUANTITY

lbm/hr

TEMPERATURE

SP.GRAVITY

Tube side
in

Tube side
Out

HOT GAS OIL

319406

319406

319406

319406

77

250

813

729

0.84

0.615

10.9

1.283

0.5

0.85

0.0743

0.06

0.05

0.079

FOULDING RESISTANCE
hr-ft2-OF/Btu

0.003

0.003

CALCULATED H.T COEFF

Btu/hr-ft2-OF

68.32

VISCOSITY

lb/ft-hr
O

SP. HEAT

Btu/lb- F

THERMAL CONDUCTIVITY
ft2-OF
PRESSURE DROP ALLOW

DESIGN H.T COEFF

Btu/hrPsi

Btu/hr-ft2-OF

56.7

LMTD

606.41

CALORIC TEMP

160

HEAT EXCHANGE
AREA REQUIRED
DIAMETER

Btu/hr
Ft

Inch

NO. OF PASSES
BAFFLE SPACING

Inch

27628619
1186
31(inner)

1.5(outer)

31 segment

NO. OF TUBES
H.E TYPE
MATERIAL OF CONSTRUCTION

151(1.875 sq. pitch)

Fixed Tube sheet exch.
Stainless steel

Stainless steel

78

Chapter 7

7.4

Equipment Design

Separator Design
The function of Separator is to separate the oil from the gas. We are using horizontal

Separator to separate the 314347.42 lb/hr of oil from 8730.58lb/hr of gas.

A horizontal separator would be selected when a long liquid hold-up time is required.
We need a long liquid hold up time so, we select horizontal separator.
Goil

314347.42 lbm/hr

oil

0.8767x62.4 lbm /ft3

54.71 lbm /ft3

314347.42 /54.71

5745.70 ft3/hr

GH2S

6142.58 lbm/hr

H2S

0.096 lbm /ft3

QH2S

63985.21 ft3/hr

GH2

2588 lbm/hr

H2

0.0056 lbm /ft3

Mass fraction of H2, wH2

2588/8730.58

WH2

0.3

WH2s

1 - 0.3

Qoil

79

Chapter 7

Equipment Design

WH2s

0.7

gas

WH2s * H2S + WH2 * H2

(0.7*0.096) +(0.3 * 0.0056)

gas

0.069 lbm /ft3

QH2

462142.86 ft3/hr

Qgas

Qgas+ QH2

Qgas

63985.21 + 462142.86

Qgas

526128.07 ft3/hr

Settling velocity, Ut

0.07{( oil- gas)/ gas }1/2 [23, pg-461]

Where Ut

Settling velocity, m/s,

0.07{(54.71+0.069)}/0.069}1/2

1.97 m/sec

1.97 m/sec * 3.281 ft/m

6.46 ft/sec

Ut

If a demister pad is not used, the value of Ut obtained should be multiplied by a factor
of 0.15 to provide a margin of safety and to allow for flow surges. [23] pg-461
Try a separator without a demister pad.

80

Chapter 7

Equipment Design

So,
Ut

0.15 * 6.46

0.97 ft/sec

Vapour Volumetric flow rate, Q

= 8730.58 / (3600 * 0.069)

35.15 ft3/sec

Taking hv

0.5 Dv and

Lv

5 Dv

fv

0.5, [23, pg-463]

Where
hv

Height above the liquid level

fv

Fraction of the total cross-sectional area occupied by the vapors

Dv

Vessel diameter

Lv

Length of vessel

Av

Vapour velocity, Uv

( Dv2/4)*0.5

0.393 Dv2

Q/A

35.15 / (0.393Dv2)

89.44 Dv-2

81

Chapter 7

Equipment Design

Vapour residence time required for the droplets to settle to liquid surface
Residence time required

hv/Ua

Trequired

0.5 Dv/0.97

0.52 Dv

vessel length / vapour velocity

Lv/Uv

(0.5 Dv )/(89.44 Dv-2)

