Nitric Acid Project - Final

Production of Nitric Acid for Fertilizer
Applications
Prepared by:
Mamdouh Al-anazi
Mohammed Al-Ajlan
Sultan Al-Sebeai
Hussni Mandeeli
Supervised by:
Dr. Farag Abd El-Salam
Dr. Malik Al-Ahmad
Prof. Tariq Al-Fariss
Submitted in partial Fulfillment of the Requirement for the Degree of Bachelor

ofScience in chemical Engineering in the college of Engineering
Riyadh
1434 1435 H
2013 2014 G
Table of Contents
Contents
Acknowledgement
Summery
Problem Statement
Objectives
Scope of Work
Chapter 1: Introduction
1.1
Backgrounds and History
1.2
The Nitric Acid Production Processes
1.2.1
The single Pressure Process
1.2.2
The Dual Pressure Process
1.2.3
The Process Selection
1.2.4
The Process Selection Conclusion
1.3
Main Uses of Nitric Acid
1.4
Physical Properties
1.5
Chemical Properties
1.6
Safety Properties
1.7
Market Survey
1.7.1
Economic Outlook
1.8
Preliminary Hazard Analysis
1.8.1
Summary of Previous Plant Accident
1.8.2
Inherent Safety Aspects
1.8.3
Local Safety and Environmental Regulations
1.9
Site Feasibility Study
1.9.1
Selection Criteria
1.9.2
Potential Site location
Chapter 2: Material Balance
2.1
Process Description
2.1.1
Process Flow Sheet
2.1.2
Justification of Equipment Selection
2.2
Overall Material Balance
2.3
Reactor Material Balance
2.4
Oxidation Material Balance
2.5
Absorber Material Balance
Chapter 3: Energy Balance
3.1
Vaporizer Energy Balance
3.2
Compressor Energy Balance
3.3
Superheater Energy Balance
3.4
Mixer Energy Balance
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3.5
Reactor Energy Balance
3.6
1st Cooler Energy Balance
3.7
Oxidation Energy Balance
3.8
2nd Cooler Energy Balance
3.9
Absorber Energy Balance
Chapter 4: Design and Sizing Equipment
4.1
Sizing of Pump
4.2
Design of Vaporizer
4.3
Sizing of Compressor
4.4
Design of Superheater
4.5
Sizing of Mixer
4.6
Design of Reactor
4.7
Design of 1st Cooler
4.8
Design of Oxidation
4.9
Design of 2nd Cooler
4.10
Design of Absorber
4.11
Design of Nitric Acid Tank
Chapter 5: Control Loop
5.1
Introduction
5.2
Control of Vaporizer
5.3
Control of Reactor
5.4
Control of Absorber
Chapter 6: Economic Analysis
6.1
Estimation of Capital Investment Items Based on
Delivered Equipment
6.2
Equipment Cost (at 2011)
6.3
Total Production Cost (TPC)
Chapter 7: Process Integration
Chapter 8: Safety and Loss Prevention
8.1
Plant Layout
8.2
Safety of Materials
8.3
Hazard and Operability Studies
Chapter 9: Waste Treatment
Conclusion
Reference
Appendices A: Material Safety Data
Appendices B: Physical Properties Data
Appendices C: Detailed Material Balance Calculation
Appendices D: Detailed Energy Balance Calculation
Appendices E: Equipment Design References
Appendices F: Computer Simulation by CHEMCAD
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Acknowledgement
First, thanks are to Allah who helped us throughout this work. Then, it is our
pleasure to thank those people who helped us in the completion of this project. Also,
we would like to express our deep gratitude and apprec ation to our dear supervisors:
Dr.Farag Abd El-Salam, Prof. Tariq Al-Fariss and Dr. Malik Al-Ahmad for their
support, advise, valuable scientific knowledge and patience throughout this project.
We would like to express our sincere thanks to the department of chemical
engineering at the College of Engineering, King Saud University, for giving us this
opportunity to carry out this project and we are grateful to our colleagues at King
Saud University for their inspiration, help and encouragement without which we
would not have been able to complete this project too. Last but not least we thank our
dear families and relatives for their assistance and encouragement.
Summary
The results of the design project for the commercial production of nitric acid are
presented. The project has been performed in two stages. The first part covers a
literature review on various processes for nitric acid production, selection of the suit
table processes, materials and energy balance calculations as well as the feasibility of
the project. The second part presents the detailed equipment designs. From the
investigation into project feasibility, it is proposed to construct a plant that will
deliver 100000 tons per year of 60%(wt.) Nitric acid. This capacity is based on 8000
hours of operation per year, i.e. 330 days. It is envisaged that this nitric acid
production facility will be centered within a larger chemical complex to be located in
the eastern region of Saudi Arabia. Other plants on this site will include an ammonia
plant and an ammonium nitrate plant. Approximately 70% of the product acid will be
consumed in situ for the production of ammonium nitrate Fertilizer. The remaining
acid will be available to exploit the neighboring export market. The process chosen
for the nitric acid plant is the "single-pressure process" based on the technology
developed by C & I Girdler. The most important use is undoubtedly in the production
of ammonium nitrate for the fertilizer and explosives industries, which accounts for
approximately 65% of the world production of nitric acid. So we made all our
production to be used in the fertilizer.
Problem Statement
It is required to design a suitable process for the production of 100,000-ton/year of
nitric acid from ammonia (60% concentration).
Objectives
The objectives of this design project include the following:
To integrate chemical engineering knowledge in a detailed design of chemical
plants.
To design a nitric acid plant which is economically attractive, safe to workers and
society and reduce harm to the environment?
To develop oneself in the applications of all the elements of knowledge and skills
that have been accumulated throughout the undergraduate program for solving
design related problems for typical process industrial plant.
To develop the skills for working as a team and to nurture leadership qualities.
Scope of work
This project is subjected to the designing phase of the process plant. All researches
and literatures used for this project falls under the scope of the chemical
compositions, current productions of nitric acid, preliminary hazards analysis, process
design configurations and selections, and configuration of plant equipment (i.e.
reactor, separation system, heat integration, etc.). The designing phase is then
executed using manual engineering calculations .The project is aimed at achieving the
objective of the plant design process.
Chapter 1
Introduction
The initial design problem is to determine whether: it is both economically and

