Design of Ammonia Production Plant

with Membrane Separation Technology

1. Muhammad AsimShahzad 2008-NUST-BE-Chem-68
2. Muhammad Mujahid 2009-NUST-BE-Chem-14
3. Muhammad Numan 2009-NUST-BE-Chem-16
4. Mubeen Mukhtar 2009-NUST-BE-Chem-67
This work is submitted as a FYP report in partial fulfillment of the
requirement for the degree of
(BE in Chemical Engineering)

Project Supervisor: Dr. Arshad Hussain

School of Chemical and Materials Engineering (SCME)
National University of Sciences & Technology (NUST), H-12
Islamabad, Pakistan
June 2013
I n the N ame of A l l ah, the M ost G raci ous, the M ost M erci f ul

















CERTIFICATE
This is to certify that work in this dissertation/report has been completed by
Muhammad Mujahid, Mubeen Mukhtar, Muhammad Numan and Muhammad
Asim Shahzad under my supervision at School of Chemical and Materials
Engineering, National University of Sciences and Technology, H-12, Islamabad,
Pakistan.




Supervisor:
Dr. Arshad Hussain
HoD Chemical Engineering
School of Chemical and Materials Engineering (SCME)
National University of Sciences and Technology (NUST)




Submitted through:

HoD Principal/Dean
Chemical Engineering SCME NUST









Dedicated to our Beloved Parents and Respected Teachers !














ACKNOWLEDGEMENTS




All praises to ALMIGHTY ALLAH, who provided us with the strength to accomplish the final year

Before anybody else we thank our Parents who have always been a source of moral support and
driving force behind whatever we do. We are indebted to our project advisor Dr. Arshad Hussain for
his worthy discussions, encouragement, inspiring guidance, remarkable suggestions, keen interest,
constructive criticism& friendly discussions which enabled us to complete this report. He spared a lot
of his precious time in advising & helping us in writing this report. Without his painstaking tuition,
kind patronization, sincere coaching and continuous consultation, we would not have been able to
complete this arduous task successfully.


We are also grateful to Mr. Shahid Hussain Ansari, Mr. Umair Sikandar, Mr. Nauman Ahmed and all
the Teachers for their profound gratitude and superb guidance in connection with the project.







Authors





project. All respects are for His HOLY PROPHET (Alayehis Salam), whose teachings are
true source of knowledge& guidancefor wholemankind.

ABSTRACT

Fertilizer Industry which constitutes the backbone of the agriculture, the largest GDP
contributing sector in Pakistan is of strategic importance. There is an ever increasing demand of
fertilizers especially urea. Exceeding expense on the import bills of this crucial commodity
requires expensive foreign exchange. Therefore Pakistan has a huge growth potential for urea
industry. Ammonia production is the first step before manufacturing urea. So ammonia
technology always remains the field of key interest for chemical engineering students.
This project consists of comprehensive design of ammonia plant in generalized manner. It
includes literature review and process selection, creation of PFDs with material and energy
balances, designing of process equipment, cost estimation and analysis of ammonia plant.
This project also includes the design of membrane unit capable of recovering maximumquantity
of H2 frompurge gas of ammonia synthesis loop in spite of conventional cryogenic separation
technique being used in major ammonia production plants in Pakistan. Prior to H2 recovery,
NH3 is being recovered frompurge gas by water scrubbing.

Table of Contents
Certificate.......................................................................................................................... ii
Acknowledgements........................................................................................................... iv
Abstract ............................................................................................................................ v
List of tables...vi
List of Figures ...vi
Table of Contents................................................................................................................vii
1 INTRODUCTION ..1
2 LITERATURE REVIEW 2
2.1 Process Selection and Description ...2
2.2 LTS and HTS design.6
2.3 Carbon Dioxide Removal.15
2.4 Ammonia Convertor.17
2.5 Hydrogen Recovery Unit..23
3 MEMBRANE SEPARATION TECHNOLOGY24
3.1 Membranes for Hydrogen Separation.....24
3.2 Why Polyimide? ..25
3.3 Hollow Fibers Preparation...25
3.4 Hollow Fiber Module...27
3.5 Asymmetric Membrane Transport Mechanism.,.28
3.6 Working of Hollow Fiber Module..30
4 MATERIALS BALANCE ....32
4.1 NG and Recycle Stream Mixing Point32
4.2 Desulfurizer.33
4.3 Feed Gas and Steam Mixing Point..34
4.4 Primary Reformer...35
4.5 Secondary Reformer...36
4.6 High Temperature Shift Converter - HTSC...37
4.7 Low Temperature Shift Converter LTSC...38
4.8 2
nd
KO Drum.39
4.9 CO
2
Absorption.....40
4.10 Methanator...41
4.11 3
rd
KO Drum41
4.12 1
st
Stage of Compressor...42
4.13 2
nd
and 3
rd
Stage of Compressor...43
4.14 Make up Gas Mixing Point..43
4.15 Separator..44
4.16 Ammonia Synthesis Convertor44
4.17 Purge Gas Exit Point45
4.18 Ammonia Recovery Unit - ARU.46
4.19 Recovered NH
3
Mixing Point..46
4.20 Hydrogen Recovery Unit - HRU.47
5 ENERGY BALANCE..48
6 EQUIPMENT DESIGNING51
6.1 High Temperature Shift Converter51
6.2 Low Temperature Shift Converter56
6.3 ABSORPTION COLUMN61
6.4 DESIGN STEPS OF AMMONIA REACTOR.....67
6.5 AMMONIA RECOVERY UNIT..74
6.6 Hydrogen Recovery Unit...78
7 COST ESTIMATION82
7.1 Cost Index Calculation82
7.2 Fixed Costs.82
7.3 Cost of Equipment..84
7.4 Operating Cost: ..86
7.5 Variable Costs: ..86
7.6 Fixed Cost..87
8 INDUSTRIAL APPLICATIONS.89
8.1 Fertilizer.89
8.2 Precursor to Nitrogenous Compounds..89
8.3 Cleaner..89
8.4 Refrigeration R717.89
8.5 Remediation of Gaseous Emissions..89
8.6 Fuel...90
8.7 Stimulant in Sports90
8.8 Textile: .90
8.9 Lifting Gas: ..90
8.10 Wood Working: .91
9 CONCLUSIONS.92
9.1 Recoveries Importance.92
9.2 Membrane Separation Technology..92
10 References.93



List of Tables
Table 2.1 Comparison of Carbon Dioxide absorption Processes .15
Table 3.1 Engineering Strategies for Hydrogen Separation membrane24
Table 3.2 Comparison of Membranes for Hydrogen Separation...25
Table 3.3 Influence of Operating Variables...31
Table 9.1 Comparison of Polymer membrane and Cryogenic separation..85


List of Figures
Figure 2.1 Process steps of Ammonia Production..2
Figure 2.2 Equilibrium CO concentration in LTS......12
Figure 2.3 Sulfur and Temperature Profile For used LYS Catalyst...13
Figure 2.4 S -300 Ammonia Converter ..............22
Figure 3.1 Experimental set-up for hollow fiber spinning..27
Figure 6.1 Fixed bed Reacor51
Figure 6.2 Reaction Mechanism...52

1

mmonia is a compound of nitrogen and hydrogen with the formula NH3. It is a colorless
gas with a characteristic pungent odor. Ammonia contributes significantly to the
nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers.
Ammonia, either directly or indirectly, is also a building block for the synthesis of many
pharmaceuticals. Although in wide use, ammonia is both caustic and hazardous. In 2006,
worldwide production was estimated at 146.5 million tones. It is used in commercial cleaning
products.
Ammonia, as used commercially, is often called anhydrous ammonia. This termemphasizes the
absence of water in the material. Because NH3 boils at -33.34 C (-28.012 F), the liquid must be
stored under high pressure or at low temperature. Its heat of vaporization is, however,
sufficiently high so that NH3 can be readily handled in ordinary beakers, in a fume hood (i.e., if
it is already a liquid it will not boil readily). "Household ammonia" or "ammoniumhydroxide" is
a solution of NH3 in water. The strength of such solutions is measured in units of Baume
(density), with 26 degrees Baume (about 30% w/w ammonia at 15.5 C) being the typical high
concentration commercial product. Household ammonia ranges in concentration from 5 to 10
weight percent ammonia. Ammonia is an intermediate product in the manufacture of nitrogenous
fertilizers. It is also used for direct application to the soil and in aqua condition with solutions of
other nitrogenous fertilizers like ammonium nitrate and/or urea. Besides these, ammonia finds
application in the production of nitric acid, soda ash, cleaning agents, leather tanning, petroleum
refining, pulp & paper industry, textiles, refrigeration, rubber & synthetic resin industries,
explosives and food & beverage industries.





A

1 INTRODUCTION
Natural gas. naphtha Fuel oil. coal
~
,~
.l!;~
g=>
~~
~
s
"" ~
..,
~
Air C7>
~
c:
s
Q)
::-

!t
.c:
(/)
~
,g
Xl
~
g
''=
s
!E
a
;f
HT shift
conversion
Shift conversion
(CoMo cat.]
Ammonia syntnesis
2

2.1 Process Selection and Description
In the past years large amount of work is done on designing new and energy conservative
process for the production of Ammonia. The main drive behind designing of year process for
ammonia is to reduce the Energy requirement. Below are mentioned few process developed by
different Companies throughout, for steamreforming. Before going through different process let
us have a look at the components of an Ammonia plant.

Fig 2.1 Process steps of Ammonia Production

2 LITERATURE REVIEW
3

This process combines the use of excess air (up to 25%) in the secondary reformer with a very
active synthesis catalyst. In LCA process the heat generated in the secondary reformer is utilized
in primary reformer by direct heat exchange in a tubular Gas Heated Reformer (GHR). The CO
shift is performed in a single stage shift reactor at 2500
o
C using special copper basic catalyst.
CO
2
, inserts and excess nitrogen are removed from raw synthesis gas by pressure swing
absorption. Ammonia synthesis takes place at low pressure of below 100 kg/cm2g using ICIs
highly active cobalt promoted catalyst. Net energy consumption of around 7.2 Gcal/ MT of
ammonia has been demonstrated for 450 MT per day plant.
2.1.2 Kellogg Brown and Roots Advanced Ammonia Process:
KAAP uses a high pressure heat exchange based steamreforming process integrated with a low
pressure advanced ammonia synthesis process. Raw synthesis gas is produced by steam
reforming of hydrocarbons in a heat exchange based systemunder pressure, based on Kellogg
Brown and Root Reforming Exchange System(KRES). KRES also reduces energy consumption
and capital cost besides reduced emission and enhanced reliability. After sulfur removal, the
auto-thermal reformer and reforming exchanger which operate in parallel, convert 100% feed
into raw synthesis gas in the presence of steamusing nickel catalyst. In auto-thermal reformer,
enriched air supplies nitrogen.
The heat of combustion of partially reformed gas supplies energy to remaining hydrocarbon feed.
The exit gas of auto thermal reformer is fed on the shell side of the KRES and thus heat of
combustion is supplied to the reforming reaction taking place inside the tubes. KRES exit gas is
cooled in waste heat boiler where high pressure steamis generated. After cooling, the gas is sent
to the CO shift converters (high temperature and low temperature). CO2 is removed fromthe
process gas using hot potassiumcarbonate solution, methyl diethanol amine (MDEA) etc. After
CO2 removal, methanation and gas drying processes are carried out. The gas is then compressed
and mixed with recycle streamof synthesis loop where gas mixture is sent to converter designed
by KAAP.
2.1.3 Krupp Uhde GmbH Ammonia Process:
The Krupp Uhde GmbH process uses conventional steamreforming for synthesis gas generation
(front end) and a medium- pressure ammonia synthesis loop. The primary reforming is carried
out at pressure 40 bars and temperature range of 800- 850
o
C. The steamreformer is top fired
and tubes are made of centrifugal high alloy steel which enhances reliability. Process air is added
in secondary reformer through nozzles installed in the wall of vessel. This provides proper
mixing of the air and reformer gas. Subsequent high pressure steamgeneration & superheating,
guarantee maximumheat usage to achieve energy efficiency. Carbon monoxide is converted to
carbon dioxide in HT and LT shift converters.
2.1.1 ICI Leading Concept Ammonia (LCA) Process:
4

The MDEA or Benfield systemis used for carbon dioxide removal. The ammonia synthesis loop
uses two ammonia converters with three catalyst beds with waste heat boiler located downstream
of each reactor. The converters have small grain iron catalyst. The radial flow concept minimizes
pressure drop and allows maximum ammonia conversion.
2.1.4 The Linde Ammonia Concept (LAC) Ammonia Process:
The LAC process consists essentially of a modern hydrogen plant, a standard nitrogen unit and a
high efficiency ammonia synthesis loop. Secondary reformer, one shift conversion and
methanation steps have been eliminated in this process. The primary reformer is top fired and
operates at an exit temperature of about 850
o
C. The CO shift conversion is carried out at 250
o
C
in a single stage in the tube cooled isothermal shift converter and gas is sent to pressure swing
absorption (PSA) unit wherein the process gas is purified to 99.99 mole % hydrogen. A low
temperature air separation in cold box is used to produce pure nitrogen.
BASFs MDEA process has been eliminated in this process used for CO
2
removal. The ammonia
synthesis loop is based on Casale axial - radial three bed converter with internal heat exchanger
giving a high conversion. The energy consumption (feed +fuel) is 7 Gcal/ MT of ammonia.
2.1.5 Haldor Topsoe A/S Process:
The companys low energy ammonia process uses the conventional sequence of process steps
which are optimized by the introduction of improved catalysts, new equipment design and
extensive process optimization studies. A pre-reformer containing nickel catalyst has been also
provided upstreamof primary reformer for converting all the higher hydrocarbons, so that only
methane, carbon monoxide, carbon dioxide, hydrogen and steamare present in the product gas.
Firing in primary reformer is reduced by 15% due to pre- reformer. Highly active shift catalyst
ensures the lowest carbon monoxide at the exit of converters and thus highest utilization of
feedstock. New temperature resistant iron free catalyst makes it possible to operate at low steam
to carbon ratio at high temperature shift converter. The company has also developed Heat
Exchange Reforming Process (HERA). Low energy CO
2
removal processes, such as selexol,
MDEA or low heat potassium carbonate, are used. Topsoe has developed new converters
especially for high conversion loops. The S- 250 loop features an S- 200 two bed radial flow
converter followed by a boiler and S- 50 single bed radial flow converter in series. A new three
bed radial flow S- 300 converter has also been developed which is cheaper than S - 250
configuration and conversion is about the same.
Special focus should be paid to the following features:
Improved reformer design
New nozzle burner for secondary reformer
Modified S-200 ammonia converter design
Condensate stripping with mediumpressure steam
5

Improved catalysts such as e.g. the shape-optimized secondary reforming catalyst
With regard to recovery of the hydrogen in the purge gas fromthe ammonia synthesis loop,
membrane technology is used today in ammonia plants. The operating principle is that the
pressure difference is used as the driving force for the hydrogen to permeate the membrane. In
contrast to the cryogenic unit, this means that the hydrogen-rich streamis recovered at a lower
pressure. The recovered hydrogen is added to the make-up gas upstream the synthesis gas
compressor.
After going through all the above process and having a look at their positive and negative points,
we took all the positive points fromthe above process and tried to develop a new process
Haldor Topsoe A/S Process. In this process the new things which we have introduce are that
we are using aMDEA for CO
2
Removal. In this process we are using a molecular sieve,
Methanator and a CO
2
absorber in a single train which provides us with extra life for Ammonia
converter Catalyst. We have also used radial flow S - 300 Ammonia converter which gives
higher conversion.
Looking at the investment cost, the reformer cost goes up more or less proportionally with the
number of tubes, and since the reformer cost is a significant part of the overall plant cost, it is
important to keep the reformer size small, and thereby minimize the plant cost. Froman energy
point of view, there is no doubt that this scheme is very energy efficient, and gives the lowest
specific energy consumption figures of all currently studied schemes considered for large scale
plants.