0.0056 Dv3

Residence time required

Actual residence time

So,

0.0056 Dv3

Dv2

92.86

Dv

9.64 ft say 10 ft

5745.70 ft3 /hr * 1hr/ 3600 sec

1.6 ft3/sec

Actual residence time

Tactual
For satisfactory separation

0.52 Dv

Liquid Holdup Time

Qoil

Liquid cross sectional area, AL

=

= 3.14 (10)2/ 4x0.5

39.25 ft2
82

Chapter 7
Length, Lv

Equipment Design
=

5* Dv

5* 10

Lv

50 ft

Hold up volume

Lv * AL

50 * 39.25

1962.5 ft3

Liquid volume / Liquid flow rate

1962.5 ft3/ 1.6 ft3 sec-1

1226.56 sec

20.5 min

Stainless Steel

Hold up time

Material of construction

83

Chapter 7

Equipment Design

Table 7.4: Specification sheet for Separator

Description

Units

Duty

Charge oil Flow rate

lbm/hr

323078

Gas Flow rate

lbm/hr

8730.58

Liquid flow rate

lbm/hr

314347.42

Operating Temperature

100

Settling Velocity

ft/sec

6.46

Dia of separator

ft

10

Length of separator

ft

50

Hold up time

min

20.5

Material of construction

Stainless steel

84

Chapter 7

7.5

Equipment Design

Scrubber Design
Lean DEA
M2
M1

Scrubber

H2= 2588 lbm/hr

M3
H2= 2588 lbm/hr

H2S = 6142.58 lbm/hr

M4
Rich DEA

Suppose 0.2 mol % of H2S goes with H2

Moles of H2S in

6142.58 lb/hr * lbmol/ 34 lb

180.66 lbmol / hr

0.002 * 180.66

0.36 lbmol /hr or 12.24 lbm/hr

H2S to be Scrubbed

6142.58 12.24 = 6130.34 lbm/hr

Fraction Absorbed, Eal

(moles in moles out) / moles in

(180.66-0.36)/180.66

Eal

0.998

(Lo/Vn+1) min

KI* EaI

11.5 * 0.998

11.48

Moles of H2S in H2

85

Chapter 7

Equipment Design

Value of Kl is taken from equilibrium charts for avg. Tower condition i.e.
T = 90 F0
Operating (Lo/Vn+1)

and p = 60 psig

11.48 x 1.25

14.35

Operating Absorption Factor (Aio):

(Aio)

(Lo / Vn+ 1) (1/ K I )

14.35x1/ 11.5

1.25

For Optimum Economic Design:

1.2 < Aio< 2.0
As Aio is within the range so our design is optimum and economic.
Theoretical trays can be found out by;
n+1

n+1

Eai

(Aio

- Aio)/ (Aio

- 1) [24]

(n+1) log (Aio)

log {(Aio -Eal)/(1- Eal)}

(n+1) log (1.25)

log {(1.25-0.99)/(1- 0.998)}

21

Absorption efficiency,

55-60%

Actual plates, N

n/

21/0.6

86

Chapter 7

Equipment Design

35

Liquid (DEA) flow rate, L

6165.1 lbm/ hr

Density of DEA

67.8 lbm/ft3

Gas flow rate, G

6142.58 + 2588

8730.58 lb /hr

Density of gas

=
P1V1/T1

359/492

?
P2V2/T2

(As P1=P2)

V2/560

V2

408.62 ft3 /lbmol

gas

M.Wavg/ volume

M.Wavg

WH2s * M.WH2S + WH2 * MWH2

WH2s& WH2 are mass fraction of H2S and H2 respectively.

=

0.7 * 34 + 0.3*2

M.Wavg

24.4 lbm/lbmol

gas

24.4 / 408.62

0.06 lbm/ft3

L/G (P V/PL)1/2

FLV

Where, FLV dimensionless flow parameter

87

Chapter 7

FLV

Equipment Design
=

6165.1/ 8730.58 * (0.06/67.8)1/2

0.021

Assume tray spacing is 24 inch

Csb

0.39 ft/sec [25]

For liquids with surface tension that is different from 20 dyne/cm.

Csb

Csb(/20)0.2

20 dyne/ cm (for given liquid)

Uvf

Csb{ (PL-Pv)/ Pv }1/2 [25]

0.39 * {(67.8 0.06)/0.06}1/2

13.1 ft/sec

Uvf

Where, Uvf is flooding vapour velocity

The design vapor velocity is determined based on the percentage of flooding allowed.
Uv

Uvf * (% flooding)/100

Where, Uv is designed vapour velocity

Assume 85% of flooding velocity is used
Uv

13.1 * (85)/100

11.14 ft/sec

The tower area, At is given by equation

88

Chapter 7

Equipment Design

At

Qv/Uv

Qv

G/v

8730.58 / 0.06

145509.67 ft3/hr * 1hr/3600sec

Qv

40.42 ft3/sec

Then, At

40.42 / 11.14

At

3.63 ft2

Since 12% area is used for down comer.

So total area of column;
At

3.63 * 1.2

At

4.4 ft2

(4*At/) 0.5

(4*4.4/) 0.5

2.4 ft

Take standard form Ludwig p-72, table 8.5

D

2.5 ft

Area of column

*2.52/4

4.91 ft2
89

Chapter 7

Equipment Design

Table 7.5: Specification sheet for Scrubber

Description

Units

Duty

Charge Gas Flow rate

lbm/hr

8730.58

H2S to be Scrubbed

lbm/hr

6130.34

Lean DEA solution flow rate

lbm/hr

6165.1

Absorption factor

1.25

Absorption Efficiency

60 %

Tray Spacing

Inch

24

Velocity

ft/sec

13.1

Dia of Column

ft

2.5

Area of column

ft

4.91

Operating Temperature

100

Material of construction

Stainless steel

90

Chapter 7

7.6

Equipment Design

Stripper Design
Fuel gas = 10117.21 lbm/hr

Stripper
Oil = = 314347.42 lbm/hr
Gas oil = 304230.21 lbm/hr
(Desulphurized)
Stripper is designed to separate 10117.21 lbm/hr of fuel gas from 314347.42 lbm/hr of oil.
Assumption:
L

5d

Separation takes place within two minutes.