To increase the amount of Hydrogen in the process gas
A reactor is a vessel used to carry out the desired reaction under a
controlled set of conditions. This unit is said to be the heart of the process industry, and in
fact, all the other units usually act as its auxiliaries.
2.2 LTS and HTS design
Objective:
Reactor:
Introduction:
Every industrial chemical process is designed to produce
economically a desired product from a variety of starting materials through a succession of
treatment steps. The raw materials undergo a number of physical treatment steps to put them
in the form in which they can be reacted chemically. In the next step they pass through the
reactor. The products of the reaction must then undergo further physical treatment
separations, purification, etc. For the final desired product to be obtained. Design of
equipment for the physical treatment steps is studied in the unit operations. Economically this
may be an inconsequential unit, perhaps a simple mixing tank. Frequently, however, THE
CHEMICAL TREATMENT STEP IS THE HEART OF THE PROCESS, the thing that
makes or breaks the process economically. Design of the reactor is no routine matter, and
many alternatives can be proposed for a process. In searching for the optimum it is not just
the cost of the reactor that must be minimized. One design may have low reactor cost but the
materials leaving the unit may be such that their treatment requires a much higher cost than
alternative designs. Hence, the economics of the overall process must be considered. Reactor
design uses information, knowledge and experience from a variety of areas Thermodynamics,
Chemical kinetics, Fluid mechanics, Heat transfer, Mass transfer, and Economics. Chemical
reaction engineering is the synthesis of all these factors with the aim of properly designing a
chemical reactor. To find what a reactor is able to do we need to know the Kinetics, the
contacting pattern and the performance equations. In the designing of reactor we want to
know that what size and type of reactor and method of operation are best for a given job.
Because this may require that the conditions in the reactor vary with position as well as time,
this question can only be answered by a proper integration of the rate equation for the
operation. This may pose difficulties because of the temperature and the composition of the
6


reacting fluid may vary point to point within the reactor, depending on the endothermic or
exothermic character of the reaction, the rate of heat addition or removal from the system,
and the flow pattern of the fluid through the vessels. In effect, then, many factors must be
accounted for in predicting the performance of a reactor.
Classification of chemical reactors can be achieved in two different kinds.
1. Depending upon the nature of reactants and product
(a) Homogeneous Reactors
(b) Heterogeneous Reactors
2. Depending upon the mode of operation
(a) Batch Reactors
(b) Continuous Reactors ( Stirred tank reactor, Tubular flow Reactor)

In Homogeneous Reactors only one phase, usually a gas
or a liquid, is present. If more than one reactant is involved, provision must of course be
made for mixing them together to form a homogeneous whole. Often mixing the reactants is
the way of starting off the reaction, although some times the reactants are mixed and then
brought to the required temperature.
In Heterogeneous Reactors two or possibly three,
phases are involved, common examples are gas liquid, liquid solid, and liquid liquid
systems. In cases where one of the phases is a solid, it is quite often present as a catalyst; gas
solid catalytic reactors particularly form an important class of Heterogeneous catalytic
Reactors. In a gas solid catalytic reactor, the reaction takes place on the surface of catalyst
and hence heterogeneous. However, bubbling a gas through a liquid may serve just to
dissolve the gas in the liquid where it then reacts homogeneously. The reaction is then
homogeneous but the reactor is heterogeneous itself. Generally, a heterogeneous reactor
exhibits a greater variety of configurations and contacting pattern than homogeneous reactors.
Another kind of classification which cuts cross
the homogeneous heterogeneous division is the mode of operation. Batch wise operation
has carried out small scale preparative reactions in the laboratory. There are many situations,
Classification of Reactors:
Homogeneous Reactors:
Heterogeneous Reactors:
Batch and Continuous Reactors:
7


however, especially in large scale operations, where considerable advantage occurs by
carrying out the chemical reaction continuously in the flow reactor.

Continuous reactor

Batch reactor
1. It is used for low
residence time
operations.
2. It has low operating cost.
3. Production variation
takes time to attain
steady state.
4. Continuous flow reactors
are smaller than batch
reactors providing the
same productivity.
1. It is used for high
residence time
operations.
2. Its operating cost is high
3. Production can be varied
easily during each batch.
4. Batch reactors are larger
than continuous reactors
providing the same
productivity.


As we have very high flow rate in our process so we are going to use a continuous flow
reactor. Flow the below comparison we will come to know which continuous flow reactor is
best to fulfill our purpose.
There are mainly three types of continuous flow reactors:
1. Fixed Bed reactor.
2. Fluidized bed reactor.
3. CSTR reactor.


Difference between continuous and batch reactor:
Continuous flow reactors:
8



Fixed bed reactor

Fluidized bed reactor

CSTR reactor
1. They primarily used for
gas phase solid
catalyzed reaction &
gas solid reactions.
2. Pressure drop is low.
3. High catalyst load per
unit volume of reactor.
4. Catalyst replacement is
relatively hard.
5. Relatively low heat and
mass transfer.
1. It is also mostly
used for gas
phase solid
catalyzed reaction
and gas solid
reactions.
2. Pressure drop is
high.
3. Catalyst is
regenerated
continuously.
4. High heat and
mass transfer.
1.Useful for Liquid-Liquid
system.
2.Useful for slow reactions
requiring large hold up time.
3.Useful where high mixing is
required.
4.High heat and mass transfer
efficiencies.
5.High power consumption per
unit volume of fluid.

The points which should be considered in
case of selection of type of reactor are given below.
1- Conversion.
2- Selectivity.
3- Productivity.
4- Yield.
5- Heat exchange.
6- Mixing.
7- Catalyst Distribution.
8- Hold-up Time.
9- Availability.
10- Compatibility with processing.
11- Energy utilization.
12- Safety.
13- Economics.

Selection Criteria of Rector:
9


We have selected fixed bed reactor. Reasons are given below.
1. Very high Flow rate is required thats why we are using fixed bed reactor.
2. The reactor is adiabatic in nature (no heat transfer media is used) because it aids in the
reaction.
3. Fixed bed reactors have a low pressure drop.
4. There is no requirement of catalyst regeneration.
5. Low operation cost.
Now we turn our attention to the reaction
taking place in the reactor. Water Gas shift reaction is taking place in the reactor. There are
three types of fixed bed reactors in which Water gas shift reaction can be carried out. Water
gas Shift reaction is defined as

Water gas Shift Converter is an reactor in which Carbon monoxide reacts with water to
Produce Carbon dioxide and Hydrogen, at certain temperature and Pressure Condition, in
the presence of catalyst.
CO + H
2
O CO
2 +
H
2
H

298
= 41.1kJmol
1

We will go through their theory and type of catalyst that they use one by one.
1. High Temperature Shift Converter.
2. Intermediate temperature Shift Converter.
3. Low Temperature Shift Converter.
In the unreduced state the HTS
catalyst is iron (III) oxide (Fe
2
O
3
) containing additionally 5 - 10 % chromic oxide (Cr
2
0
3
).
During operation, it is reduced more or less stoichiometrically to the composition of
magnetite (Fe
2
O
3
) 15931 - 15951. The catalyst is active in the temperature range of 300 - 500
"C. Steam surplus is not only necessary for thermodynamic reasons but also to suppress
undesirable side reactions. Decreasing the steam surplus lowers the oxygen to carbon ratio in
the HTS to such an extent that the atmosphere can reduce magnetite partially to metallic iron.
In addition the Koudouard reaction can occur under these conditions. The resulting carbon is
deposited within the catalyst particles causing their disintegration, and iron carbides will be
formed, which are effective Fischer - Tropsch catalysts that lead to the formation of some
High Temperature Shift Converter:
Water Gas Shift reaction:
10


methane and higher hydrocarbons. The minimum steam surplus depends on the CO/CO,
ratio, lower values allowing lower steam surplus. Thus in conventional plant operation at 32 -
35 bar with CO/CO, of 1.65 -2.13, an S/C ratio in the primary reformer of around 3.0 seemed
to be the minimum with respect to the HT shift, whereas for concepts with reduced primary
reforming and a CO/CO
2
ratio of 1.2 and S/C ratio of 2.8 was sufficient. Newly introduced
HTS catalysts with additional copper promotion (e.g. 3 %) suppress this side reaction and are
therefore less sensitive to lower steam-to-gas ratios. The presence of MgO and ZnO should
also effect some reduction of methane formation. A review of catalyst research, surface
science investigations and relevant literature is given in. The function of Cr
2
O
3
is mainly to
prevent the sintering of the iron oxide, which leads to a reduction of surface area. But
attempts to substitute Cr by Ce or Zr [604] - [607] (because in commercial Fe/Cr catalysts a
minor amount of the chromium is still present as Cr
6+
resulted in a lower activity of these Cr-
free catalysts. In the production of the HTS catalyst, mixed iron(III)hydroxide and
chromium(III)- hydroxide are precipitated from an aqueous solution of ferrous sulfate and
chromic acid by addition of sodium hydroxide solution while agitating with air to perform the
oxidation of Fe
2
to Fe
3
and injecting steam for temperature adjustment. The oxide slurry is
washed in alternating agitating and settler operations (to achieve very low residual sulfur
content). The washed hydroxides are spray-dried and the resulting powder is granulated with
an additive which serves as lubricant and binder and then pressed into tablets of the required
size 6 x 6 mm, 9 x 5 m, 9 x 9 mm are standard, but other dimensions are possible, too). Some
manufactures use iron nitrate instead of iron sulfate as raw material. The BET surface area of
commercial Fe-Cr HT shift catalysts is between 30 and 80 m2/g, depending on Cr
2
O
3
content
and calcining temperature. The space velocities in commercial HT reactors are today
approximately 3500 - 4500 h
-1
. The classical HTS iron catalyst is resistant against sulfur
compounds, but this is of greater importance in partial oxidation processes and less for the
practically sulfur- free steam reforming gas. In some ammonia process schemes operating
without a secondary reformer and applying pressure swing adsorption (PSA) for further
purification (KTI PARC), only a HTS is used.
Relatively new process
concept is the intermediate temperature shift, which performs the reaction in a single step.
The catalyst is based on a copper- zinc alumina formulation and optimized for operating in a
wider temperature range (200 - 350
0
C) than the standard LTS catalyst (190 - 275
0
C). The
Intermediate Temperature Shift Converter:
11
04 j
I
Composition of gas at entry.
vol-% (dry)
Hz : 59.94
N2 . 20.47
CO : 3.11
CO
2
: 1591
A : 0.26
CH
4
: 0.32
t 0. 3
~
3
~ 0.2
<Ji
~
80.1.
o
180 200 220 240 260
Converter outlet temperature. C __


reaction heat can be removed by use of a tube-cooled reactor raising steam or heating water
for gas saturation to supply process steam in the reforming section (Linde LAC, ICI Catalco
LCA). In a new plant using the spiral wound Linde reactor, a methane slip of only 0.7 mol %
(dry basis) is achieved. Further purification is performed by PSA. Generally the shift
conversion reactors have an axial gas flow pattern, but recently radial gas flow configurations
have been chosen in some instances. The lower gas velocities result in reduced pressure drop,
which saves compression energy and allows the use of smaller catalyst tablets ( 3 x 3 mm or 2
x 2 mm), which because of the higher activity can achieve a lower CO leakage. In a 1000 t/d
plant without hydrogen recovery the ammonia production would be increased by 10 t/d.
Ammonia Casale has patented radial flow designs for both HTS and LTS. In a recent revamp
the pressure drop was reduced from 0.55 to 0.35 bar in the HTS and from 0.55 to 0.22 in the
LTS. The CO leakage from the LTS could lowered to 0.11 % from 0.25 % 16.
The classical iron - chromium
catalyst exhibits a sufficient activity only above temperatures of 320 - 360
0
C. The
introduction of the new copper - zinc based low-temperature shift catalyst in 1963, made it
possible to take advantage of the lower equilibrium CO concentrations at temperatures
around 200
0
C. As can be seen from the diagram, a rather low CO concentration even at very
low steam/gas ratios should be attainable with a sufficiently active LTS catalyst. In
combination with methanation. it was possible to replace the energy consuming copper liquid
scrubbing stage, which was used in old plants to remove the comparatively high residual CO
content (around 3%) after the HTS.

Equilibrium CO concentration in LTS
Low Temperature Shift Converter:
12
100000
Catalyst temperature
230
r
10000
r
220
3=
<-:>
E
1000
D
0
~ cD
c::t..
210 ---
~
~
.a.
Sulfur - =:;
CD
~
c/
100
E
~
10
Top Reactor height Bottom


The LTS catalyst, supplied in pellets like the HTS catalyst, consists of 40-55 % copper oxide,
20 - 30 % zinc oxide, the balance being alumina. The catalyst properties are influenced far
more by the formulation and manufacturing procedure than by its chemical composition. It
makes a great difference whether the individually prepared components are just mixed
physically as oxides or are incorporated by co-precipitation. The latter procedure assures a
rather fine distribution of the copper oxide crystals, which are well separated from each other
by zinc oxide and even smaller alumina crystals. This retards sintering of the copper
cristallites in the reduced catalyst during prolonged operation. The co-precipitation step of the
catalyst manufacturing sequence has to be very carefully controlled with respect to
temperature, pH, and agitation to achieve the desired result. Commercial pellet sizes range
from 6.4 x 3.2 mm to 3.5 x 3 mm; the surface area is around 60 - 120 m'/g, and the pore
volume 0.35 - 0.45 ml/g. The copper oxide is reduced in situ with hydrogen and a carrier gas
(usually nitrogen) to form the fine copper crystallites of about lo-' cm on which the activity
depends. Sulfur, usually present as H
2
S, has to be below 0.1 ppm, but even with such low
concentrations, the catalyst is slowly poisoned. The ZnO adsorbs the sulfur and it finally
transforms into bulk ZnS. When the ZnO is exhausted in a given layer of the catalyst, the H,S
causes deactivation of the copper by sintering. The poisoning process moves through the
catalyst as a relatively sharp front and can be seen in the change of the catalyst temperature
profile over time. The LTS catalyst is protected by a guard bed, formerly loaded with ZnO,
but nowadays usually with LTS catalyst. Changing the guard bed more frequently prolongs
the service life of the main LTS catalyst bed. Without a guard bed the lifetime is normally 2-4
years, depending on gas quality. With an upstream guard bed.

Sulfur and Temperature Profile For used LYS Catalyst
13


Changed at appropriate intervals the life time of the main bed can be extended to 6 10
years. Traces of chlorine compounds, which may be introduced with the natural gas or more
often with the process air to the secondary reformer, may also deactivate the LTS catalyst by
accelerating the sintering of the copper particles. Unlike sulfur poisoning, chlorine is more
diffusely distributed over the whole catalyst bed by migration as volatile zinc and copper
chlorides. A chlorine guard catalyst for installation upstream of the LTS is offered by catalyst
vendors. As chemical composition and formulation of the LTS catalyst are very similar to
methanol production catalysts, small quantities of methanol are formed and found in the
process condensate after cooling the LTS effluent. In a consecutive reaction, amines (mainly
methylamine) are formed from the methanol and traces of ammonia originating from the
secondary reformer and the HTS. These pollutants are removed from the process condensate
by steam stripping and ion exchange. Byproduct formation is higher with fresh catalyst and
declines with operating time. New catalyst types with increased activity and higher selectivity
have reduced the problem. The tendency for methanol formation increases with decreasing
steam/gas ratio.
We have used High temperature and Low temperature shift converter in our process due to
following reasons:
1. There not sufficient and reliable data available for intermediate shift converter and it
is not frequently used in the Ammonia plants.
2. In HTS at high temperature we get very high rate of reaction at the cost of low
conversion. In LTS we get a high conversion at the cost of low rate of reaction. The
combination of these two gives us a very high yield of water gas shift reaction.
3. They are help in generation of steam which fulfill the seam requirements for the
ammonia Plant.
14
15

Carbon dioxide is an undesirable constituent in the synthesis gas because it poisons the ammonia
synthesis catalysts. Commercially available hot potassium carbonate processes are Benfield
process, Glycine Vetrocoke process and Catacarb process, while Alkanolamines processes are
Monoethanolamine (MEA) and aMDEA.
Table 2.1 Comparison of Carbon Dioxide absorption Processes
MEA Catacarb Benfield Vetrocoke BASF
aMDEA
Absorbent Monoethanol
amine
Potassium
Carbonate
Potassium
Carbonate
Potassium
Carbonate
Methyl
diethanol
amine
Activator Amine Guard
IV 3
Boric acid DEA Glycine Peprazine
Concentration
%
25-30 25-30 20-25 35-50
Corrosion
Problems
Yes Yes Yes Yes Nil
Corrosion
Inhibitor
V2O5 V2O5 As2O5 Nil
Foaming
Problems
High High High High Low
Degradation
and Volatility
2

Degrades at
high
temperature,
volatile
Non-volatile,
No
degradation
Non-volatile,
No
degradation
Non-
volatile,
No
degradation
Non-volatile,
No
degradation
CO2 Slip in
product gas
(ppm)
1

100 500 300 100
CO2 purity %
1
99 98.5 99.4 99.95
Energy
Required
Kcal/kgmol of
CO2
1

25000 19000 16000 9500
Toxicity Toxic
corrosion
inhibitors
Toxic
corrosion
inhibitors
Toxic
corrosion
inhibitors
Toxic
corrosion
inhibitors
Biodegradabl
e and non-
toxic solvent

2.3.1 Carbon Dioxide Absorption Processes
2.3 Carbon Dioxide Removal
16

The main selection criteria are high solubility of carbon dioxide and, equally important, high
absorption selectivity of carbon dioxide. Furthermore, easy desorption is highly desirable, as it
reduces the necessary regeneration temperature and pressure difference. In order to prevent the
loss of solvent, a low vapor pressure and high thermal stability as well as long-termstability are
benecial. Additionally, the cost and environmental toxicity of the solvents have to be taken into
account, especially when evaporative loss and chemical degradation are taken into account.

BASF aMDEA process is highly energy efficient due to the elevated acid gas loadings
achievable with the solvent; this enables using low circulation rates and reduced energy
consumption, as well as reducing equipment size. BASF has used piperazine in its activated
MDEA formulations. Piperazine is ten times more reactive than MEA.
Owing to the low vapor pressure of MDEA and the activator, there are no losses of the active
solvent components. The carbon dioxide binds much less strongly to MDEA than to MEA, and
the solvent character is more like a hybrid between a strong chemical and a purely physical
solvent. On account of the relative weak binding forces, a substantial amount of carbon dioxide
can be recovered simply by flashing to low pressure, and only a small amount has to be
recovered by stripping. The process is very versatile: increasing the activator concentration shifts
the character of the solvent more to the chemical side and vice versa.

In BASF aMDEA process, the gas is treated in a two stage absorber using partially regenerated
solution in the bottomstage and completely regenerated solution in the top stage. Rich solution
fromthe bottomof the absorber passes through a hydraulic turbine for energy recovery and is
then flashed in the high pressure flash unit where most of the dissolved inert gases are released.
The rich solution then flows to the low pressure flash unit, which operates close to atmospheric
pressure. Hot overhead gas fromthe thermal stripping column is passed through the solution in
the low pressure flash tank to improve the efficiency of CO
2
removal in this vessel. A significant
portion of the CO
2
contained in the rich solution is stripped in the low pressure flash tank.
Partially regenerated solution fromthe low pressure tank is split into two portions. The larger
portion is fed to the bottom stage of the absorber while the balance flows to the re-boiled
stripping column. Completely regenerated solution from the striping column is fed to the top
absorption stage, completing the cycle.
BASF aMDEA process is highly energy efficient due to the elevated acid gas loadings
achievable with the solvent; this enables using low circulation rates and reduced energy
consumption, as well as reducing equipment size. BASF has used piperazine in its activated
MDEA formulations. Piperazine is 10 times more reactive than MEA.

2.3.2 BASF aMDEA Process:


Basically reactor is a vessel which is used to carry out
the specific set of reactions under the specific conditions. Normally reactors are also
classified on the basis of phases which they deal. There are two general types of phases:
Homogenous phase.
Heterogeneous phase.
In case of gas-solid phase reactions. Heterogeneous phase reactors are considered.
Heterogeneous catalytic reactors are the most important single class of reactors utilized by
the chemical industry. Whether their importance is measured by the wholesale value of the
goods produced, the processing capacity, or the overall investment in the reactors and
associated peripheral equipment, there is no doubt as to the prime economic role that reactors
of this type play in modern technological society.

Heterogeneous reactors
are further classified on the basis of catalyst position or motion. Generally divided into two
types:
1. Reactors in which the solid catalyst particles remain in a fixed position relative to one
another (fixed bed, trickle bed, and moving bed reactors).
2. Reactors in which the particles are suspended in a fluid and are constantly moving
about (fluidized bed and slurry reactors).
As in our case, our reaction medium is gas-solid, in which gases reacts on the surface of solid
so first type of reactor is to be considered here. Fixed bed reactors are named as fixed because
the catalyst bed is fixed. Fixed bed reactor is further classifies on the basis of the type of
fixed bed which is given below:
A single large bed.
Multiple horizontal beds supported on trays arranged in a vertical stack.
Multiple parallel packed tubes in a single shell.
Multiple beds each in their own shell.
The use of multiple catalyst sections usually arises because of the need to maintain adequate
temperature control within the system. Other constraints leading to the use of multiple beds
Key Features of Heterogeneous Reactors:
Ammonia Converter
INTRODUCTION:
17


include those of pressure drop or adequate fluid distribution. In addition to the shell and tube
configuration, some of the possibilities for

heat transfer to or from fixed bed reactors include the use of internal heat exchangers, annular
cooling spaces or cooling thimbles, and circulation of a portion of the reacting gases through
an external heat exchanger.
The packing itself may consist of spherical, cylindrical, or randomly shaped pellets, wire
screens or gauzes, crushed particles, or a variety of other physical configurations. The
structure of the catalyst pellets is such that the internal surface area far exceeds the superficial
(external) surface area, so that the contact area is, in principle, independent of pellet size. To
make effective use of the internal surface area, one must use a pellet size that minimizes
diffusion resistance within the catalyst pellet but that also gives rise to an appropriate
pressure drop across the catalyst bed. The most commonly used direction of reactant flow is
downward through the bed. This approach gives a stable bed that will not fluidize, dance, or
lift out of the reactor. This approach minimizes catalyst attrition and potential entrainment of
catalyst fines.

1. Low costs for construction and quite simple, operation, and maintenance relative to
moving bed or fluidized bed operation.
2. It requires a minimum of auxiliary equipment.
3. Appropriate for use in small commercial units.
4. Supporting facilities would be economically prohibitive.
5. Another major advantage of this mode of operation is implicit in the use of the term
"fixed bed reactor"; i.e., there are no problems in separating the catalyst from the
reactor effluent stream.
6. Another important attribute of fixed bed reactors is the wide variation in space times
at
which they can be operated.
Catalysts change the reaction mechanism and therefore the rate of the
reaction. If the reaction rate increases, the reaction volume will decrease, reducing the cost of
the reactor. Many chemical syntheses are impractical without using a catalyst. From the early
Advantages of Fixed Bed Reactor:
Catalyst:
18

Atypical compositionof an
industrial ammonia-synthesis
catalyst
CompositioninActivatedform(%)
Fe
2
0
3
1.1- 1.7
FeO 1.... 3-1.... 6
Fe 79.7- 81.6
CaO 0.1-0.2
Si0
2
0.1- 0.7
l\IIgO 0.3- 0.6
AI
2
0
3
1.5- 2.1
K
2
0 0.2-0.5
Porosity 40-50


days of ammonia production to the present, the only catalysts that have been used have been
iron catalysts promoted with nonreducible oxides. Recently, a ruthenium-based catalyst
promoted with rubidium has found industrial application. The basic composition of iron
catalysts is still very similar to that of the first catalyst developed by BASF.
Freshly reduced commercial iron catalysts that contain aluminum, potassium, and calcium
oxides as basic promoters consist of approximately 30-nm primary crystallites; the spaces
between them form an interconnecting system of pores.
Selected Catalyst:
Triply promoted Iron oxide catalyst is used
The iron catalyst consists of magnetite (Fe
3
O
4
)
which is enriched
(Promoted) most frequently with Al- and K- (or
Ca, Mg, Si)-oxides.
Catalyst is produced by fusing (melting) magnetite
ore with the other
Promoters at 1700
o
C and pouring melt into water to
form fine particles.
Iron being a transition metal with partially occupied
d-bands represents a surface suitable for adsorption
and dissociation of N
2
molecules.
Others catalysis are:
Os, Ru are equally active with Fe.
Ru is most active in ammonia decomposition.
Mo, U and Mn show quite high activity in ammonia synthesis
However, they reduce the inner surface or
lower the temperature stability and the resistance to oxygen-containing catalyst poisons and
the synthesis gas purity. Promoters can be classified in different groups according to the
specific action of the metal oxides:

Influence of the Promoters:
19


Structural stabilizers, such as Al
2
O
3
produce a high inner surface during reduction and
stabilize it under thermal stress by restraining iron crystallite growth. The ability of the
various metal oxides to create a high specific surface decreases in the following order:
Al
2
O
3
> TiO
2
> Cr
2
0
3
> MgO > MnO = CaO > SiO
2
> BeO
So-called electronic promoters, such as the alkali oxides, enhance the specific activity (based
on a unit surface) of iron - alumina catalysts.
Effect of Potassium:
Potassium increases intrinsic activity (increasing desorption rate).
Potassium increases the binding energy of the molecular N
2
precursor on Fe and
thereby assists the formation of atomic nitrogen.
Potassium acts as an electron donor enhancing N
2
reduction.
Potassium on Fe surface prevents the S poisoning on Fe.
Potassium enhances the reduction through an amide intermediate formation.
A promoter oxide of aluminum (3%) and potassium (1%) prevents sintering.

The activity of an ammonia synthesis catalyst may be lowered
by certain substances, commonly referred to as poisons. These substances can be minor
gaseous constituents of the synthesis gas or solids introduced into the catalysts during the
manufacturing procedure, derived from impurities in the natural magnetite from which the
catalyst is made. In contrast to temporary poisons, permanent poisons can be detected on the
catalyst by chemical analysis. Oxygen-containing compounds such as H
2
O, CO, CO
2
, and O
2
,
are the most common temporary poisons encountered in ammonia.


Catalyst Poisons:
20

Tllpuill 81IlIdlal
~iIf

Ammonia converters are classified by
flow type
1. Radial Flow.
2. Axial Flow.
3. Cross Flow.
Cooling method
1. Quench cooling.
2. Indirect cooling
One design uses 2 radial beds with quench gas injection
between them.
A similar radial flow design uses an inter-bed heat
exchanger in the first catalyst bed.
Cold ammonia synthesis gas is introduced from the
bottom of the converter through the second catalyst bed
then through the heat exchanger in the first catalyst bed.
The cold gas flow through the second bed also provides
indirect heat exchange.
An additional heat exchanger is located at the bottom of
the reactor to cool the reacted gases.

This reactor is a cross- flow converter
design where gas flows through the
catalyst bed perpendicular to the axis of
the vessel.
It is available in both quench and
indirectly cooled versions.



AMMONIA CONVERTER CLASSIFICATION:
Topsoe radial flow converter:
Kellogg horizontal converter:
21
A t 1AI N GAS I NLET
B I NLET FOR GAS TO
LOWER THE TUBE SI DE
C COLD BY- PASS I NLET
D GAS OUTLET
PRESSURE SHELL
2 OUTER ANNULUS
3 OUTER BASKET SHELL
4 BASKET I NSULATl ON
5 BASKET COVER
6 I NTERBED HEAT EXCHANGER c iHE)
7 TRANSFER PI PE
8 SCREEN PANELS
9 1st CATALYST BED
10 CENTRE SCREEN
11 COVER PLATE
12 CATALYST SUPPORT
13 2nd BED SUPPORT FLANGE
14 2nd CATALYST BED
15 3r d CATALYST BED


This reactor consists of 4 catalyst beds held on
separate grids.
Quench gas is introduced in the spaces between the
beds.
A heat exchanger is located at the top of the vessel.
With the S-300 converter, the catalyst volume can be reduced by approx. 20%
100% radial flow through the catalyst beds to obtain low pressure and high
conversion with a small size catalyst Particle.
Indirect cooling of the gas in the heat exchangers between the catalysts.
Total converter feed flow passes through all beds .stable operation with great
flexibility in operating range simple temperature control.

S-300 Ammonia Converter
Kellogg axial flow converter:

Topsoe radial flow converter S-300:
22
23

Old ammonia plants do not use recovery units. Mostly, the new plants are using cryogenic
separation technology for hydrogen recovery.
Cryogenic separation technique is a complex systemthat requires great operator attention and
large space to accommodate. It can cause health and safety problems because of the very low
temperatures and explosion.
As membrane technology for gas processing becomes wider spread and more accepted, there will
undoubtedly be more applications. There will always be special applications in which membrane
technology will uniquely fit. Membrane technology is a new emerging technique for hydrogen
recovery frompurge gas that offers the following advantages:
It is simple, straightforward and, therefore, easy to operate and maintain.
It can operate under fluctuating feed conditions
It offers unique operating flexibility when planned or unexpected process changes occur.
Increment in capacity requirements can be handled by the simple addition of more
separators. Some turndown is accommodated automatically.
It can be easily fitted into small or crowded plant areas because of the simplicity and
compact size of the skid mounted system.
It offers low capital cost and energy requirements.
It is environment friendly.








2.5 Hydrogen Recovery Unit
24

Broadly, hydrogen selective membranes (based on the materials used) can be categorized into
two types: organic (polymer) and inorganic (metallic, carbon, and ceramic). High-purity
hydrogen (up to 99.99%) could be available through dense metallic membranes and especially
through Pd and its alloys, but the commercial application of metallic membranes faces today
important limitations due to drawbacks like:
Poisoning effect that hydrogen sulfide (H2S) and other feed stocks have on the hydrogen
transport mechanism.
High cost for the preparation of Pd membranes.
Mechanical stability.
The key advantages of polymer membranes are the ability to cope with high pressure drops and
low cost. Polymers also provide a range of properties including permeability, mechanical
stability, and ease of process ability that are important for gas separation. Therefore, the
separation of H
2
by polymeric membranes has become an attractive existing technology.
Another property of membranes used for subdivision, is the membrane structure and connected
to this way in which transport through the membrane takes place. Porous membranes enable
transport through their pores, whereas dense membranes allow transport through the bulk of the
material.
Finally, the morphology or structural make-up of membranes can also be used for classification.
Symmetrical membranes have a homogeneous structure. Asymmetric membranes consist of
several layers with different characteristics. There can also be a gradual transition froma dense
membrane to a porous support. Membranes consisting of different layers of different materials
are called composite membranes.
Table 3.1 Engineering Strategies for Hydrogen Separation membrane
Selectivity General H2 Selectivity H2 Rejection
D
H2
/D
gas
>>>1 >>>>1 >>1
S
H2
/S
gas
<<1 <1 <<<1
P
H2
/P
gas
>1 >>>1 <1

D is the Diffusivity coefficient
S is the Sorption Coefficient
P is Permeability

3 MEMBRANE SEPARATION TECHNOLOGY
3.1 Membranes for Hydrogen Separation
25

Table 3.2 Comparison of Membranes for Hydrogen Separation
Dense
Polymer
Micro
porous
Ceramic
Dense
Metallic
Porous
Carbon
Dense
Ceramic
Temperature
Range
<100
o
C 200-600
o
C 300-600
o
C 500-900
o
C 600-900
o
C
H2
Selectivity
Low 5-139 >1000 4-20 >1000
Poisoning
Issues
HCl, Sox H
2
S, HCl,
CO
Strong
adsorbing
vapors,
organics
H
2
S
Materials Polymers Silica,
alumina,
titania,
zeolites
Palladium
alloy
Carbon Proton
conducting
ceramics
Transport
Mechanism
Solution
diffusion
Molecular
sieving
Solution
diffusion
Surface
diffusion,
molecular
sieving
Solution
diffusion
Development
Status
Commercial
by Air
Products,
Linde, Air
Liquid
Prototype
tubular silica
membranes
Commercial
by Johnson
Mathey
Small
membrane
modules
commercial
Small
samples
available
for testing
While choosing a membrane, there are four important parameters that must be considered:
1. Permselectivity for the required component
2. Mechanical strength
3. Chemical resistance
4. Thermal stability
After investigating permselectivity for hydrogen gas, mechanical strength to withstand such high
pressure of 122 atm, chemical resistance to incoming gases feed i.e. no chemical reaction occurs
with the gases, fromthe literature, polyimide was our first priority.
3.3 Hollow Fibers Preparation
Modern membrane fabrication is based on the LoebSourirajan technique, which allows the
generation of asymmetric membrane morphologies. Membranes prepared according to this

3.2 Why Polyimide?
26

formation principle, consist of an extremely thin layer, which determines the separation
properties and a thicker porous support layer, which provides for the required mechanical
strength of the whole membrane.
The process of making asymmetric hollow fiber membranes is called spinning. The polymer
solution used in making the membranes is commonly called a dope. The dope typically
consists of the polymer, a solvent, and a non-solvent.
Three main routes are known to prepare hollow fiber membranes;
1. Melt spinning
2. Dry spinning
3. Wet spinning (or dry/wet spinning).
The latter is the most important technique for the preparation of industrial hollow fiber
membranes. The majority of the hollow fibers employed in technical membrane processes are
spun by a wet spinning (or dry/wet spinning) technique. Any type of membrane morphology can
be obtained with this technique since many parameters involved can be varied.
In this process, the polymer solution is extruded into a non-solvent bath where de-mixing occurs
because of exchange of solvent and non-solvent, a high polymer concentration is created near the
outer surface, which is necessary to forma dense (gas selective) membrane top layer. Between
the spinneret and non-solvent bath there is an air gap where in fact the membrane formation
starts. This implies that a good control of this phase is a first requirement. The membrane
formation process can be controlled by the choice of the non-solvent which is extruded through
the outer opening as a thin film adhering to the polymer solution. Both the asymmetric
microfiltration and ultrafiltration hollow fibers can be prepared as well as integrally skinned
hollow fibers with a defect-free top layer suitable for gas separation and pervaporation.
Vers and Smolders distinguished two different de-mixing processes:
1. Delayed de-mixing: Where the ratio of solvent outflow and non-solvent inflow is
relatively large, which results in a certain time interval between immersion of the
polymer solution in the non-solvent bath and the onset of de-mixing.
2. Instantaneous de-mixing: Where liquid-liquid de-mixing takes place immediately after
the polymer solution is in contact with the non-solvent.
Vant Hof et al. showed, around 1992, that asymmetric membrane could be made using a dual
coagulation bath method, The first bath consists of a non-solvent with reduced non-solvency
power or reduced miscibility with solvent so that delayed de-mixing occurs (via increased
solvent outflow compared to non-solvent inflow), to forma dense region on the outside. The
second bath contains a strong non-solvent which promotes instantaneous de-mixing and
complete phase separation.
7
27

There is an air gap between the spinneret and non-solvent and this air gap has a large impact on
the ultimate membrane properties. In order to control the processes in the air gap, a new type of
spinneret has been developed where the extrusion mouth has three openings. This new triple
orifice allows a much better control of the conditions applicable for the spinning of all types of
hollow fibers. For the preparation of commercial membranes the phase inversion process is
generally applied. In this process, a polymer solution is immersed into a non-solvent bath where
phase separation (liquid-liquid de-mixing) occurs as a result of the exchange of solvent and non-
solvent. The first bath consists of a non-solvent with reduced non-solvency power or reduced
miscibility with solvent in air gap so that delayed de-mixing occurs (via increased solvent
outflow compared to non-solvent inflow), to forma dense region on the outside. The second bath
contains a strong non-solvent which promotes instantaneous de-mixing and complete phase
separation. After solidification of the polymer an asymmetric membrane with a relatively dense
top layer remains. The fibers obtained were dried in air after rinsing in running water for two
days followed by immersion in ethanol for 8 hours and then in hexane for another 8 hours.