Volume of tower

1.5 volume of oil

Oil out, G

304230.21 lbm/hr

oil

54.71 lbm/ft3

G/oil

304230.21/54.71

5560.8 ft3/hr

Q, Volumetric flow of oil

Quantity of oil on stripper for two minutes

=

(5560.8*2)/60

91

Chapter 7

Equipment Design
=

185.4 ft3

Volume of tower, VT

1.5 * 185.4

VT

278.1 ft3

VT

(*d2*L)/4

VT

(*5d3)/4

d3

4/5*(VT/)

4/5*(278.1/)

d3

70.82 ft3

4.14 ft

5*d

5*4.14

20.7 ft

Material of construction of tubes

Stainless steel

(assume, L=5d)

92

Chapter 7

Equipment Design

Table 7.6: Specification sheet for Stripper

Description

Units

Duty

Charge oil Flow rate

lbm/hr

314347.42

Fuel gas Flow rate

lbm/hr

10117.21

Desulphurized gas oil flow rate

lbm/hr

304230.21

Operating Temperature

300

Volumetric flow of oil

ft3/hr

5560.8

Volume of tower

ft3

278.1

Dia of tower

ft

4.14

Length of tower

ft

20.7

Operating time

min

Material of construction

Stainless steel

93

Chapter No. 8
Instrumentation & Process Control
8.1

Instrumentation

Instruments are provided to monitor the key process variables during plant operation.
They may be incorporated in automatic control loops or used for the manual monitoring of
the process operation. They may also be part of an automatic computer data logging system.
Instruments monitoring critical process variables will be fitted with automatic alarms to alert
the operators to critical and hazardous situations.
It is desirable that the process variable to be monitored be measured directly.
However, this is often impractical and some dependent variable that is easier to measure,
monitored in its place. For example, in the control of distillation columns the continuous online, analysis of the over-head product is desirable but it is difficult and expensive to achieve
reliably, so temperature is often monitored as an indication of composition. [26]

8.2

Instrumentation and Control Objective

There might be lot of control objectives depending upon the situation, condition and
equipment. Some of common and major objectives of instrumentation and control schemes
are given following:
8.2.1

Safer Plant Operation

a) To keep the process variables within known safe operating limits.
b) To detect dangerous situations as they develop and to provide alarms and
automatic shut-down systems.
c) To provide inter locks and alarms to prevent dangerous operating procedures.

8.2.2

Production Rate
a) To achieve the design product output.
b) To increase production rate by fast and accurate control action

8.2.3

Product Quality
To maintain the product composition within the specified quality standards

94

Chapter 8

Instrumentation & Process Control

8.2.4 Cost
To operate at the lowest production cost, commensurate with the other objectives.
These are not separate objectives and must be considered together. The order in which they
are listed is not meant to imply the precedence of any objective over another, other than that
of putting safety first. In a typical chemical processing plant these objectives are achieved by
a combination of automatic control, manual monitoring and laboratory analysis.

8.3

Components of Control System

8.3.1

Process
Any operation or series of operations that produces a desired final result is a process.

In this discussion the process is the CO2 recovery from reformed natural gas.
8.3.2

Measuring Means

Of all the parts of the control system the measuring element is perhaps the most
important. If measurements are not made properly the remainder of the system cannot operate
satisfactorily. The measured available is dozen to represent the desired condition in the
process.
8.3.2.1

Analysis of Measurement Variables to be Measured

Measured
a) Pressure measurements
b) Temperature measurements
c) Flow Rate measurements
d) Level measurements
Variables to be recorded
Indicated temperature, composition, pressure, etc
8.3.3

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. In the controller there is also an error-detecting mechanism which compares the
measured variables with the desired value of the measured variable, the difference being the
error.

95

Chapter 8
8.3.4

Instrumentation & Process Control

Final Control Element

The final control element receives the signal from the controller and by some
predetermined relationships changes the energy input to the process.

8.4

Classification of Controller

In general the process controllers can be classified as:

Pneumatic controllers

Electronic controllers

Hydraulic controllers

In the H2S recovery from H2 gas 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.
ii) The pneumatic controller appears to be safer in a potentially explosive atmosphere
which is often present in the petro-chemical industry.
iii) Transmission distances are short. Pneumatic and electronic transmission systems are
generally equal up to about 250 to 300 feet. Above this distance, electronic systems
begin to offer savings.

8.5

Modes of control

The various types of controls are called "modes" and they determine the type of
response obtained. In other words these describe the action of the controller that is the
relationship of output signal to the input or error signal. It must be noted that it is error that
actuates the controller. The four basic modes of control are:
a.
b.
c.
d.

On-off Control
Integral Control
Proportional Control
Rate or Derivative Control

96

Chapter 8

Instrumentation & Process Control

In industry purely integral, proportional or derivative modes seldom occur alone in

the control system.
Table 8.1: Different types of controllers
Mode

Advantage

Disadvantage

On-off

Simple, inexpensive

Constant cycling

Proportional

Time lag is not included

Almost has an offset

Integral

Eliminates offset

Adds time lag to the system

Derivative

Speeds up the response

Responds to noise

8.6

Alarms and Safety Trips and Interlocks

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:

A sensor to monitor the control variable and provide an output signal when a
preset valve is exceeded (the instrument).

A link to transfer the signal to the actuator usually consisting of a system of

pneumatic or electric relays.

An actuator to carry out the required action; close or open a valve, switch off a
motor.