Figure 3.1 Experimental set-up for hollow fiber spinning (1: spinning dope reservoir, 2: bore
liquid reservoir, 3: tube-in-orifice spinneret, 4: chimney (air gap), 5: coagulation bath (water), 6:
fiber guiding wheel, 7: pulling wheel, 8: hollow fiber membrane, 9: fiber collecting reservoir
(water))

3.4 Hollow Fiber Module
A module is the smallest practical unit containing a set of membrane area and any supporting
structures. For each membrane certain module shapes are commercially available. Hollow fiber
is preferred commercially for high pressure gas separation.
productivi ty =p. A /).p
I
28

Hollow fibers are essentially self-supporting and resistant to collapse in high pressure and
environmentally difficult situations (Paul, 1994). The support is a porous substructure that
ideally has negligible resistance and lies underneath the outer skin layer, thereby providing the
mechanical strength to the fiber. Hollow fiber modules are preferably used when the feed stream
is relatively clean. Hollow fiber membranes can withstand very high pressures fromthe outside,
but are limited on pressure exerted fromthe inside of the fiber, therefore backwash rates are
limited to around twice the normal permeate rate. The feed fluid is applied on the outside of the
fibers and permeate is removed down the fiber bore.
Asymmetric hollow fibers provide high fluxes required for productive separations due to the
ability to reduce the separating layer to a thin integral skin on the outer surface of the
membrane. The high trans-membrane pressure differences capable of being handled, and the
high surface area to volume ratios and high packing densities achieved from such cylindrical
morphologies make this type of membrane structure very favorable industrially. The productivity
of a membrane can be characterized by the amount of penetrant that permeates through the
membrane within a given time period and is inversely proportional to the thickness of the
separating layer according to equation

Where
P is the intrinsic membrane permeability (a property of the material)
A is the membrane surface area for permeation
p is the trans-membrane pressure difference driving force
l is the membranes effective thickness, which can be controlled morphologically
For this reason, it is clear that a thinner skin would allow use of smaller (lighter weight) modules
and reduce capital costs for a given membrane.
3.5 Asymmetric Membrane Transport Mechanism
Generally, gas transport in non-porous (dense) membranes occurs via the solution-diffusion
mechanism, comprised of three main steps:
1. Sorption of the gaseous penetrants at the upstreamside of the membrane,
2. Diffusion of the penetrants across the membrane,
3. Desorption of the penetrants at the downstreamside of the membrane

29

3.5.1 Solution-diffusion model
Permeates dissolve in the membrane material and then diffuse through membrane down
concentration gradient. The permeates are separated because of the differences in the solubility
of the materials in the membrane and the differences in the rates at which the materials diffuse
through the membrane.
The solution diffusion mechanism is driven by a difference in the thermodynamic activities
existing at the upstreamand downstreamfaces of the membrane as well as the interacting force
working between the molecules that constitute the membrane material and the permeate
molecules. The activity difference causes a concentration difference that leads to diffusion in the
direction of decreasing activity.
3.5.1.1 Diffusion
The basis of the solution-diffusion model is the process by which matter is transported fromone
part of systemto another by a concentration gradient. The individual molecules in the membrane
medium are in constant random molecular motion, but in an isotropic medium, individual
molecules have no preferred direction of motion. Although the average displacement of an
individual molecule fromits starting point can be calculated, after a period of time nothing can
be said about the direction in which any individual molecule will move. However, if
concentration gradient of permeate molecules is formed in the medium, simple statistics show
that a net transport of matter will occur fromthe high concentration to low concentration region.
This concept was first recognized by Fick theoretically and experimentally in 1855. Fick
formulated his results as the equation now called Ficks law of diffusion, which states

Where
J
i
is the rate of transfer of component i or flux (g/cm s)
dc
i
/dx is the concentration gradient of component i
D
i
is called the diffusion coefficient (cm/s) and is a measure of the mobility of the
individual molecules.
The minus sign shows that direction of diffusion is down the concentration gradient. Diffusion is
an inherently slow process. In practical diffusion-controlled separation processes, useful fluxes
across the membrane are achieved by making the membranes very thin and creating large
concentration gradients in the membrane.
C
=KDP + 11/
c~bp
1+ bp
30

3.5.1.2 Sorption
The sorption coefficient is the termlinking the concentration of a component in the fluid phase
with its concentration in the membrane polymer phase. Because sorption is an equilibriumterm,
conventional thermodynamics can be used to calculate solubility's of gases in polymers to within
a factor of two or three. In fact, sorption coefficients of gases in polymers are relatively constant
for a wide range of chemically different polymers. Sorption coefficients of gases in polymers
remain relatively constant, as sorption in polymers behaves as though the polymers were ideal
fluids.
According to dual-sorption model, gas sorption in a polymer (cm) occurs in two types of sites.
1. The first type is filled by gas molecules dissolved in the equilibriumfree volume portion
of material. Henrys law occurs in the equilibrium free volume portion of the polymer.
2. The other fraction is assumed to be sorbed into the excess free volume elements, which
are limited, so sorption will cease when all the sites are filled. Sorption in these sites is
best approximated by a Langmuir-type absorption isotherm.
Hence, the total Sorption is given as:

3.6 Working of Hollow Fiber Module
A closed bundle of fibers is contained in a pressure vessel. The feed is entered into the shell side
at a high pressure of 122 atm; permeate passes through fiber wall and exits through open fiber
ends. Permeate is introduced into the syn compressor. Pressure at permeate side is maintained at
31 atmwhile the reject is collected fromthe top of the module and is used for burning purposes.
Membranes consist of an extremely thin layer, which determines the separation properties and a
thicker porous support layer, which provides for the required mechanical strength of the whole
membrane. For modeling of membrane separation processes, it is often assumed that the total
membrane resistance is determined only by the thin active layer of the membrane
Stage cut is an important factor in determining the performance of the system. It is the ratio of
permeate flow to the feed flow rate. To achieve the same output results i.e. same recovery and
purity of hydrogen gas, stage cut of the systemmust not be changed.

Feed
Permeate
Cl<therGases
1---1.2
H2.
31



Table 3.3 Influence of Operating Variables
Operating Variable Direction of Change Hydrogen Recovery Hydrogen Purity
Stage Cut Increases Increases Decreases
Decreases Decreases Increases
Operating Temperature Increases Increases Decreases
Decreases Decreases Increases
Pressure Differential Increases Increases Increases
Decreases Decreases Decreases








55
--5 -22 r
56
32

4 MATERIALS BALANCE
Calculated by simultaneously solving a set of 124 equations, by using MS Excel.
4.1 NG and Recycle Stream Mixing Point

Components 5-NG feed
22-recycle from
syn compressor
6-desulphurizer
inlet
mole% kmol/hr mole% kmol/hr mole% kmol/hr
H
2
0.00% 0.000 70.21% 85.195 4.55% 85.195
N
2
18.00% 315.281 28.34% 34.393 18.67% 349.674
CO
2
8.00% 140.125 0.00% 0.000 7.48% 140.125
Ar 0.00% 0.000 0.26% 0.315 0.02% 0.315
CH
4
73.80% 1292.651 1.19% 1.447 69.10% 1294.098
C
2
H
6
0.20% 3.503 0.00% 0.000 0.19% 3.503
Total 100.00% 1751.560 100.00% 121.350 100.00% 1872.910

Equations
H
2
: f
H2,22
=f
H2,6
f
H2,6
f
H2,22
=0
N
2
: f
N2,5
+f
N2,22
=f
N2,6
f
N2,6
f
N2,22
=18
CO
2
: f
C02,5
=f
C02,6
f
C02,6
=8
Ar: f
Ar,22
=f
Ar,6
f
Ar,6
f
Ar,22
=0
CH
4
: f
CH4,5
+f
CH4,22
=f
CH4,6
f
CH4,6
f
CH4,22
=73.8
C
2
H
6
: f
C2H6,5
=f
C2H6,6
f
C2H6,6
=0.2

33

4.2 Desulfurizer
Desulfurizer
S 6
S 7

Equations
H
2
: f
H2,6
=f
H2,7
f
H2,6
f
H2,7
=0
N
2
: f
N2,6
f
N2,7
=0
CO
2
: f
CO2,6
f
CO2,7
=0
Ar: f
Ar,6
f
Ar,7
=0
CH4: f
CH4,6
f
CH4,7
=0
C
2
H
6
: f
C2H6,6
f
C2H6,7
=0
Sulfur content is reduced from1-2 ppmto 1000 then 10 ppb.







Components
7-desulphurizer
outlet

mole % kmol/hr
H
2
4.55% 85.195
N
2
18.67% 349.674
CO
2
7.48% 140.125
Ar 0.02% 0.315
CH
4
69.10% 1294.098
C
2
H
6
0.19% 3.503
Total 100.00% 1872.910
s 7 ~ 1 ~ S - 8 - - - - ~S9
34

4.3 Feed Gas and Steam Mixing Point



Equations
H
2
: f
H2,7
=f
H2,9
f
H2,7
f
H2,9
=0
N
2
: f
N2,7
f
N2,9
=0
CO
2
: f
CO2,7
f
CO2,9
=0
Ar: f
Ar,7
f
Ar,9
=0
CH
4
: f
CH4,7
f
CH4,9
=0
C
2
H
6
: f
C2H6,7
f
C2H6,9
=0
H
2
O: f
H2O,8
=f
H2O,9
f
CH4
- f
H2O,9
=0
As, steam/ C ratio =2.7
H2O, 8
4,7 +226,7
= 2.7
2.7 f
CH4,7
+5.4 f
C2H6,7
f
CH4
=0



Components
8-process steam
9-primary
reformer inlet
mole % kmol/hr mole % kmol/hr
H
2
0.00% 0.000 1.58% 85.195
N
2
0.00% 0.000 6.49% 349.674
CO
2
0.00% 0.000 2.60% 140.125
Ar 0.00% 0.000 0.59% 0.315
CH
4
0.00% 0.000 24.03% 1294.098
C
2
H
6
0.00% 0.000 6.50% 3.503
H
2
O 100.00% 3512.982 65.23% 3512.982
Total 100.00% 3512.982 100.00% 5385.892
,--------i-
L '--- -
35

4.4 Primary Reformer

S 9
S 10
Primary
Reformer

Equations
The general overall reaction for steamreforming of hydrocarbons can be formulated as:
C
n
H
(2n+2)
+nH
2
O nCO +(2n+1) H
2

Specifically for methane:
CH
4
+H
2
O CO +3 H
2
H
0
298
=206 kJ/ mol
Simultaneous with this reaction water gas shift reaction proceeds as:
CO +H
2
O CO
2
+H
2
H
0
298
=-41 kJ/ mol
When this is included following overall reaction can be written:
CH
4
+2H
2
O CO
2
+4 H
2
H
0
298
=165 kJ/ mol
At the given conditions,
Conversion of methane =60 % Yield of CO =60 % Yield of CO
2
=40 %
Let conversion of ethane is 100 % and completely gives CO
H
2
: f
H2,9
+0.6(0.4)(4) f
CH4,9
+0.6(0.6)(7)f
CH4,9
+5f
C2H6,9
=f
H2,10

f
H2,9
+H2.04 f
CH4,9
+5f
C2H6,9
- f
H2,10
=0
N
2
: f
N2,9
=f
N2,10
f
N2,9
- f
N2,10
=0
CO: 0.6(o.6) f
CH4,9
+2 f
C2H6,9
=f
CO,10
0.36 f
CH4,9
+2 f
C2H6,9
- f
CO,10
=0
Components
10-primary
reformer outlet
mole % kmol/hr
H
2
39.45% 2742.671
N
2
5.03% 349.674
CO 6.80% 472.882
CO
2
6.48% 450.708
Ar 0.00% 0.315
CH
4
7.45% 517.639
H
2
O 34.79% 2418.934
Total 100.00% 6952.823
Sl 1
36

CO
2
: f
CO2,9
+0.6(0.4) f
CH4,7
=f
CO2,10
f
CO2,9
+0.24 f
CH4,7
- f
CO2,10
=0
Ar: f
Ar,9
=f
Ar,10
f
Ar,9
- f
Ar,10
=0
CH
4
: f
CH4,9
0.6 f
CH4,9
=f
CH4,10
0.4f
CH4,9
f
CH4,10
=0
H
2
O: f
H2O,9
0.6(.6) f
CH4,9
0.6(0.4)(2) f
CH4,9
2 f
C2H6,9
=f
H2O,10

-0.84 f
CH4,9
2 f
C2H6,9
+f
H2O,9
f
H2O,10
=0
4.5 Secondary Reformer

Equations
Combustion reactions (upper portion):
CH
4
+2O
2
CO
2
+2 H
2
O
H
2
+ O
2
H
2
O
CO + O
2
CO
2

Reforming reaction (lower portion):
CH
4
+H
2
O CO +3 H
2

CH
4
+2H
2
O CO
2
+4 H
2

At the given conditions,
Conversion of methane =90 % Yield of CO =90 % Yield of CO
2
=10 %
Components
11-process air
12-2ndry reformer
outlet
mole % kmol/hr mole % kmol/hr
H
2
0.00% 0.000 37.21% 3449.942
N
2
78.04% 1369.963 18.55% 1719.636
O
2
20.99% 368.471 0.00% 0.000
CO 0.00% 0.000 9.62% 892.169
CO
2
0.09% 1.580 5.38% 498.876
Ar 0.88% 15.448 0.17% 15.763
CH
4
0.00% 0.000 0.56% 51.764
H
2
O 0.00% 0.000 28.51% 2643.414
Total 100.00% 1755.462 100.00% 9271.565
37

Let only H
2
combust with O
2

H
2
: f
H2,10
2(0.2099) f
11
+0.9(0.9) (1) f
CH4,10
+0.9(0.1)(4) f
CH4,10
=f
H2,12
f
H2,10
+2.79 f
CH4,10
0.4198 f
11
f
H2,12
=0
N
2
: f
N2,10
+0.7804 f
11
=f
N2,12
f
N2,10
+0.7804 f
11
f
N2,12
=0
CO: f
CO,10
+0.9(0.9) f
CH4,10
=f
CO,12
f
CO,10
+081 f
CH4,10
- f
CO,12
=0
CO
2
: f
CO2,10
+0.9 (0.1) f
CH4,10
+0.0009 f
11
=f
CO2,12

f
CO2,10
+0.09 f
CH4,10
+0.0009 f
11
f
CO2,12
=0
Ar: f
Ar,10
+0.0088 f
11
=f
Ar,12
f
Ar,10
+0.0088 f
11
- f
Ar,12
=0
CH
4
: f
CH4,10
0.9 f
CH4,10
=f
CH4,12
0.1 f
CH4,10
- f
CH4,12
=0
H
2
O: f
H2O,10
+2(o.2099) f
11
0.9(.9) f
CH4,10
0.9(0.1)(2) f
CH4,10
=f
H2O,12
0.99 f
CH4,10
+f
H2O,10
+0.4198 f
11
f
H2O,12
=0
4.6 High Temperature Shift Converter - HTSC
HTS
Convertor
S 12
S 13

Equations
CO +H
2
O CO
2
+H
2
H
0
298
=-41.2 kJ/ mol
At given conditions, conversion =90 %
H
2
: f
H2,13
+0.9 f
CO,12
=f
H2,13
f
H2,13
+0.9 f
CO,12
- f
H2,13
=0
N
2
: f
N2,12
=f
N2,13
f
N2,12


f
N2,13
=0
CO: f
CO,12
0.9 f
CO,12
=f
CO,13
f
CO,12
0.9 f
CO,12
- f
CO,13
=0
Components
13-HTSC outlet
mole % kmol/hr
H
2
45.87% 4252.894
N
2
18.55% 1719.636
CO 0.96% 89.217
CO
2
14.04% 1301.828
Ar 0.17% 15.763
CH
4
0.56% 51.764
H
2
O 19.85% 1840.461
Total 100.00% 9271.565
38

CO
2
: f
CO2,12
+0.9 f
CO,12
=f
CO2,13
f
CO2,12
+0.9 f
CO,12
- f
CO2,13
=0
Ar: f
Ar,12
=f
Ar,13
f
Ar,12
- f
Ar,13
=0
CH
4
: f
CH4,12
=f
CH4,13
f
CH4,12
- f
CH4,13
=0
H
2
O: f
H2O,12
0.9 f
CO,12
=f
H2O,13
f
H2O,12
0.9 f
CO,12
- f
H2O,13
=0
4.7 Low Temperature Shift Converter LTSC
S 13
LTS
Convertor
S 14

Equations
CO +H
2
O CO
2
+H
2
H
0
298
=-41.2 kJ/ mol
At given conditions, conversion =80 %
H
2
: f
H2,13
0.8 f
CO,13
=f
H2,14
f
H2,13
0.8 f
CO,13
- f
H2,14
=0

N
2
: f
N2,13
=f
N2,14
f
N2,13
- f
N2,14
=0
CO: f
CO,13
- 0.8 f
CO,13
=f
CO,14
0.2 f
CO,13
- f
CO,14
=0
CO
2
: f
CO2,13
+0.8 f
CO,13
=f
CO2,14
0.8 f
CO,13
+f
CO2,13
f
CO2,14
=0
Ar: f
Ar,13
=f
Ar,14
f
Ar,13
- f
Ar,14
=0
CH
4
: f
CH4,13
=f
CH4,14
f
CH4,13
- f
CH4,14
=0
H
2
O: f
H2O,13
0.8 f
CO,13
=f
H2O,14
0.9 f
CO,13
- f
H2O,13
+ f
H2O,14
=0


Components
14-LTSC outlet
mole % kmol/hr
H
2
46.64% 4324.268
N
2
18.55% 1719.636
CO 0.19% 17.843
CO
2
14.81% 1373.202
Ar 0.17% 15.763
CH
4
0.56% 51.764
H
2
O 19.08% 1769.088
Total 100.00% 9271.565
39

4.8 2
nd
KO Drum
S 16
KO
Drum
S 16
S 14

Equations
Let 95% of H
2
O is removed
H
2
: f
H2,14
=f
H2,16
f
H2,14
f
H2,16
=0
N
2
: f
N2,14
- f
N2,16
=0
CO: f
CO,14
- f
CO,16
=0
CO
2
: f
CO2,14
f
CO2,16
=0
Ar: f
Ar,14
- f
Ar,16
=0
CH
4
: f
CH4,14
- f
CH4,16
=0
H
2
O: f
H2O,14
=f
15
+ f
H2O,16
f
H2O,14
- f
15
f
H2O,16
=0
As, f
15
=0.95 f
H2O,14
0.95 f
H2O,14
- f
15
=0





Components
15-condensate 16-KO drum outlet
mole % kmol/hr mole % kmol/hr
H
2
0.00% 0.000 56.97% 4324.268
N
2
0.00% 0.000 22.65% 1719.636
CO 0.00% 0.000 0.24% 17.843
CO
2
0.00% 0.000 18.09% 1373.202
Ar 0.00% 0.000 0.21% 15.763
CH
4
0.00% 0.000 0.68% 51.764
H
2
O 100.00% 1680.633 1.17% 88.454
Total 100.00% 1680.633 100.00% 7590.931
517
C02
Absorption
Column
516
Column
40

4.9 CO
2
Absorption

Equations
Let CO
2
removed =99.8 %
H
2
: f
H2,16
=f
H2,18
f
H2,16
f
H2,18
=0
N
2
: f
3,16
- f
3,18
=0
CO: f
CO,16
- f
CO,18
=0
CO
2
: f
CO2,16
=f
17
+f
CO2,18
f
CO2,16
- f
17
f
CO2,18
=0
Ar: f
Ar,16
- f
Ar,18
=0
CH
4
: f
CH4,16
- f
CH4,18
=0
H
2
O: f
H2O,16
f
H2O,18
=0
As, f
17
=0.998 f
CO2,16
0.998 f
CO2,16
- f
17
=0






Components
17-CO
2
to urea
plant
18-CO
2
absorber
outlet
mole % kmol/hr mole % kmol/hr
H
2
0.00% 0.000 69.52% 4324.268
N
2
0.00% 0.000 27.64% 1719.636
CO 0.00% 0.000 0.29% 17.843
CO
2
100.00% 1370.456 0.04% 2.746
Ar 0.00% 0.000 0.25% 15.763
CH
4
0.00% 0.000 0.83% 51.764
H
2
O 0.00% 0.000 1.42% 88.454
Total 100.00% 1370.456 100.00% 6220.476
41

4.10 Methanator
Methanator
S 18
S 19

Equations
Let 100 % conversion of CO and CO
2
into CH
4
CO +3 H
2
CH
4
+H
2
O
CO
2
+4 H
2
CH
4
+2H
2
O
H
2
: f
H2,18
3 f
CO,18
- 4 f
CO2,18
=f
H2,19
f
H2,18
3 f
CO,18
- 4 f
CO2,18
- f
H2,19
=0
N
2
: f
3,18
=f
3,19
f
3,18
- f
3,19
=0
Ar: f
Ar,18
- f
Ar,19
=0
CH
4
: f
CH4,18
+f
CO,18
+f
CO2,18
=f
CH4,19
f
CH4,18
+f
CO,18
+f
CO2,18
- f
CH4,19
=0
H
2
O: f
H2O,18
+f
CO,18
+2 f
CO2,18
=f
H2O,19
f
CO,18
+2f
CO2,18
+f
H2O,18
- f
H2O,19
=0

4.11 3
rd
KO Drum
KO
Drum
S 19
S 20
S 21

Components
19-methanator
outlet
mole % kmol/hr
H
2
68.94% 4259.752
N
2
27.83% 1719.636
Ar 0.26% 15.763
CH
4
1.17% 72.354
H
2
O 1.81% 111.791
Total 100.00% 6179.296
Components
20-condensate 21-KO drum outlet
mole % kmol/hr mole % kmol/hr
H
2
0.00% 0.000 70.21% 4259.752
N
2
0.00% 0.000 28.34% 1719.636
Ar 0.00% 0.000 0.26% 15.763
CH
4
0.00% 0.000 1.19% 72.354
H
2
O 100.00% 111.791 0.00% 0.000
Total 100.00% 111.791 100.00% 6067.506
42



Equations
Let 100 % of H
2
O is removed.
H
2
: f
H2,19
=f
H2, 21
f
H2,19
f
H2,21
=0
N
2
: f
3,19
- f
3,21
=0
Ar: f
Ar,19
- f
Ar,21
=0
CH
4
: f
CH4,19
- f
CH4,21
=0
H
2
O: f
H2O,19
=f
20
f
H2O,19
- f
20
=0
4.12 1
st
Stage of Compressor
S 21
S 23
S 22

Equations
Let 2% of stream21 is recycled back through stream22
H
2
: f
H2,21
=f
H2,22
+f
H2,23
f
H2,21
- f
H2,22
- f
H2,23
=0
f
H2,22
=0.02 f
H2,21
0.02 f
H2,21
- f
H2,22
=0
N
2
: f
N2,21
- f
N2,22
- f
N2,23
=0
0.02 f
N2,21
- f
N2,22
=0
Ar: f
Ar,21
- f
Ar,22
f
Ar,23
=0
0.02 f
,Ar,21
- f
Ar,22
=0
CH
4
: f
CH4,21
- f
CH4,22
f
CH4,23
=0
Components
23-compressor 1st
stage outlet
mole % kmol/hr
H
2
70.21% 4174.557
N
2
28.34% 1685.244
Ar 0.26% 15.448
CH
4
1.19% 70.907
Total 100.00% 5946.156
529
524
525
43

0.02 f
CH4,21
- f
CH4,22
=0
4.13 2
nd
and 3
rd
Stage of Compressor
S 34
S 23
S 24

Equations
H
2
: f
H2,23
+0.9328 f
34
=f
H2,24
f
H2,23
- f
H2,24
+0.9328 f
34
=0
N
2
: f
N2,23
+0.0411 f
34
=f
N2,24
f
N2,23
+0.0411 f
34
- f
N2,24
=0
Ar: f
Ar,23
+0.0111 f
34
=f
Ar,24
f
Ar,23
+0.0111 f
34
f
Ar,24
=0
CH
4
: f
CH4,23
+0.0122f
34
=f
CH4,24
f
CH4,23
+0.0122f
34
- f
CH4,24
=0
4.14 Make up Gas Mixing Point



Equations
NH
3
: f
NH3,29
=f
NH3,25
f
NH3,29
- f
NH3,25
=0
H
2
: f
H2,24
+f
H2,29
=f
H2,25
f
H2,24
+f
H2,29
- f
H2,25
=0
N
2
: f
N2,24
+f
N2,29
=f
N2,25
f
N2,24
+f
N2,29
- f
N2,25
=0
Components
24-compressor
2ndstage outlet
mole % kmol/hr
H
2
73.81% 5189.948
N
2
24.60% 1729.983
Ar 0.39% 27.531
CH
4
1.20% 84.187
Total 100.00% 7031.649
Components
25-separator inlet
mole % kmol/hr
NH
3
7.65% 3162.066
H
2
65.21% 26960.770
N
2
21.74% 8986.923
Ar 1.33% 550.618
CH
4
4.07% 1683.737
Total 100.00% 41344.114
S27 1
I I
Ammonia Synthesis
Convertor
I S28
44

Ar: f
Ar,24
+f
Ar,29
=f
Ar,25
f
Ar,24
+f
Ar,29
- f
Ar,25
=0
CH
4
: f
CH4,24
+f
CH4,29
=f
CH4,25
f
CH4,24
+f
CH4,29
- f
CH4,25
=0
4.15 Separator
Ammonia
Separator
S 25
S 26
S 27

Equations
NH
3
: f
NH3,25
=f
26
+f
NH3,27
f
NH3,25
- f
26
- f
NH3,27
=0
H
2
: f
H2,25
=f
H2,27
f
H2,25
- f
H2,27
=0
N
2
: f
N2,25
=f
N2,27
f
N2,25
- f
N2,27
=0
Ar: f
Ar,25
=f
Ar,27
f
Ar,25
- f
Ar,27
=0
CH
4
: f
CH4,25
=f
CH4,27
f
CH4,25
- f
CH4,27
=0
4.16 Ammonia Synthesis Convertor


Equations
3 H
2
+2 N
2
2 NH
3
H
0
298
=- 92.44 kJ/mol
Components
26-separator liquid
outlet
27-recycle to NH
3

covertor inlet
mole % kmol/hr mole % kmol/hr
NH
3
100.00% 2529.653 1.63% 632.413
H
2
0.00% 0.000 69.46% 26960.770
N
2
0.00% 0.000 23.15% 8986.923
Ar 0.00% 0.000 1.42% 550.618
CH
4
0.00% 0.000 4.34% 1683.737
Total 100.00% 2529.653 100.00% 38814.461
Components
28-NH
3
convertor
outlet
mole % kmol/hr
NH
3
9.22% 3328.490
H
2
63.45% 22916.655
N
2
21.15% 7638.885
Ar 1.52% 550.618
CH
4
4.66% 1683.737
Total 100.00% 36118.384
529 528
45

At given conditions single pass conversion is 15 %
NH
3
: f
NH3,27
+0.15(2)f
N2,27
=f
NH3,28
f
NH3,27
+0.30f
N2,27
- f
NH3,28
=0
H
2
: f
H2,27
-0.15 f
H2,27
=f
H2,28
0.85 f
H2,27
- f
H2,28
=0
N
2
: f
N2,27
-0.15 f
2,27
=f
N2,28
0.85 f
N2,27
- f
N2,28
=0
Ar: f
Ar,27
=f
Ar,28
f
Ar,27
- f
Ar,28
=0
CH
4
: f
CH4,27
=f
CH4,28
f
CH4,27
- f
CH4,28
=0
4.17 Purge Gas Exit Point


Equations
5% of stream28 is purged out
NH
3
: f
NH3,28
=f
NH3,29
+f
NH3,30
f
NH3,28
- f
NH3,29
- f
NH3,30
=0
f
NH3,30
=0.05 f
NH3,28


0.05 f
NH3,28
- f
NH3,30
=0

H
2
: f
H2,28
=f
H2,29
+ f
H2,30
f
H2,28
- f
H2,29
- f
H2,30
=0
f
H2,30
=0.05f
H2,28
f
H2,30
- 0.05f
H2,28
=0
N
2
: f
N2,28
=f
N2,29
+f
N2,30
f
N2,28
- f
N2,29
- f
N2,30
=0
f
N2,30
=0.05 f
N2,28
0.05 f
N2,28
- f
N2,30
= 0
Ar: f
Ar,28
=f
Ar,29
+f
Ar,30
f
Ar,28
- f
Ar,29
- f
Ar,30
=0
0.05f
Ar,28
=f
Ar,30
0.05f
Ar,28
- f
Ar,30
=0
CH
4
: f
CH4,28
=f
CH4,29
+f
CH4,30
f
CH4,28
- f
CH4,29
- f
CH4,30
=0
Components
29
30-purge gas to
ARU
mole % kmol/hr mole % kmol/hr
NH
3
9.22% 3162.066 9.22% 166.425
H
2
63.45% 21770.822 63.45% 1145.833
N
2
21.15% 7256.941 21.15% 381.944
Ar 1.52% 523.087 1.52% 27.531
CH
4
4.66% 1599.550 4.66% 84.187
Total 100.00% 34312.465 100.00% 1805.919
1
531
52_ 6 ~_ ~ ~~ 532
46

0.05f
CH4,28
= f
CH4,30
f
CH4,30
0.05 f
CH4,28
=0
4.18 Ammonia Recovery Unit - ARU
Ammonia
Recovery Unit
S 30
S 31
S 33

Equations
NH
3
: f
NH3,30
=f
31
f
NH3,30
- f
31
=0
H
2
: f
H2,30
=f
H2,33
f
H2,30
f
H2,33
=0
N
2
: f
N2,30
=f
N2,33
f
N2,30
- f
N2,33
=0
Ar: f
Ar,30
=f
Ar,33
f
Ar,30
- f
Ar,33
=0
CH
4
: f
CH4,30
=f
CH4,33
f
CH4,30
- f
CH4,33
=0
4.19 Recovered NH
3
Mixing Point

Equations
NH
3
: f
26
+f
31
=f
32
f
26
+f
31
- f
32
=0



Components
31-recovered NH
3
33-ARU outlet
mole % kmol/hr mole % kmol/hr
NH
3
100.00% 166.425 0.00% 0.000
H
2
0.00% 0.000 69.89% 1145.833
N
2
0.00% 0.000 23.30% 381.944
Ar 0.00% 0.000 1.68% 27.531
CH
4
0.00% 0.000 5.13% 84.187
Total 100.00% 166.425 100.00% 1639.495
Components
32-product NH
3

mole % kmol/hr
NH
3
100.00% 2696.077
Total 100.00% 2696.077
47



4.20 Hydrogen Recovery Unit - HRU
Hydrogen
Recovery Unit
S 34
S 33 S 35


Equations
H
2
: f
H2,33
=0.9328f
34
+ f
H2,35
f
H2,33
- 0.9328f
34
- f
H2,35
=0
As 95% of H
2
is recovered
0.9328 f
34
=0.95 f
H2,33
0.9328f
34
- 0.95 f
H2,33
=0
N
2
: f
N2,33
=0.411f
34
+f
N2,35
f
N2,33
- 0.411f
34
- f
N2,35
=0
Ar: f
Ar,33
=0.0111f
34
+f
Ar,35
f
Ar,33
- 0.0111f
34
- f
Ar,35
=0
CH
4
: f
CH4,33
=0. 0122 f
34
+f
CH4,35
f
CH4,33
- 0.0122f
34
f
CH4,35
=0






Components
34-recoverd H
2

(permeate)
35-boiler fuel gas
(raffinate)
mole % kmol/hr mole % kmol/hr
H
2
93.28% 1088.541 12.02% 57.292
N
2
4.11% 47.962 70.05% 333.982
Ar 1.11% 12.953 3.06% 14.578
CH
4
1.22% 13.237 14.88% 70.950
Total 100.00% 1166.961 100.00% 476.802
48

Calculated by using MS Excel.
Formulae
=
=

Where = + +
2
+
3

= [ ( ) +

2
(
2

2
) +

3
(
3

3
) +

4
(
4

4
) ]
=
( ) +

2
(
2

2
) +

3
(
3

3
) +

4
(
4

4
)


Reference/Base Conditions
Temperature =298.15 K Pressure =1 atm
Cp Constants
Components a B c d
NH
3
27.568 2.56E-02 9.91E-06 -6.69E-09
H
2
29.11 -1.92E-03 4.00E-06 -8.70E-10
N
2
28.9 -1.57E-03 8.08E-06 -2.87E-09
O
2
25.48 1.52E-02 -7.16E-06 1.31E-09
CO 28.16 1.68E-03 5.37E-06 -2.22E-09
CO
2
22.26 5.98E-02 -3.50E-05 7.47E-09
Ar 28.11 1.97E-03 4.80E-06 -1.97E-09
CH
4
19.89 5.02E-02 1.27E-05 -1.10E-08
C
2
H
6
6.9 1.73E-01 -6.41E-05 7.29E-09
H
2
O 32.24 1.92E-03 1.06E-05 -3.60E-09





5 ENERGY BALANCE
49

Calculations
Following table was formed in Excel using above mentioned formula and c
p
constants in order to
calculate the enthalpy of NG feed stream(S5). Enthalpies of other streams were calculated by
same method.

x (mol e
fracti on)
n (kmol/hr)
T
r

(K)
T (K) a B C d
Cp (kJ/
kmol K)
x*Cp H (kJ/h)
NH
3

0.000 0.000 298.15 308.15 27.568 2.56E-02 9.91E-06 -6.69E-09 36.062 0.000 0.00
H
2

0.000 0.000 298.15 308.15 29.11 -1.92E-03 4.00E-06 -8.70E-10 28.873 0.000 0.00
N
2

0.180 315.281 298.15 308.15 28.9 -1.57E-03 8.08E-06 -2.87E-09 29.086 5.236 91703.83
O
2

0.000 0.000 298.15 308.15 25.48 1.52E-02 -7.16E-06 1.31E-09 29.467 0.000 0.00
CO
0.000 0.000 298.15 308.15 28.16 1.68E-03 5.37E-06 -2.22E-09 29.100 0.000 0.00
CO
2

0.080 140.125 298.15 308.15 22.26 5.98E-02 -3.50E-05 7.47E-09 37.382 2.991 52381.22
Ar
0.000 0.000 298.15 308.15 28.11 1.97E-03 4.80E-06 -1.97E-09 29.093 0.000 0.00
CH
4