A safety trip can be incorporated in control loop. In this system the high-temperature
alarm operates a solenoid valve, releasing the air on the pneumatic activator closing the valve
on high temperature.

97

Chapter 8

Instrumentation & Process Control

Interlocks
Where it is necessary to follow the fixed sequence of operations for example, during a plant
start-up and shut-down, or in batch operations-inter-locks are included to prevent operators
departed from the required sequence. They may be incorporated in the control system design,
as pneumatic and electric relays or may be mechanical interlocks.

8.7

Types of Controllers

8.7.4

Flow Controllers

Flow-indicator-controllers are used to control the amount of liquid. Also all manually
set streams require some flow indication or some easy means for occasional sample
measurement. They are also used to control feed rate into a process unit. Orifice plates are by
far the most common type of flow rate sensor. Normally, orifice plates are designed to give
pressure drops in the range of 20 to 200inch of water. Venture tubes and turbine meters are
also used.
8.7.5

Temperature Controller

Thermocouples are the most commonly used temperature sensing devices. The two
dissimilar wires produce a millivolt emf that varies with the "hot-junction" temperature. Iron
constrictant thermocouples are commonly used over the 0 to 1300F temperature range.
8.7.6

Pressure Controller

Bourdon tubes, bellows and diaphragms are used to sense pressure and differential
pressure. For example, in a mechanical system the process pressure force is balanced by the
movement of a spring. The spring position can be related to process pressure.
8.7.7

Level Controller

Liquid levels are detected in a variety of ways. The three most common are:
1. Following the position of a float, that is lighter them the fluid.
2. Measuring the apparent weight of a heavy cylinder as it buoyed up more or less by
the liquid (these are called displacement meters).
3. Measuring the difference between static pressure of two fixed elevation, one on
the vapor which is 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.

98

Chapter 8

8.8

Instrumentation & Process Control

Transmitter

The transmitter is the interface between the process and its control system. The job of
the transmitter is to convert the sensor signal (milli volts, mechanical movement, pressure
differential, etc.) into a control signal 3 to 15 psig air-pressure signal, 1 to 5 or 10 to 50 milli
ampere electrical signal, etc.

8.9

Control Valves

The interface with the process at the other end of the control loop is made by the final
control element is an automatic control valve which throttles the flow of a stem that opens or
closes an orifice opening as the stem is raised or lowered. The stem is attached to a
diaphragm that is driven by changing air-pressure above the diaphragm. The force of the air
pressure is opposed by a spring.[25]

8.10 Automatic Control

Automatic control instrumentation, if properly maintained, are tireless, immune to
monotony, and not subjected to distraction. Thus they have a great advantage over human
operation for the monotonous vet very highly necessary lob monitoring for the plant
variables such as flow rates, plant temperature, steam composition etc. and detecting the
disturbance which may arise
Properly adjusted and set, control instruments can eliminate the experience aspect of
human. Thus the same response, and always the correct response, can be counted anytime a
particular disturbance occurs. Instrument is quicker also to detect and apply the required
correction than any human could be.
Automation control offers many possibilities for improving plant and personnel safety by:

Closer control of critical or dangerous processes.

Removal of operation personnel from vicinity of potentially dangerous operations.
Better working conditions for personnel by eliminating the necessity for exposure to
inclement weather etc.

8.11 Economics Effects of Installing Instruments

Instrumentation that is installed on a savings basis usually effects chemical plant
operation in one of the following ways.
Reduction no equipment investment by the elimination of intermediate storage, excess
capacity, standby machinery, and unnecessary purification step.

99

Chapter 8

Instrumentation & Process Control

8.12 Indicator and Recorder Operation

Indicating and recording instruments display the measured values of a process
variable for instance, temperature. This process variable may act directly on the instrument,
or a transducer mm be used to convert the process variable to a different signal.
Measurement signal is the directly applied to the indicating or recording instrument
and may not be identical with the process variable.
Indicators and recorders which respond to an electrical measurement signal are classed as
electrical indicators and recorders. Non-electrical indicators and recorders are classed as
mechanical instruments. Measurements signal for mechanical instruments include mechanical
force, pressure, temperature, humidity etc. when these variables operate directly, to provide a
display by mechanical means.
A collective general description of the instruments used will be given which may be
conveniently into following steps.
Temperature measurements and control.
Weight measurement and control.
Flow measurement and control
Temperature lowering alarms.

8.13

Temperature Recorder (T.R)

The thermocouple is one of the most common temperature measuring devices. Chromelalomel thermocouple is suggested for the process.
8.13.1 Temperature Indicator Controller (T.LC)
The normal method for controlling a heat exchanger to measure the exit temperature
of the fluid being processed and adjust the input of the cooling or heating medium to hold the
desired temperature. Therefore, the temperatures are recorder-controller are installed to
control the heat exchangers.
8.13.2 Pressure Indicator Controllers (P.I.C)
This instrument is used to pressure of the separator.
8.13.3 Level Controller
This is used to control the level of liquid in separator.
8.13.4 Gate Valve
This is used for in-off services requiring infrequent throttling.
100

Chapter 8

Instrumentation & Process Control

8.13.5 Globe Valve

This valve is used for throttling service because of increased resistance to flow.
8.13.6 Check Valve
This is used to prevent the back flow in lines.