0.738 1292.651 298.15 308.15 19.89 5.02E-02 1.27E-05 -1.10E-08 35.980 26.553 465092.78
C
2
H
6

0.002 3.503 298.15 308.15 6.9 1.73E-01 -6.41E-05 7.29E-09 53.569 0.107 1876.59
H
2
O
0.000 0.000 298.15 308.15 32.24 1.92E-03 1.06E-05 -3.60E-09 33.692 0.000 0.00
Total
1.000 1751.560

34.886 6.11E+05

Following calculations were done in Excel to find outlet temperature of HTSC. Similar
calculations were done for LTSC, methanator and ammonia synthesis convertor.
As H
out
=- H
rxn
+H
in
(kJ/h)
At given conditions, molar H
rxn
=-4.00E+04 kJ/kmol
Therefore, H
rxn
=-4.00E+04 kJ/kmol * 802.952 kmol/h =-3.21E+07 kJ/h
H
out
=-(-3.21E+07) +5.67E+07 =8.88E+07 kJ/h
As, H
out
=n c
p
(T - T
r
)
For calculating c
p
, following table was formed in Excel.

x (mol e
fracti on)
n
(kmol /hr)
T
r
(K) T (K) a B C d
Cp (kJ/kmol
K)
x*Cp
NH
3

0.000 0.000 298.15 493.15 27.568 2.56E-02 9.91E-06 -6.69E-09 38.851 0.000
H
2
0.459 4252.894 298.15 493.15 29.11 -1.92E-03 4.00E-06 -8.70E-10 28.934 13.272
N
2
0.185 1719.636 298.15 493.15 28.9 -1.57E-03 8.08E-06 -2.87E-09 29.380 5.449
O
2
0.000 0.000 298.15 493.15 25.48 1.52E-02 -7.16E-06 1.31E-09 30.437 0.000
CO 0.010 89.217 298.15 493.15 28.16 1.68E-03 5.37E-06 -2.22E-09 29.535 0.284
CO
2
0.140 1301.828 298.15 493.15 22.26 5.98E-02 -3.50E-05 7.47E-09 40.823 5.732
Ar 0.002 15.763 298.15 493.15 28.11 1.97E-03 4.80E-06 -1.97E-09 29.526 0.050
CH
4

0.006 51.764 298.15 493.15 19.89 5.02E-02 1.27E-05 -1.10E-08 41.071 0.229
C
2
H
6

0.000 0.000 298.15 493.15 6.9 1.73E-01 -6.41E-05 7.29E-09 65.476 0.000
H
2
O
0.199 1840.461 298.15 493.15 32.24 1.92E-03 1.06E-05 -3.60E-09 34.450 6.838
Total
1.000 9271.565

31.856
50


Therefore, temperature at HTSC outlet, T =598.83 K or 325.68 C
Results
Stream No.
Temperature
(C)
Pressure
(kg/cm2 g)
Flow rate
(kmol/h)
Enthalpy
(kJ/h)
5-NG feed 35 40 1751.560 6.11E+05
6-desulphurizer inlet 400 40 1872.910 2.95E+07
7-desulphurizer outlet 390 39 1872.910 2.86E+07
8-process steam 380 38 3512.982 4.39E+07
9-mixer outlet 370 37 5385.892 6.94E+07
9-primary reformer inlet 600 35 5385.892 4.96E+07
10-2ndry reformer inlet 810 32 6952.823 1.95E+08
11-compressed air 35 175 1755.462 5.12E+05
11-preheated compressed air 600 32 1755.462 3.09E+07
12-2ndry reformer outlet 945 31 9271.565 2.89E+08
12-HTSC inlet 220 30 9271.565 5.67E+07
13-HTSC outlet 325 29 9271.565 8.88E+07
13-LTSC inlet 210 29 9271.565 5.46E+07
14-LTSC outlet 220 28.5 9271.565 5.74E+07
14-KO drum inlet 75 28 9271.565 1.45E+07
16-CO
2
absorber inlet 75 28 7590.931 1.17E+07
17-CO
2
to urea plant 40 0.2 1370.456 7.71E+05
18-stripper outlet 50 26.6 6220.476 4.52E+06
18-methanator inlet 320 26.5 6220.476 5.39E+07
19-methanator outlet 343.5 26.2 6179.296 5.92E+07
19-KO drum inlet 40 26 6179.296 2.70E+06
21-KO drum outlet 40 26 6067.506 2.64E+06
22-recycle to desulphuriser 45 40 121.350 7.04E+04
24-fresh make up gas 42 135 7031.649 3.47E+06
27-NH
3
convertor inlet 255 144 38814.461 2.66E+08
28-NH
3
convertor outlet 454.78 141 36118.384 5.09E+08
30-purge gas 10 135 1805.919 -8.08E+05
33-HRU intlet 40 125 1639.495 7.21E+05
34-recovered H
2
55 40 1088.541 9.44E+05
35-boiler fuel gas 55 39 2724.988 2.39E+06


Ceramic balls
Catalyst bed
Ceramic
baIls.__
Naphlha+H2
products

6.1 High Temperature Shift Converter:
Designing Steps:
1. Selecting the type of reactor.
2. Material Balance.
3. Energy Balance.
4. Catalyst Selection.
5. Estimating the rate of reaction.
6. Determining the weight of the catalyst.
7. Finding the volume of bed.
8. Length, diameter and volume of the reactor calculation.
9. Pressure drop Calculations.
Selecting the Type of Reactor:
As we have already concluded from above
discussion that we are using fixed bed adiabatic reactor.


Alumina
Balls
Catalyst
Bed
Alumina
Balls
Reactants
Product
6 EQUIPMENT DESIGNING

51

o
II
c

(X)+O O-():O
\. / \.:/
M ]\,1
()
II
/C\.
_() 0
" / M
_ 0
/
~1
+(~()~
-
H H H H
\/ I I
H~O
+ 0-0
o_()
O-lJ 0
+
H~
/
.
/
-,
/ \ /
'.
.
[V I ] \<t
M 1\1
r - d S t Fast Slow



Catalyst Selection:
The catalyst used for HTS is HTS catalyst is iron oxide
(Fe
2
O
3
) containing additionally 5 - 10 % chromic oxide (Cr
2
0,). (The catalyst SK-201-2 is
chromium oxide promoted iron oxide.)
Temperature and pressure condition are:
Temperature = 320 to 500
0
C.
Pressure = 33 to 36 atm.
Catalyst Specification are given below:
Porosity = = 0.455.
Particle Density = 2021 Kg/m
3

Bulk Density = 1123 Kg/m
3

Particle Size = D
p
= 0.006 m
Estimating the rate of reaction:
The mechanism by which reaction is
HTS takes place is

Figure Reaction Mechanism

52
k = rate constant
=exp (15.95 - 8 8 2 0 j T ) f or i ron catal yst
K = equi l i bri um constant
=exp (- 4.33 + 8 2 4 0 1 T ) f or 1060 < T < 1360
I ron catal yst I j J = 0.816 + O .184P f or P < 11.8
= 1.53 + 0.123P f or 11.8 < P < 20.0
= 4.0 f or P >20.0
X,a Vs, l/-I ra
~ 80~--~~~~~---------
, = = = = = = = = = = ~~~; ; ~; ; =
;:- I 60
40
20~------------------~-
0. 1 0. 2 0. 3 0. 4 0. 5 0. 6 0. 1 0. 8


The rate Equation which we have used is








Area Under the curve is = 62.4

53
V o l u m e O f b e d = V o l u m e o f c a t a l y s t
l-qJ


Determining the Weight of the Catalyst:
The weight of the catalyst can be
determined by using the follow formula :

Where:
X
a
= 75 %
F
Ao
= 1281.918 lb- mol
Area under the Curve = 62.4
So than

W = 80000 Lb or
W = 36.36 Tons
Particle Density = 2021 kg/m
3

Volume of Catalyst = 18 m
3

Finding the volume of bed and volume of the reactor:
Volume of Catalyst = 18 m
3

Porosity () = 0.455

Volume of bed = 32.4 m
3

Length and diameter Reactor:
L/D ratio = 1.8.
Crossectional Area of Bed = 6.34 m
2

Length of Bed = 5.1 m.
Diameter of Bed = 2.84 m.
Length of Reactor = 6 m .
54
f J . P G 1 - c p 150 ( l - c p ) , u + 1 . 7 5 G
---
L
pg
D
r p
3 D p
c p

Pressure drop Calculations:
According to Erguns equations

Length = 5.2 m
Bulk density () = 1122.79 kg/m
3

G = 23893 kg/hr.m
2

D
p
= 6 mm
g
c
= 12.8 x 10
7
m Kg
m
/hr
2
Kg
f

Porosity () = 0.445
Viscosity () = 2.05410
-5
Kg/m.sec
Pressure Drop (P) = 43 Kpa

55
Ceramic balls
Catalyst bed
Ceramic
baIIs___
Naphtha+H2
products

6.2 Low Temperature Shift Converter:
Designing Steps:
1. Selecting the type of reactor.
2. Material Balance.
3. Energy Balance.
4. Catalyst Selection.
5. Estimating the rate of reaction.
6. Determining the weight of the catalyst.
7. Finding the volume of bed.
8. Length, diameter and volume of the reactor calculation.
9. Pressure drop Calculations.
Selecting the Type of Reactor:
As we have already concluded from above
discussion that we are using fixed bed adiabatic reactor.


Alumina
Balls
Catalyst
Bed
Alumina
Balls
Reactants
Product
56

Catalyst Selection:
The catalyst used for LTS is Oxides of Copper, Zinc, and
Chromium or Aluminium. (The LK-821-2 catalysts consist of oxides of copper, Zinc, and
Chromium or Aluminum)
Temperature and pressure condition are:
Temperature = 170 to 250
0
C.
Pressure = 32 to 35 atm.
Catalyst Specification are given below:
Porosity = = 0.455.
Particle Density = 2486 Kg/m
3

Bulk Density = 1443 Kg/m
3

Particle Size = D
p
= 0.006 m
Estimating the rate of reaction:
The mechanism by which reaction in
LTS takes place is

57
( - r e o ) =~ k ( Y C O Y H 2 0 - Y C 0
2
Y H ) K ) / ( 3 7 9 P b )
K = e q u i l i b r i u m c o n s t a n t
= e x p ( - 4 , 1 1 + ~ 6 4 0 I T )f o r 7 6 0 ~ T ~ 1 0 6 0
: k =r a t e c o n s t a n t
- , , ttl
= = e x p ( 1 2.88 - 3 3 4 0 1 T ) f o r c o p p e r - zi n c c a t a l ys t
C o p p e r - zi n c c a t a l ys t ~ =0 .86 + O . 1 4 P f o r P <24 .8
= 4 .33 f o r P > 24 .8
, X : , a Vs 1/-[ra
305 -.---------------
300 ~----------
295 +- - ~;: - - - - - - - - - - - -
290 +- - - ~~- - - - - - -
275 +- - - - - - - ~.: : __- - -
27 0 + -----------~~--
265 +- - - - - - = = = = = = = = ;;;;;;;;~~~-
26 0 +- - - - .- - - - - - - - - - .- - - - - - - - , - - - - - - - - - - - r - - - - - - - +- - - - - - - ,
0 .2 0 .4 0 .6 0 .8 1




The rate Equation which we have used is








Area Under the curve is = 62.4
58
V o l u m e O f b e d = V o l u m e o f c a t a l y s t
l-qJ


Determining the Weight of the Catalyst:
The weight of the catalyst can be
determined by using the follow formula :

Where:
X
a
= 90 %
F
Ao
= 388.146 lb- mol
Area under the Curve = 254.25
So than

W = 98700 Lb or
W = 44.86Tons
Particle Density = 2486.2 kg/m
3

Volume of Catalyst = 18 m
3

Finding the volume of bed and volume of the reactor:
Volume of Catalyst = 18 m
3

Porosity () = 0.455

Volume of bed = 32.4 m
3

Length and diameter Reactor:
L/D ratio = 1.8.
Crossectional Area of Bed = 6.34 m
2

Length of Bed = 5.1 m.
Diameter of Bed = 2.84 m.
Length of Reactor = 6 m .
59
IlP G 1-!p 150 (1-!p ) J l +1.75G
---
L
pg D (f)3 Dp
c P 'r


Pressure drop Calculations:
According to Erguns equations

Length = 5.2 m
Bulk density () = 1443.6 kg/m
3

G = 23893 kg/hr.m
2

D
p
= 6 mm
g
c
= 12.8 x 10
7
m Kg
m
/hr
2
Kg
f

Porosity () = 0.445
Viscosity () = 1.66310
-5
Kg/m.sec


Pressure Drop (P) = 33 Kpa

60
V*
vv
J
L*
vv
Percentage flooding =[ K 4 at design pressure drOP] 1/2
K4 at flooding
61

1.5 inch Carbon Steel IMTP
Moles of CO
2
entering =1373.202 kmol/h
Loading Point =0.6 mol of CO2/mol of MDEA
Moles of MDEA required =1373.202/.6 =2288.67 kmol/h
Mass of MDEA required =2288.67 119.16 =272717.92 kg/h
Mass of water required =272717.92/0.6 =454529.867 kg/h
Moles of water required =454529.867/18.02 =25223.63 kmol/h
Total molar flow in of solvent =2288.67 +25223.63 =27512.3 kmol/h
Total mass flow in of solvent =272717.92 +454529.867 =727247.787 kg/h
For 99.8 % CO2 absorption
CO2 absorbed =1373.202 .998 =1370.456 kmol/h
Total Molar flow out of solvent =27512.3 +1370.456 =28882.756 kmol/h

L
w
=Solvent mass flow into the column =727247.787 kg/h
V
w
=Gas mass flow into the column =15.93 7590.931 =120923.5 kg/h

L
=Density of solvent =1016.8 kg/m
3

v
=Density of gas =14.18 kg/m
3

F
LV
=0.71

Pressure drop =15 mmof H2O/mof packing
K
4
at design pressure drop =0.27
6.3 Absorption Column
10.0
6.0
4..0
2..0
1.0
r
0.6
0.4
K4
I
0.2
0.1
0.06
0.04
0.02
-
:--
--
r-.
..:::::
P 7.Y f l .
r-
P ar ar notor 0cur vOS." pr o"sur o dr op
":>. inmmotwatGr/mgtro of packGd
8~ ...... <:Ol 'l "'919ht
...._ _
- - .:::::::::::::; :~>? 9
{"4 fv
r---~~r--
-
~l.
--r-..
- ....; ; :
~
.....
rc>,/
-
-
I'-
~......
-
--...
r - - ....
.......... '
~ ......
()
-r-
..........
~
t-
-
~"""
~
~ ~
(4)
I --
r - - .::
~
0.02 0.04 0.06 0.1 0.2 0.4 0.6 1.0 2.0 4.0 6.0 10.0
---FLV--_
Pv(PL - Pv)
62

K
4
at flooding =0.88
Percentage flooding =55 %


Gas Mass Velocity

F
p
=24 m
-1

L
=2.748 10
-3
K
4
=0.27
Operating mass velocity =V
w
=6.63 kg/m
2
s


63

Column Diameter
Area of column =A
c
=mass flow rate/mass velocity
Gas mass flow rate =120923.5/3600 =33.59 kg/s
Mass velocity =6.63 kg/m
2
s
A
c
=5.07 m
2

Diameter of column =D
c
=(4A
c
/)
1/2
=2.54 m
Rounded off
D
c
=2.6 m
A
c
=5.30 m
2


Effective Interfacial Area

a =150.8 m
2
/m
3

L
w
=727247.787/(3600 5.30) =38.12 kg/m
2
s

L
=Liquid surface tension =48.5 10
-3
N/m

c
=Critical surface tension of packing =55 10
-3
N/m
a
w
=141.1 m
2
/m
3


Liquid film mass transfer co-efficient

D
L
=.443 10
-9
m
2
/s
kcs RT == s,(V~ ) 0.7 ( /.Lv ) 1/3(ad p)-2.0
a o; au.; PvDv
He
keClvvP
Lm
H
L
= ---
kLawCt
64

d
p
=Diameter of packing =0.038 m
k
L
=3.02 10
-4
m/s

Gas film mass transfer co-efficient

V
w
=6.63 kg/m
2
s
D
v
=Vapor diffusivity =1.38 10
-5
m
2
/s

v
=Viscosity of vapors =8.99 10
-5
kg/ms
R =Universal gas constant =0.08314 bar m
3
/kmol k
k
G
=7.3 10
-4
kmol/s bar m
2


Gas film transfer unit height

G
m
=Molar gas flow per unit column area =7590.931/(3600 5.30) =0.3978 kmol/m
2
s
P =30.3 bar
H
G
=0.13 m

Liquid film transfer unit height

L
m
=Molar liquid flow per unit column area =27512.3/(3600 5.30) =1.442 kmol/m
2
s
C
t
=Density/ Molecular weight =1016.8/26.42 =38.49 kmol/m
3

65

H
L
=0.88 m

Height of transfer units

mG
m
/L
m
=0.75
H
OG
=0.79 m

Number of transfer units
Y1 =Mole fraction of CO2 in entering gas =0.1809
Y2 =Mole fraction of CO2 in leaving gas =.0004
Y1/Y2 =425
mG
m
/L
m
=0.75 (Colburn suggested 0.7-0.8)
N
OG
=19

28 5:3 2 I4 12 II
10 0'95 0'9 085
24
j I
I II
1 /
I
II'
I
I J II /
II
I I V
V
1 'I II 7
V
[ I ~ 1. 1
/ /
I , . -
~ I / / v
[ 7 / 1/
v
j 'I
1/ /
v
l, . -
I
j j
~ /
v
L , ;
I I 17
LI / . / t>
I I
j v
V . / V
~
I
1/ II ~ /" . / V
l , . . -
I V
v
V /'
V L . - - -
I I /I ~ II
- 7
VV
~~
I I /V
j I. ;
1,.0'/
1/i/' t-
II 1/) 7
, / V
I. - - ' V7Vv
1/I /V
v
v - i. - ' V/
v
_ . . . ~
II 1// /
v v
V ~
V_/
. . . -
~
_ . . . ~
II .rr>v.......
v.......
. /
10- "1;
.>t- -
10- "
~. . . . . . . . I-
-
IIJ Ill. . V//~ v /~ ~
i;'
I ;~
c:- - -___
~
-
I- - t:.
~ .
IJ II Ii
~~y~ ~
r- -
i- - t : : : . . . . .
I . . - - : : : : : ;: : ;;
~~~o
It J
r/~~
~~
~ t : : : : : : : :
~
'-
'- ~
)
h~~
~I ;
~
~
J /.~
~~ ~
~
I
L/. Z~
;: . . . . - >-
~
22
20
16
16
14
12
10
8
6
4
2
o
I 2 5 10 20
100 200
08
0750
07
065
06
055
05
04
03
02
01
1000
66



Height of Column
Z =HOG NOG
Z =15 m
Height for liquid distribution and re-distribution =2 m
Total height of column =17 m

Pressure drop =0.27 in H2O/ft of packing
Wetting rate =2.5 10
-4
m
3
/ms



1. Material balance calculations.
2. Selection of appropriate ammonia convertor.
3. Evaluating available data.
4. Solve the rate expression.
5. Determine the volume of beds.
6. Determine the amount of a catalyst.
7. Determine the total volume of the reactor.
8. Determine the length and diameter of the beds.
9. Calculate the pressure drop.
Overall 28% conversion based on limiting reactant.
Max 17% per pass conversion.
First bed inlet is 60% of the total inlet of the reactor.
For 2nd & 3rd bed 20% of the inlet flow is introduced as a quenched stream.




Design Calculations of Ammonia Reactor:
As the reactor selection and
catalyst selection is already been done. Now by solving the rate expression and volume
calculations are given below:
Volume & Amount of Catalyst of First Bed:
-ra vs Xa plot gives area
under the curve and simply by multiplying with flow rate we get volume of reactor.
ASSUMPTIONS:
6.4 Ammonia Reactor:
67
X
V
n
:=; Fn.o J ~
-r~
o .



Volume of bed 1 = (Flow rate)*(area under the curve)
= (12693)*(0.00175)
Volume of bed 1 = 22 m
3
Weight of the catalyst = Wn = Vn*
Weight of catalyst bed 1 = (22)*(4900)
W
1
= 10910
3
kg
Volume & Amount of Catalyst of Second Bed:


Volume of bed 2 = (Flow rate)*(area under the curve)
= (16036)*(0.001775)
Volume of bed 2 = 28 m
3

Weight of the catalyst = W
n
= V
n
*
Weight of catalyst bed 2 = (28)*(4900)
W
2
= 13910
3
kg

Volume & Amount of Catalyst of Third Bed:

Volume of bed 3 = (Flow rate)*(area under the curve)
= (19477)*(0.00165)
Volume of bed 3 = 32 m3
Weight of the catalyst = Wn = Vn*
Weight of catalyst bed 3 = (32)*(4900)
W
3
= 157103 kg
Volume of catalyst bed = V
1
+V
2
+V
3

= 83 m
3

68


Volume of reactor = (vol of catalyst )/(1- )
= (83)/(1-0.35)
Vr = 127 m
3

Area of bed = volumetric flow rate / superficial velocity
A
r
= 5 m
2

Diameter of reactor = (4A
r
/)
1/2

Dr = 2.6 m

Length of bed = L
n
= V
n
/A
B

Length of bed 1 = 4.2 m
Length of bed 2 = 5.4 m


Length of bed 3 = 6.1 m
Total length of beds = 16 m

Length of reactor = L
b
+Li (length allowance in 3m)
= 16+3
L
t
= 19 m

Pressure Drop Calculations:


Nomenclature:
Mass velocity G =12.70 kg/m
2
sec Density = 2650 kg/m
3

Viscosity = 0.00002411 kg/m.sec Particle dia D
p
= 4 mm
Pressure drop = 204.4 kPa
P = 204 kPa
Heat exchanger is the equipment
used to exchange heat between two fluids at different temperature through a fixed wall
without mixing the two fluids. Basic purpose of heat exchanger is to control the temperature
between the beds so that we get maximum conversion on optimum conditions. Reduce the
2nd Bed temperature from 475
o
c to 425
o
c.
G
D D g
G
L
P
p p c
75 . 1
1 150 1
3
Interbed Bed Heat Exchanger:
69
Shell...side
Shell...side fluid outlet
Quenched gas
Ti =200 c
Pi = 198 atm
Flowrate=4.5*104 kg/hI
1
Ti= 253c
Pi = 197.5atlll
Flowrate= 4.5*10
4
kg/lu
I
2
nd
Bed outlet
Ti=475c
Pi =197 atm
Flowrate= 1.8*10
5
kg/hr
ri.475 -c
Pi = 196.5 attn
Flowrate= 1.8* 105
kgllu




Design steps of Interbed Heat Exchanger:
1. Finding the physical properties & Exchanger selection.
2. Heat load.
3. LMTD.
4. Assume overall heat transfer coefficient.
5. Calculate area required.
6. Assume geometry.
7. Calculate individual heat transfer coefficient.
8. Calculation of overall heat transfer coefficient.
9. Calculations of pressure drop in shell and tube side.

Exchanger Streams Specification:

70

















Heat Load calculations:
Process gas:
Q = m c
p
(Th
,out
Th
in
)
= 7804.7kw
LMTD:




Calculation of heat transfer area:
Assumption of U
d

Assumed U
d
= 700 W/m
2
K
Heat Load =Q = 7804.7kw
LMTD = 223
o
C
F
t
= 0.99
A=Q/(U
d
. LMTD*F
t
)
=50m
2
No of tubes:
selected triangular pitch tube layout having following specification:
Length of Tube = 4 m
Specification Process gas Quenched gas
Flow rate 1.8 *10
5
(Kg/hr) 4.5*10
4
(Kg/hr)
Inlet Temperature 475
o
C 200
o
C
Outlet Temperature 425
o
C 253
o
C
Pressure 197 atm 197 atm
Shell Side Tube Side
Process gas Quench gas
C
p
3.07 kJ/kg.K 11.43 kJ/kg.K
0.00002411 Kg/m.s 0.0000229 Kg/m.s
36.79 kg/m
3
39.03 kg/m
3

k 0.1682 W/m.K 0.1647 W/m.K
C
T T
T T
T T T T
LMTD
in c out h
out c in h
in c out h out c in h 0
, ,
, ,
, , , ,
223
ln
71


Tube internal Dia = 0.015748 m
Tube External Dia = 0.01905 m

Surface area of one tube = .d
o
L = 0.239268 m
2

Number tubes =A/.d
o
L= 208
Selected number of tubes = 217

Calculations along Tube side:
Linear velocity
Number of Passes = 1
Flow area per tube = r
2
= 0.00019468 m
2

Total number of tubes in one pass = 217
Total Flow area in one pass = 0.040660472 m
2

Volumetric flow rate of quench gas = 0.325469012 m
3
/sec
Velocity of quench = flow rate/flow area
= 8 m/sec (valid velocity range 1-15 m/s)
Calculation of film coefficient (h
i
):
Reynold No. = Dv/
= 214845
Prandtle No. = C
p
/K
= 1.68
L/Di = 63.5
J
H
=

120
hi = Jh(k/Di)(Re)(Pr)
0.33
(/
w
)
0.14

= 665 W/m.
0
C

Calculations along Shell side:
Shell sides Velocity calculation:
Gas Volumetric Flow rate = 1.38 m
3
/sec
Baffle spacing =1m
Pitch = P = 0.0254 m
Internal dia Of shell = Ds = 0.4381 m
Clearance = c = 0.00635 m
Flow area of shell =a
s
= cBD
s
/P
o = 0.109525 m
2

72


Velocity of gas on shell side = flow rate/flow area
= 12.6 m/sec
Equivalent Dia for shell:
De = 4[(0.5P)(0.86P)-(d
o
2
/8)]/ d
o
/2
Pitch = 0.0254 m
External Dia Of tube = 0.01905m
D
e
= 0.018 m
H
o
calculations
R
e
= U
s.
.D
H
/ = 347367
P
r
= C
P
/ K = 0.44
J
H
= 200


h
o
= 1417 W/m.
0
C

Pressure drop Calculation along Tube side:
Reynolds Number = 214845.2274
f = 0.0085
G
t
=312.41781223kg/m
2
.s
Length of shell =4m
Number of tube passes=1
g=9.8m/s2
Density=39.03kg/m
2

di =0.015748
Pressure Drop P
t=
275.5kg/m
2

= 2.7Kpa
Pressure drop Calculation along Shell side:
Re=347367.1437
f =0.03
Internal Dia of Shell =0.4381m
Density=36.79kg/m3
g=9.8m/s
2

D
H=
0.018052335m
Mass flow rate G
S=
463.9301022kg/m
2
.sec
N
b=
3
Pressure Drop in the shell = 869 kg/m
2

Pressure Drop in the shell=8.5Kpa

73
L*
w
J V*
w
Percentageflooding=[ K 4 atdesignpressuredrO P] 1/2
K 4 atflooding
74

1 inch Carbon Raschig rings
Moles of NH
3
entering =166.4245 kmol/h
Loading Point =0.12 kg of NH
3
/kg of water
Mass of NH
3
entering the column =166.42 17 =2829.31 kg/h
Mass of water required =2829.31/.12 =23577.6 kg/h
Moles of water required =1308 kmol/h
For 100% NH
3
absorption
NH
3
absorbed =166.42 kmol/h
Total Molar flow out (solvent) =166.42 +1308 =1474.42 kmol/h
Material Balance on Ammonia
L
a
x
a
+Vy =Lx +V
a
y
a

1308(0) +1805.919(.092) =1474.42x +1639.495(0)
x =0.12

L
w
=Solvent mass flow into the column =23577.6 kg/h
V
w
=Gas mass flow into the column =18276 kg/h

L
=Density of solvent =1000 kg/m
3

v
=Density of gas =14.25 kg/m
3

F
LV
=0.15

Pressure drop =30 mmof H2O/mof packing
6.5 Ammonia Recovery Unit
K4-
C
lpl~~)O.l
13.1(V*)2p r-r-:
1N P
Pv(PL - Pv)
75

K
4
at design pressure drop =1
K
4
at flooding =2.7
Percentage flooding =37 %

Gas Mass Velocity

F
p
=155 m
-1

L
=viscosity of water =1 10
-3
Ns/m
2

K
4
=1
Operating mass velocity =V
w
=5.25 kg/m
2
s

Column Diameter
Area of column =A
c
=mass flow rate/mass velocity
Gas mass flow rate =18276/3600 =5.077 kg/s
Mass velocity =5.25 kg/m
2
s
A
c
=0.97 m
2

Diameter of column =D
c
=(4A
c
/)
1/2
=1.11 m
Rounded off
D
c
=1.2 m
A
c
=1.13 m
2



kG RT =s,(V~ ) 0 0 7 ( /-Lv ) 1/3(ad
p
)-2.0
a D'; au.; PvDv
76


a =190 m
2
/m
3

L
w
=23577.6/(3600 1.13) =5.80 kg/m
2
s

L
=Liquid surface tension =73 10
-3
N/m

c
=Critical surface tension of packing =61 10
-3
N/m(ceramic)
a
w
=118 m
2
/m
3


Liquid film mass transfer co-efficient

D
L
=1.24 10
-9
m
2
/s
d
p
=Diameter of packing =0.025 m
k
L
=9.6 10
-5
m/s

Gas Film Mass Transfer Co-Efficient

V
w
=5.25 kg/m
2
s
D
v
=Vapor diffusivity =2.63 10
-5
m
2
/s

v
=Viscosity of vapors =9.09 10
-5
kg/ms
R =Universal gas constant =0.08314 bar m
3
/kmol k
k
G
=1.6510
-3
kmol/s bar m
2

Effective Interfacial Area
He
Gm
kcawP
HOG
77


Gas Film Transfer Unit Height

G
m
=Molar gas flow rate per unit column area =1805.919/(3600 1.13) =0.44 kmol/m
2
s
P =2.36 bar
H
G
=0.02 m

Liquid film transfer unit height

L
m
=Molar liquid flow per unit column area =1308/(3600 1.13) =.322 kmol/m
2
s
C
t
=Density/ Molecular weight =1000/18.02 =55.5 kmol/m
3

H
L
=0.512 m

Height of transfer units

mG
m
/L
m
=0.75
H
OG
=0.404 m

Number of transfer units
Y1 =Mole fraction of NH3 in entering gas =0.092
Y2 =Mole fraction of NH3 in leaving gas =0.004
Y1/Y2 =23
78

mG
m
/L
m
=0.75 (Colburn suggested 0.7-0.8)
N
OG
=7.5

Height of Column
Z =HOG NOG
Height of column =3.03 m

Pressure drop =0.26 in H2O/ft of packing
Wetting rate =3.07 10
-5
m
3
/ms

6.6 Hydrogen Recovery Unit
Permeance of Hydrogen =P
H2
=2.6 x10
-4

cm
3
/ cm
2
.sec.cmHg
Permeance of Nitrogen=P
N2
=3.47 x 10
-6
cm
3
/ cm
2
.sec.cmHg
Permeance of Methane =P
CH4
=2.48 x 10
-6
cm
3
/ cm
2
.sec.cmHg
Permeance of Argon =P
Ar
=1.5 x 10
-6
cm
3
/ cm
2
.sec.cmHg
Selectivites

H2/N2
=75

H2/CH4
=105

H2/Ar
=173
Feed compoaition:
x
fH2
=0.699
x
fN2
=0.233
x
fCH4
=0.051
x
fAr
=0.017

79


Stage cut = = 0.6
q
f
=
1639.495 9.43
0.45
= 34400 m
3
/h
q
p
= q
f
=0.6 x 34400 =20640 m
3
/h =5.73 x 10
6
cm
3
/s
Outer diameter of fiber =OD=300 m
Inner diameter of fiber =ID =150 m
Thickness =t =75 m
Fiber length =1m
Fiber Pot length =0.1m
No. of fibers / m
2
of area =500000 / 377 =1326 fibers / m
2

High pressure (feed stream) =P
h
=125 kg/ cm
2
.g =9272 cmHg
Low Pressure (permeate stream) =P
l
=31 kg/cm
2
.g =2356 cmHg

Assume y
PH2
=0.932

A
m
=Area of membrane =q
p
y
pH2
t / P
H2.
[P
h
/(1- ) (x
fH2
-
ypH2
) y
pH2
p
l
]
A
m
=147447 cm
2


y
PN2
={p
h
x
fN2
/ (1-)} / [{(/(1 - )} P
h
+P
l
+q
p
t / A
m
P
N2
]
y
PN2
=0.0539

y
PCH4
={p
h
x
fCH4
/ (1-)} / [{(/(1 - )} P
h
+P
l
+q
p
t / A
m
P
CH4
]
y
PCH4
=0.009

80

y
PAr
={p
h
x
fAr
/ (1-)} / [{(/(1 - )} P
h
+P
l
+q
p
t / A
m
P
Ar
]
y
PAr
=0.002

y
pn
=y
PH2
+y
PN2
+y
PCH4
+y
Par
y
pn
=0.932 +0.054 +0.009 +0.002 =0.997

Now For y
PH2
= 0.934

A
m
=Area of membrane =q
p
y
pH2
t / P
H2.
[P
h
/(1- ) (x
fH2
-
ypH2
) y
pH2
p
l
]
A
m
=152512 cm
2

y
PN2
=0.055
y
PCH4
=0.009
y
PAr
=0.002
y
pn
=y
PH2
+y
PN2
+y
PCH4
+y
Par
=0.934 +0.055 +0.009 +0.002
y
pn
=1

q
o
=q
f
q
P
=34400 20640 =13760 m
3
/ h
Reject flow rate =13760 m
3
/ h

Now for reject stream
x
oH2
=[{x
fH2
/ (1- )} { ( y
PH2
) / (1 - )}]
x
oH2
=0.347
x
oN2
=0.5
x
oCH4
=0.114
81

x
oAr
=0.039
x
on
=x
oH2
+x
oN2
+x
oCH4
+x
oAr
=0.347 +0.5 +0.114 +0.039 =1.0
x
on
=1
Area =16 m
2
(approximately)
Permeate Reject Feed

H
2
0.934 0.347 0.699
N
2
0.055 0.5 0.233
CH
4
0.009 0.114 0.051
Ar 0.002 0.039 0.017

Checking
For H
2
(overall material balance)
x
f
q
f
=y
P
q
P
+x
o
q
o

24046 24052 hence proved
For N
2
(overall material balance)
x
f
q
f
=y
P
q
P
+x
o
q
o

8015 =8015 hence proved
For 1 m
2
area, no. of fibers required =1327
For 16 m
2
area, no. of fibers required =16 x 1327 =21232 fibers
For 4 hollow fiber modules =21232 / 4 =5308 fibers / module
Fiber length =1 m
Fiber pot length =0.1 m
Height of hollow fiber module =1 +0.1 +0.1
Height of hollow fiber module =1.2 m


82

7.1 Cost Index Calculation
Cost index in 2002 =390.4
Annual escalation rate =2.5%
With a difference of 11 years;
Cost index in 2013 =390.4 x (1.025)
11
=512.24 .
Cost in any unknown year can be calculated as:
Cost index in year A =Cost in year B x
Cost index in year A
Cost index in year B


7.2 Fixed Costs
7.2.1 High Temperature Shift Converter:
Volume of the reactor =4.93 m
3
At 300 psi,
Cost in 2002 =$ 1500
C
e
=CS
n
=1500 x (4.93)
0.4
=$ 28394
Cost in 2013 =28394 x 512.24/ 390.4
=$ 37255
7.2.2 Low Temperature Shift Converter:
Volume of the reactor =4 m
3
At 300 psi,
Cost in 2002 =$ 1500
C
e
=CS
n
=1500 x (4)
0.4
=$ 24000
Cost in 2013 =24000 x 512.24/ 390.4
=$31490
7 COST ESTIMATION
83


7.2.3 CO
2
Absorption Column:
Bare vessel cost =$70,000
Material ratio =1, carbon steel
Pressure factor =1.4
Purchased cost =70,000 x 1 x 1.4 =$ 98,000
Cost of packing =25000 / m
3
x 22.3 =$ 56312.5
Total cost =98,000 +56312.5 =$154312.5
Cost in 2013 =154312 x 1.313
=$ 202611

7.2.4 Methanator:
Volume of the reactor =8.05 m
3
At 300 psi,
C
e
=CS
n
=1500 x (8.05)
0.4
=$34546
Cost in 2013 =34546 x 1.313
=$45360

7.2.5 Ammonia Converter:
Volume of the reactor =123.17 m
3
At 1500 psi,
C
e
=CS
n
=1500 x (123.17)
0.4
=$ 102871
Cost in 2013 =102871 x 1.313
=$ 135069

84

7.2.6 Heat Exchanger:
Using Carbon steel shell and Stainless steel tubes;
Material ratio =1
Pressure factor =1
Type factor =0.8
Heat transfer area =124.887 m
2

Cost in year 2004 =$110,000
Purchased Cost =Cost x Pressure Factor x Type Factor