101

Chapter 8

Instrumentation & Process Control

102

Chapter No. 9
The HAZOP (hazard and operability) Method
9.1

Introduction:
9.1.1

The HAZOP Concept:

The HAZOP process is based on the principle that a team approach to hazard analysis will
identify more problems than when individuals working separately combine results. The
HAZOP team is made up of individuals with varying backgrounds and expertise. The
expertise is brought together during HAZOP sessions and through a collective brainstorming
effort that stimulates creativity and new ideas, a thorough review of the process under
consideration is made.

9.1.2

The HAZOP Process

The HAZOP team focuses on specific portions of the process called nodes. Generally
these are identified from the P&ID of the process before the study begins. A process
parameter is identified, say flow, and an intention is created for the node under consideration.
Then a series of guideword is combined with the parameters flow to create a deviation. For
example, the guideword no is combined with the parameter flow to give the deviation no
flow. The team then focuses on listing all the credible causes of a no flow deviation
beginning with the cause that can result in the worst possible consequence the team can think
of at the time. Once the causes are recorded the team lists of consequences, safeguards and
ant recommendations demand appropriate. The process is repeated for the next deviation and
so on until the completion of the node. The team moves on to the next node and repeats the
process.

9.1.3

HAZOP Objectives:

The objectives of HAZOP study are following:

1. To identify (area of the design that may possess a significant hazard potential.
2. To identify and study features of the design that influence of a hazardous incident
occurring.
3. To familiarize the study team with the design information available.
4. To ensure that a systematic study is made of the areas of significant hazard
potential.
5. To identify the pertinent design information not currently available to the team.
6. To provide a mechanism for feedback to the client of the study team`s detailed
comments.

103

Chapter 9

9.1.4

HAZOP Method

Why HAZOP, not Design Review?

1. Design review is normally a check, where the contributors work alone, so interaction
is not possible.
2. HAZOP is a design review, but is structured, systematic and complete.
3. It involves a skilled team working together and interacting to identify and solve the
problems.

9.1.5

Why HAZOP, not what if or FMEA?

1. What if studies are similar to HAZOP, but are normally less systematic and
complete.
They require less time, but provide less comfort!
2. FMEA is sometimes carried out as a team exercise, when it can be similar to
HAZOP. However, it concentrates on single components rather than the systems.
3. A very power full combination is possible, using HAZOP first to identify issues and
consequences, then using FMEA to review the controls, alarms and interlock,
component by component.

9.1.6

Application of HAZOP

HAZOP is effective at any stage of the plant`s life;

1. Design phase
2. Running plant
3. Modifications
Complete HAZOP needs management and commitment.
Field of application of HAZOP
1. Continuous process
2. Bath process

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Chapter 9

HAZOP Method

9.1.7

Advantages of HAZOP

i.

Systematic and comprehensive technique.

ii.

Team work.

iii.

Everyone is responsible for his or her work, so no one can blame can blame the
others.

iv.

Everyone is available in discussion.

v.

Ownership is divided among the participants.

9.1.8

Limitations of HAZOP

a. Qualitative technique
b. Very time consuming and laborious for complex systems.
c. Required detailed drawings design.

4. Guide word would need to be developed.

9.2

Philosophy-Hazards vs. Operability Study:

HAZOPs concentrate on identifying both hazards as well as operability problems. While the
HAZOP study is designed to identify hazards through a systematic approach, more than
80%of study recommendations are operability problems and are not, of themselves, hazards.
Although hazard identification is the main focus, operability problems should be identified to
the extent that they have the potential to lead to process hazard, results in an environmental
violation or have a negative impact on profitability. A definition of hazard and operability is
given below:

9.2.1

Definition:

Hazard
Any operation that could possibly cause a catastrophic release of toxic, flammable or
explosive chemicals or any action that could result in injury to personal.

Operability
Any operation inside the design envelope that would cause a shutdown that could possibly
lead to a violation of environmental, health or safety regulations or negatively impact
profitability.

105

Chapter 9

9.3

HAZOP Method

Technical Approach to HAZOP:

9.3.1

Guidewords, Selection of parameters and Deviation:

The HAZOP process creates deviations from the process design intent by combining guide
words (No, more, less, etc.) with process parameters resulting in a possible deviation from
design intent, for example, when the guide word No is combined with the parameter flow
the deviation no flow results. The team should then list all credible causes that will in a no
flow condition for the node. A sample list of guide words is given below. It should be pointed
out that not all guideword/parameters combination will be meaningful.

9.3.2

Guidewords:

No or not-no part of the intent is achieved and nothing else occurs (e.g., no flow)
More-quantitative increase (e.g., higher temperature)
Less-quantitative decrease (e.g., lower pressure),
Part of-qualitative decrease (e.g., only one of two components in mixture)
Reverse-opposite (e.g., backflow)
Other than-no part of the intent is achieved and something completely different occurs (e.g.,
flow of wrong material) [16]
As well as-qualitative increase (e.g., an impurity) The application of parameters will depend
on the type of process being considered , the equipment in the process and the process intent,
the HAZOP-PC software include two pop-up menus that lists both specific parameters and
general parameters, The most common specific parameters that should be considered are
flow, temperature, pressure, and where appropriate, level. In almost all instances, these
parameters should be evaluated for every node. The scribe shall document, without
exception, the teams comments concerning these parameters.
Additionally, the node should be screened for application of the remaining specific
parameters (see list below) and for the list of applicable general parameters (see PHApro3TMsoftware). These should be recorded Only if there is a hazard or operability problem
associated with the parameter. A sample set of parameters includes the following:

9.3.3

Specific Parameters

Flow
Temperature
Pressure
Composition
Phase
Level
106

Chapter 9

HAZOP Method
Instrumentation.
Relief

9.4

The HAZOP (Hazard and operability) Method:

Sampling
Corrosion/Erosion
Services/Utilities
Maintenance
Addition
Safety
Reaction
Inserting/Purging
Contamination

Requirements; Specific parameters should be considered by team when evaluating each node.
If a particular parameter does not change from one node to the next then it is not necessary to
repeat all of the deviation that were considered in the previous node.
Merely refer to the case in the deviations column of the node presently being considered.

9.5

The System for HAZOP Method:

1. Those system, engineered designs and written procedures that are designed to prevent
catastrophic release of hazardous or flammable material.
2. Those systems that are designed to detect and give early warning following the
initiating cause of a release of hazardous or flammable material.
3. Those system or written procedures that mitigate the consequences of a release of
hazardous or flammable material.

The team should use care when listing safeguard, Hazard analysis require an evaluation of the
consequences of failure of engineering and administrative controls, so a careful determination
of whether or not these items can actually be considered safeguard must be made. in addition
, the team should consider realistic multiple failures simultaneous events when considering
whether or not any of the above safeguards will actually function as such in the event of an
occurrence.

107

Chapter 9

9.6

HAZOP Method

HAZOP study for sulfur:

General:
Synonyms: sulfur, brimstone, flour sulfur, flower of sulfur, precipitated sulfur,
sublimed sulfur, bensulfoid, flower of sulfur, , precipitated sulfur, agri-sul, asulfasupra,
collokit, colsul, cosan, crystex, devisulfur, elosal, gofrativ, hexasul, kolofog, kolospray,
kristex, kulumus, microwetulf, sofril, sperlox-s, spersul, sufran, sulfex, sukfidal, sulforon,
sulkolsulsol, tesuloid, thiolux, thiovit, thiozol, wettasul.
Use: added to soil to increase acidity, chemical reagent
Molecular formula: S

Physical data:
Appearance: yellow powder or fused solid, or amber to yellow crystals
Melting point: 116 0C (depending upon form)
Boiling point: 445 0C
Vapour density (air=1): 8.8
Density (g/cm3): 2.01
Flash point: 188 0C
Flammable Limits: LEL: 3.3 UEL: 46.0
Water solubility: negligible.

Stability:
Stable, Dust may form a flammable or explosive mixture with air. Incompatible with
strong oxidizing agents, most common metals, hydrogen, chlorine, fluorine.

Toxicology:
Eye, skin and respiratory irritant.

Personal protection:
Safety glasses. [27]

108

Chapter 9

9.7

HAZOP Method

HAZOP study for H2S:

General:
Synonyms : hydrogen sulphide , hepatic acid, sewer gas, sulfur hydride,
dihydrogenmonosulfide, dihydrogenmonosulfide, sulfur hydride, stinkdamp, sulfureted
hydrogen.

Physical data:
Appearance: colorless gas with strong odour of rotten eggs(odour threshold ca.0.2 ppt)
Melting point: -85 0C
Boiling point: -60 0C
Vapour density: 1.19
Vapour pressure: [typical cylinder pressure ca.17 bar]
Critical pressure: 88 atm
Specific gravity: 0.993 g/ml (liquid at BP), 1.539 g/l at 0C, 760 mm Hg (gas)
Flash point: -82 0C
Explosion limit: 4.3%-46%
Autoignition temperature: 260 0C

Stability:
Stable high flammable, may form explosive mixture with air. Note wide explosive limits.
Incompatible with strong oxidizing agents, many metals. Many react violently with metal
oxides, copper, fluorine, sodium, ethanol.

Toxicology:
Highly toxic-may be fatal if inhaled. Inhalation of a single breath at a concentration of 1000
ppm (0.1%) may cause coma. Corrosive when moist. Skin contact may cause burns, There is
a rapid loss of sense of smell on exposure to gas concentrations above 150 ppm, and this
means that the extent of exposure may be underestimated.
Perception threshold ranges from 0.5 ppt to 0.1 ppm. Irritant, Asphyxiant.