Purchased Cost =110,000 x 1 x 0.8 =$ 88,000
Cost index in 2004 =390.4 x (1.0250)
2
Cost in 2013 =88,000 x 499.74/410.164
=$ 106000
7.3 Cost of Equipment
7.3.1 Purchase cost of equipment
PCE =HTS +LTS +Methanator +Ammonia converter +Absorber +12 x HX
PCE =37255 +31490 +45360 +135061 +120667 +(12 x 106000)
PCE =$1,641,833

Using Table 6.1, Coulson Vol. 6;
f
1
=equipment erection =0.45
f
2
=piping =0.45
f
3
=instrumentation =0.15
f
4
=electrical =0.1
f
5
=building, process =0.1
f
6
=utilities =0.45
85

f
7
=storage =0.2
f
8
=site development =0.05
f
9
=ancillary buildings =0.2
7.3.2 Physical plant cost:
PPC =PCE x [1 +(f
1
+f
2
+..+f
9
)]
PPC =1641833 x [1 +(0.4 +0.7 +0.2 +
0.1 +0.15 +0.5 +0.15 +0.05 +0.15)]
PPC =$ 5582232

f
10
(design and engg.) =030
f
11
(contractors fee) =0.05
f
12
(contingency) =0.1

7.3.3 Fixed Capital Cost:
FCC =PPC [1 +(f
10
+f
11
+f
12
)]
FCC =5582232 x [1 +(0.3 +0.05 +0.1)]
FCC =$ 8094236
WORKING CAPITAL =5% OF FCC
WC =FCC x 0.05 =$ 404712
Total investment for the project cost comes out to be
Total Project Cost =FCC +WC
Total Project Cost =$ 84,989,480


86

7.4 Operating Cost:
Operating time =365 0.95 =347 days/year
Operating time =8328 h/yr

7.5 Variable Costs:
7.5.1 Pump Operating Cost:
According to PEPCO sources;
Unit price of electricity =Rs. 8.9 /kWh
Power of pump =28.47 kW
Annual consumption =28.47 x 8328 =237098.16 kWh
Pump operating cost =(Rs. 8.9 x 237098.16 x $1)/Rs. 102
Pump operating cost =$ 22780

7.5.2 Compressor
Power required =992.863 kW
Cost in 2002 =$ 825,724
Cost in 2013 =825724 x 499.74/ 390.4 =825724 x 1.28

7.5.3 Utilities
i. Steam Cost
Cost of steam=Rs. 3110 /(tonne / hr)
Total steamrequirement =1.01 tonne/hr
Cost of steam=3110 x 1.01 =Rs. 3141.1
Annual cost =3141.1 x 8328 x $1 / Rs. 102 =$ 256461.6
87


ii. Cooling Water Cost
Cost of cooling water =1.025 c/t0nne
Cooling water requirement =200 tonne / hr
Cost of cooling water =200 x 8328 x 1.o25 x10
-3

Annual cooling water cost =$ 1707.24

Total Variable Cost =CW + Steam+1Pump +4 Compressor
Total Variable Cost =$ 43,567,820

7.6 Fixed Cost
Fixed Cpital Cost =FCC=$ 8,498,948
Maintenance cost =5% x FCC =369,904.37
Capital Charges =10 % x FCC =739,808.74
Insurance =1% x FCC =$ 73,980.874
Local taxes =2% x FCC =$ 147,961.75
Royalties =1% x FCC =$73,980.874
Operating labor =30 % x FCC =$ 2219426.22
Plant overhead =50% x Operating labor cost =$ 1,109,713.11
Total fixed cost =$ 54,393,260
Direct production cost =fixed cost +variable cost
Direct production cost =$ 9769108

Sales Expense +general overhead +R & D =20 % x Direct Production Cost
Sales Expense +general overhead +R & D =$1,863,798.85
88

Annual production cost =$ 5,728,406.04 +$ 1,145,681.21

ANNUAL PRODUCTION COST =$ 117,553,290
Production Cost =Annual production cost/ammonia production cost
Production cost =117,553,290 / (1100 x 347) =$ 30.8 / T

For 1100 MTPD
Production Cost =$ 338900/day












89

8.1 Fertilizer
Approximately 83% (as of 2004) of ammonia is used as fertilizers either as its salts or as
solutions. Consuming more than 1% of all man-made power, the production of ammonia is a
significant component of the world energy budget.
8.2 Precursor to Nitrogenous Compounds
Ammonia is directly or indirectly the precursor to most nitrogen-containing compounds.
Virtually all synthetic nitrogen compounds are derived from ammonia. An important derivative
is nitric acid. Nitric acid is used for the production of fertilizers, explosives, and many organo-
nitrogen compounds.
8.3 Cleaner
Household ammonia is a solution of NH3 in water (i.e., ammoniumhydroxide) used as a general
purpose cleaner for many surfaces. Because ammonia results in a relatively streak-free shine, one
of its most common uses is to clean glass, porcelain and stainless steel. It is also frequently used
for cleaning ovens and soaking items to loosen baked-on grime. Household ammonia ranges in
concentration from5 to 10 weight percent ammonia.
8.4 Refrigeration R717
Because of its favorable vaporization properties, ammonia is an attractive refrigerant. It was
commonly used prior to the popularization of chlorofluorocarbons (Freons). Anhydrous
ammonia is widely used in industrial refrigeration applications and hockey rinks because of its
high energy and low cost. The Kalina cycle, which is of growing importance to geothermal
power plants, depends on the wide boiling range of the ammonia-water mixture. Ammonia is
used less frequently in commercial applications, such as in grocery store freezer cases and
refrigerated displays due to its toxicity.
8.5 Remediation of Gaseous Emissions
Ammonia is used to scrub SO
2
fromthe burning of fossil fuels, and the resulting product is
converted to ammonium sulfate for use as fertilizer. Ammonia neutralizes the nitrogen oxides
(NOx) pollutants emitted by diesel engines. This technology, called SCR (selective catalytic
reduction), relies on a vanadium-based catalyst.

8 INDUSTRIAL APPLICATIONS
90

8.6 Fuel
Ammonia was used during World War II to power buses in Belgium, and in engine and solar
energy applications prior to 1900. Liquid ammonia was used as the fuel of the rocket airplane,
theX-15. Although not as powerful as other fuels, it left no soot in the reusable rocket engine and
its density approximately matches the density of the oxidizer, liquid oxygen, which simplified
the aircraft's design. Ammonia has been proposed as a practical alternative to fossil fuel for
internal combustion engines. The calorific value of ammonia is 22.5 MJ/kg (9690 BTU/lb)
which is about half that of diesel. In a normal engine, in which the water vapor is not condensed,
the calorific value of ammonia will be about 21% less than this figure. It can be used in existing
engines with only minor modifications to carburetors/injectors.
To meet these demands, significant capital would be required to increase present production
levels. Although the second most produced chemical, the scale of ammonia production is a small
fraction of world petroleumusage. It could be manufactured fromrenewable energy sources, as
well as coal or nuclear power. It is however significantly less efficient than batteries. The 60
MW Rjukan damin Telemark, Norway produced ammonia via electrolysis of water for many
years from1913 producing fertilizer for much of Europe. If produced fromcoal, the CO
2
can be
readily sequestrated (the combustion products are nitrogen and water). In 1981 a Canadian
company converted a 1981 Chevrolet Impala to operate using ammonia as fuel. Ammonia
engines or ammonia motors, using ammonia as a working fluid, have been proposed and
occasionally used. The principle is similar to that used in a fireless locomotive, but with
ammonia as the working fluid, instead of steamor compressed air. Ammonia engines were used
experimentally in the 19th century by Goldsworthy Gurney in the UK and in streetcars in New
Orleans in the USA.
8.7 Stimulant in Sports
Ammonia has found significant use in various sports particularly the strength sports of power
lifting and Olympic weightlifting as a respiratory stimulant.
8.8 Textile:
Liquid ammonia is used for treatment of cotton materials; give properties like mercerization
using alkalis. In particular, it is used for pre-washing of wool.
8.9 Lifting Gas:
At standard temperature and pressure ammonia is lighter than air, and has approximately 60% of
the lifting power of hydrogen or helium. Ammonia has sometimes been used to fill weather
balloons as a lifting gas. Because of its relatively high boiling point (compared to heliumand
91

hydrogen), ammonia could potentially be refrigerated and liquefied aboard an airship to reduce
lift and add ballast (and returned to a gas to add lift and reduce ballast).
8.10 Wood Working:
Ammonia was historically used to darken quarter sawn white oak in Arts & Crafts and Mission
style furniture. Ammonia fumes react with the natural tannins in the wood and cause it to change
colors.














92

9.1 Recoveries Importance
Frommaterial balance calculations it has been estimated that by recovering NH
3
& H
2
fromsyn
loop purge gas, NG feed required for designated capacity reduces up to 10% that depict the
importance of recoveries in an ammonia plant. The use of recoveries also lowers the equipment
sizes in syn gas production area, especially the primary reformer size; hence lowering the overall
capital cast of plant.
9.2 Membrane Separation Technology
Hydrogen recovery from Polymer membranes has got several advantages as compared to
cryogenic technique as shown in table:
Table 9.1 Comparison of Polymer membrane and Cryogenic separation
Property Membrane Separator Cryogenic Separator
Initial Capital Cost $ 3,000 $ 7,000
Energy requirement .208 KWh/ kmol H
2
.442 KWh/ kmol H
2

% H
2
recovery 80 % 95 %
Eco friendly Yes No
Start-up time Minutes Hours











9 CONCLUSIONS
93





[1] E. Page, Engineering Page >Heat Exchangers >Typical Overall Heat Transfer
Coefficients.
[2] D.Q. Kern, Process Heat Transfer, First Edition ed., Mc-Graw Hill, 1983. [3]
XCELTHERMMK1 Engineering Properties.
[4] H.P. Bloch, A Practical Guide to Compressor Technology, Second ed., J ohn
Wiley & Sons, Inc., Hoboken, New J ersey, 2006.
[5] T.A. Adams Ii, P.I. Barton, International J ournal of Hydrogen Energy 34 (2009)
8877-8891.
[6] H.S. Fogler, Elements of Chemical Reaction Engineering, Third ed., Prentice- Hall,
Inc., New J ersey, USA, 1999.
[7] Temperature and Allowable Stresses for Pipes. [8]
F.J . Krieger, 1951.
[9] R.K. Sinnott, Chemical Engineering Design, Fourth ed., Elsevier Butterworth-
Heinemann, 2005.
[10] K.D.T. Max S. Peters, Plant Design and Economics for Chemical Engineers, Fourth
ed., McGraw-Hill Book Co., Singapore, 1991.
[11] C.Y. Wen, P.W. Chen, K. Kato, A.F. Galli, J ournal Name: Prepr. Pap. - Am. Chem.
Soc., Div. Fuel Chem.; (United States); J ournal Volume: 12:3 (1968) Medium: X; Size: Pages:
104-163.
[12] H.F. Rase, Chemical Reactor Design for Process Plants, First ed., J ohn Wiley & Sons
Inc., 1977.
[13] E. Page, Engineering Page >Heat Exchangers >Typical Overall Heat Transfer
Coefficients.
[14] D.Q. Kern, Process Heat Transfer, First Edition ed., Mc-Graw Hill, 1983. [15]
XCELTHERMMK1 Engineering Properties.
[16] H.P. Bloch, A Practical Guide to Compressor Technology, Second ed., J ohn
Wiley & Sons, Inc., Hoboken, New J ersey, 2006.
[17] T.A. Adams Ii, P.I. Barton, International J ournal of Hydrogen Energy 34 (2009)
8877-8891.
[18] H.S. Fogler, Elements of Chemical Reaction Engineering, Third ed., Prentice- Hall,
Inc., New J ersey, USA, 1999.
[19] Temperature and Allowable Stresses for Pipes. [20]
F.J . Krieger, 1951.
[21] R.K. Sinnott, Chemical Engineering Design, Fourth ed., Elsevier Butterworth-
Heinemann, 2005.
[22] K.D.T. Max S. Peters, Plant Design and Economics for Chemical Engineers, Fourth
ed., McGraw-Hill Book Co., Singapore, 1991.
[23] C.Y. Wen, P.W. Chen, K. Kato, A.F. Galli, J ournal Name: Prepr. Pap. - Am. Chem.
Soc., Div. Fuel Chem.; (United States); J ournal Volume: 12:3 (1968) Medium: X; Size: Pages:
104-163.
[24] H.F. Rase, Chemical Reactor Design for Process Plants, First ed., J ohn Wiley & Sons
Inc., 1977.
10 REFERENCES
94




[24] A Practical Guide To Compressor Technology. Bloch, Heinz P.
[25] Timmerhaus and Peters. [Online] www.mhhe.com/engcs.
[26] Chemical Process Industries. Gupta, O.P.
[27] R.K. Sinnott, Chemical Engineering Design, Fourth ed., Elsevier Butterworth-Heinemann, 2005.
[28] Ortrud Aschenbrenner and Peter Styring, Comparative study of solvent properties for carbon
dioxide absorption, paper, 9th June 2010.
[29] Gary Maxwell, Synthetic Nitrogen Products: A Practical Guide to the Products and Processes
Arthur L Kohl and Richard Nielsen, Gas Purification, Fifth ed.,
[30] Saeid Mokhatab and WilliamA. Poe, Handbook of Natural Gas Transmission and Processing,
Second ed.

[31] Kusuki et. al.,US patent, Gas Separation Asymmetric Membrane, 1992.
[32] Schendel et. al., Hydrocarbon Processing, 1983
[33] Emrani et. al., A Decision Tree for Technology Selection of Nitrogen Production Plants,
Journal of Chemical and PetroleumEngineering, 2011.
[34] D.T. Coker and B.D. Freeman, Modeling Multicomponent Gas Separation using Hollow Fiber
Membrane Contractors, 1998.
[35] A. Keith Fritzsche and James E. Kurz, The Separation of Gases by Membrane
[36] Duke et. al., Inorganic Membranes for Hydrogen Production and Purification: A Critical Review
and Perspective, Journel ofColloid and Interface Science, 2007
[37] Oana Cristina David, Membrane Technologies for hydrogen and Carbon monoxide Recovery
fromResidual Gas Streams, 2012
[38] Chunqing Liu et. al., Patent: Polyimide Gas Separation Membranes, 2012
[39] Albrecht et. al., Preparation of highly asymmetric hollow fiber membranes frompoly(ether
imide) by a modified drywet phase inversion technique using a triple spinneret, Journal of Membrane
Science, 2005.
[40] Krol et. al., Polyimide hollow fiber gas separation membranes: preparation and the
suppression of plasticization in propane/propylene environments, Journal of Membrane Science, 2001.
[41] G.H. Koops et. al., Wet spinning of integrally skinned hollow fiber membranes by a modified
dual-bath coagulation method using a triple orifice spinneret, Journal of Membrane Science, 1994. [42]
Vont Hof et.al., Preparation of asymmetric gas separation membranes with high selectivity by a dual-bath
coagulation method, Journal of Membrane Science, 1992.
[43] Imona C. Omole, Crosslinked Polyimide Hollow Fiber Membranes for Aggressive Natural
Gas Feed.