Personal protection:
Safety glasses, rubber gloves, good ventilation. Remove all sources of ignition from the
working area. [28]
109

Chapter 9

9.8

HAZOP Method

Recommendations for the Storage of Gas Oil

Many of the problems which may arise during the storage of Gas Oil can easily be prevented
by good housekeeping which should include:
Regular draining of tanks to remove water, so helping to prevent the possibility of
microbiological contamination.
Periodic inspection of tanks for evidence of corrosion.
Periodic internal cleaning of tanks to remove any accumulated sludge.
Avoidance of translucent plastic tanks for storage purposes.[29]

110

Chapter No.10
Cost Estimation
10.1 Why estimation?
Before the plant to be operated, specified money must be supplied to purchase and
install the equipment. The capital needed to supply the necessary plant facilities is called
fixed capital investment while that for the operation of the plant is called the working
principal and sum of two capitals is called total capital investment.
An acceptable plant design must present a process that is capable of operating under
conditions which will yield a profit. Since, Net profit total income-all expenses. It is essential
that chemical engineer be aware of the many different types of cost involved in
manufacturing processes. Capital must be allocated for direct plant expenses; such as those
for raw materials, labor, and equipment. Besides direct expenses, many other indirect
expenses are incurred, and these must be included if a complete analysis of the total cost is to
be obtained. Some examples of these indirect expenses are administrative salaries, product
distribution costs and cost for interplant communication. [16,23]

10.2 Cost Estimation of equipments

CE

CB * (Q/QB)M [30] 1

Where CE

equipment cost with capacity Q

CB

known base cost for equipment with capacity QB

constant depending on equipment type

Ce

C*Sn [23]

Ce

purchased equipment cost, $,

characteristic size parameter,

cost constant

index for that type of equipment.

.. 2

Where,

111

Chapter 10

Cost Estimation

=
CE Index 2013 (average)

577.4

CE index 2006(average)

500

CE index 2004 (average)

444

CE index 2000 (average)

435.8

Fired heater (Furnace)

C

$ 540 *2 [23]

$ 1080

0.77

3.3*104 kW

Now put these values in equation 2

=

$ 1080 * (3.3*104)0.77

$ 3.26*106

CE, in year 2013

$ 3.26*106 (577.4/444)

CE, in year 2013

$ 4.24 *106

QB

80 m2

CB

$ 3.28 * 104

0.68 [30]

Ce

Heat Exchanger

Capacity of exchanger, Q

110.183 m2

112

Chapter 10

Cost Estimation

Now put these values in equation 1

CE

$ 3.28 * 104 * (110.183/80)0.68

CE

$ 4.08 * 104

CE

$ 4.08 * 104 * (577.4/435.8)

CE

$ 5.40 * 104

Reactor
Material of construction = Stainless steel
Ce

a + bSn

Ce

Purchased equipment cost on a US gulf cost basis Jan 2007

a,b

Cost constants

Size parameter

Exponent of that type of equipment

157.6 m3

53000 + (28000 (157.6)0.8)

$ 1656995

Putting values

Purchased cost in 2007

$ 1656995

Average inflation rate from 2007 to 2013 = 2.5%

Purchased cost in 2013

1656995 * (1.025)7

$ 1969646.35

113

Chapter 10

Cost Estimation

Pump
Material of construction = Carbon steel
Ce

a + bSn

Putting values in formula

Ce

6900 + (206 (46)0.9)

Purchased cost in 2007

$ 13361.74

Average inflation rate from 2007 to 2013 = 2.5%

Purchased cost in 2013

$13361.74 * (1.025)7

$ 15882.91

Scrubber
QB

0.1 m3

CB

$ 4.92 * 103

0.53 [30]

Capacity of Scrubber, Q

1.74 m3

Now put these values in equation 1

CE

$ 4.92 * 103 * (1.74/0.1)0.53

CE

$ 2.24 * 104

CE

$ 2.24 * 104 * (577.4/435.8)

CE

$ 2.97 * 104

0.1 m3

Stripper
QB

114

Chapter 10

Cost Estimation

CB

$ 4.92 * 103

0.53 [30]

Capacity of Stripper, Q

7.87 m3

Now put these values in equation 1

CE

$ 4.92 * 103 * (7.87/0.1)0.53

CE

$ 4.98 * 104

CE

$ 4.98 * 104 * (577.4/435.8)

CE

$ 6.6 * 104

QB

70.88ft2

CB

$ 60781.22

0.49 [16]

Separator

Capacity of exchanger, Q

78.50 m2

Now put these values in equation 1

CE

$ 60781.22* (78.50/70.88)0.49

CE

$ 63899.72

CE

$ 63899.72 * (577.4/500)

CE

$ 73791.5

Cost of Raw material

Cost of Diethanolamine in 1998

$ 1.70/kg [23]

Cost of Diethanolamine in 2013

$ 1.70 * (577.4/390)

$ 2.52/kg
115

Chapter 10

Cost Estimation

Cost of hydrogen

4.19/kg [31] or $ 7.17/kg

Total Purchased Cost

Equipments

Cost
$ 4240000

Fired heater

$ 54000

Heat exchanger
Reactor

$ 1970000

Separator

$ 73791.5

Scrubber

$ 29700

Stripper

$ 66000

Centrifugal Pump

$ 15883
$ 6449374.5

Total

10.3 Fixed capital investment

10.3.1 Direct cost
Component
Purchased equipment, E'
Delivery, fraction of E'

% Fix Capital Investment

10

Subtotal: delivered equipment

Cost million $
6.449
0.645
7.094

Purchased equipment installation

40

2.838

Instrumentation&Controls(installed)

11

0.780

Piping (installed)

90

6.385

Electrical systems (installed)

60

4.256

Buildings (including services)

10

0.709

Yard improvements

03

0.213

Service facilities (installed)

20

1.419

Total direct costs

23.694

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Chapter 10

10.3.2

Cost Estimation

Indirect cost

Component
Engineering and supervision

% Fix Capital Investment

10

Cost million $
0.709

Construction expenses

09

0.638

Legal expenses

04

0.284

Contractor's fee

04

0.284

Contingency

07

0.497

Total indirect costs

2.412

Fix capital investment

Direct cost + Indirect cost

F.C.I

D.C

23.694 + 2.412

$ 26.106 *106

F.C.I

I.C

Working capital
Allowing 5% of fix capital investment to cover the cost of initial charge
Working capital

0.05 * $ 26.106 *106

Working capital

$ 1.305*106

10.4 Total capital investment

Total capital investment

Total capital investment

fixed capital investment + working capital

$ 26.106 *106 + $ 1.305*106

$ 27.411*106

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Chapter 10

Cost Estimation

10.5 Production cost per year

10.5.1

Variable cost

Name of Material

Raw Materials
Price, $/liter
Annual Amount,
million liter/y

Annual raw
materials cost,
million $/y

Gas Oil
0.50
1450.700
Hydrogen
0.01
47965.000
Diethanolamine
2.74
0.062
Total annual cost of raw materials =

Item

Factor

Raw materials
Operating labor
Operating supervision
Utilities
Maintenance and repairs
Operating supplies
Laboratory charges
Royalties (if not on lump-sum
basis)

10.5.2

Basis

725.35
306.98
0.17
1032.50

Basis cost,
million $/y

Cost,
million $/y

0.15

of operating labor

0.885

0.05

of FCI
of maintenance &
repair
of operating labor

26.816

1032.496
0.885
0.133
2.025
1.341

1.341
0.885

0.201
0.133

1172.281

11.723
1048.768

0.15
0.15

0.01 of co
Variable cost =

Fixed cost

Item
Taxes (property)
Financing
(interest)
Insurance
Rent

Basis cost, million

$/y
26.816

Factor

Basis

0.02

of FCI

0
0.01
0

of FCI
26.816
of FCI
26.816
of FCI
26.816
Fixed Charges =

Cost, million
$/y
0.536
0.000
0.268
0.000
0.804

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Chapter 10

10.5.3

Cost Estimation

Plant overhead
Item

Factor

Plant overhead,
general

10.5.4

0.6

Basis cost,
million $/y

Basis

of labor, supervision and

maintenance
2.358
Plant Overhead =

Cost,
million $/y
1.415
1.415

General expenses
Basis cost,
million $/y

Cost,
million $/y

2.358

0.472

of co

1155.449

57.772

of co

1155.449

46.218
104.462

Item

Factor

Administration
Distribution &
selling
Research &
Development
General Expense =

0.2

of labor, supervision and

maintenance

0.05
0.04

Total product cost

Basis

$1155.449*106/year

Manufacturing cost =

T.P.C general expenses

Manufacturing cost =

$1050.987*106/year

Total annual value of products =

$ 1173 *106

Assume that the Fixed Capital Investment depreciate by straight line method for 10 years.

Gross income

Depreciation, D

(V-Vs)/N

F.C.I

$ 26.106 *106

Vs

No. of years, N

10

($ 26.106 *106)/ 10

$ 2.6106*106

Total Income - Total Product Cost Annual depreciation

119

Chapter 10

Cost Estimation
=

$ 1173 *106 - $ 1155.449*106 - $ 2.6106*106

Gross income

$ 14.94 *106

Net profit

Gross income Taxes

0.40 * Gross income

0.40 * $ 14.94 *106

Tax

$ 5.98 *106

Net Profit

Gross income Taxes

$ 14.94 *106 - $ 5.98*106

Net Profit

$ 8.96 *106

Annual cash flow

Net income + Depreciation

$ 8.96 *106 + $ 2.6106*106

$ 11.57 *106

Let the tax rate is 4%

Tax

Annual cash flow

10.6 Rate of Return

Rate of return

Rate of return

Net profit * 100/ total capital investment

$ 8.96 *106 * 100/$ 27.411*106

32.68 %

10.7 Pay out period

Pay out period

Pay out period

depreciable fixed capital investment/after tax cash flow

$ 26.106 *106/$ 11.57 *106

2.26 year

120

References

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J. G. Speight, The Chemistry and Technology of Petroleum, Fourth Edition: Taylor

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http://en.wikipedia.org/wiki/petroleum

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J. C. Macrae, An introduction to the study of fuel: Elsevier Pub. Co., 1966.

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Oilfield Processing of Petroleum: Crude oil By Francis S. Manning, Richard E.

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J. H. Gary and G. E. Handwerk, Petroleum Refining: Taylor & Francis, 2001.

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Nelson,W.L Petroleum Refinery Engineering McGraw-Hill Book Company Inc.

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http://en.wikipedia.org/wiki/hydrodesulfurization

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MOLECULAR MODELING OF GAS OIL HYDRODESULFURIZATION by Gang

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24. RULES OF THUMB FOR CHEMICAL ENGINEERS A manual of quick, accurate
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122