technically feasible to establish a facility to produce nitric acid in the world. This is a
diverse and complex undertaking that necessitates a full investigation into the uses,
properties, market, process technology, and production economics, associated with
this particular chemical. Having considered these aspects and several others, an
appropriate plant to fulfill the assessed market requirements is sized and specified
accordingly. [1], [10]
1.1 Backgrounds and History

Nitric acid is a colorless, highly corrosive liquid and a very powerful oxidizing
agent that in the highly pure state is not entirely stable and must be prepared from its
azeotrope by distillation with concentrated sulfuric acid. Nitric acid gradually yellows
because of decomposition to nitrogen dioxide. Solutions containing more than 80%
nitric acid are called fuming nitric acids. [1], [4]
Reagent-grade nitric acid is a water solution containing about 68% by weight nitric
acid. This strength corresponds to the constant-boiling mixture of the acid with water,
which is 68.4% by weight nitric acid and boils at 121.9C. Nitric acid is completely
miscible with water and forms a monohydrate (HNO3.H2O, melting point: - 38C) and
a dehydrate (HNO3.2H2O, melting point: -18.5C). [7]
Scholars have known nitric acid for many centuries. Probably the earliest
description of its synthesis occurs in the writings of the Arabic alchemist Abu Musa
Jabir Ibn Hayyan (c. 721c. 815), better known by his Latinized name of Geber. The
compound was widely used by the alchemists, although they knew nothing of its
chemical composition. It was not until the middle of the seventeenth century that an
improved method for making nitric acid was invented by German chemist Johann
Rudolf Glauber (16041670). Glauber produced the acid by adding concentrated
sulfuric acid (H2SO4) to saltpeter (potassium nitrate; KNO3). A similar method is still
used for the laboratory preparation of nitric acid, although it has little or no
commercial or industrial value. [7]
The chemical nature and composition of nitric acid were first determined in 1784
by the English chemist and physicist Henry Cavendish (17311810). Cavendish
8
applied an electric spark to moist air and found that a new compound - nitric acid was formed. Cavendish was later able to determine the acids chemical and physical
properties and its chemical composition. The method of preparation most commonly
used for nitric acid today was one invented in 1901 by the Russian born German
chemist Friedrich Wilhelm Ostwald (18531932). The Ostwald process involves the
oxidation of ammonia over a catalyst of platinum or a platinum-rhodium mixture. [2]
Today, nitric acid is one of the most important chemical compounds used in
industry. It ranks number thirteen among all chemicals produced in the United States
each year. In 2005, about 6.7 million metric tons (7.4 million short tons) of the
compound were produced in the United States. [1]
1.2 The Nitric Acid Production Processes:

All commercially produced nitric acid is now prepared by the oxidation of
ammonia. The requirement for a nitric acid product of 60%(wt.) Immediately restricts
the choice of a recommended production process. Only two processes are possible,
both highly efficient, each offering distinct advantages under different market
conditions. [1]
These two main Processes are:
1.2.1 The Single-Pressure Process

The Single-Pressure process was developed to take full advantage of operating
pressure in enabling equipment sizes to be reduced throughout the process. A single
compression step is used to raise the pressure through the entire process sufficiently to
favor absorption. Operating pressures range from 800 kPa as used by the Sumitomo
Chemical Company Ltd. to 1100 kPa as used in the C&l Girdler single-pressure
process. Increased ammonia oxidation and complete ammonia/air mixing, and
uniform flow distribution can minimize increased consumption of ammonia due to the
higher-pressure operation across the gauze "inside the reactor". The higher oxidation
temperature results in an increased consumption of platinum and rhodium and the

need to rework the gauze every five to seven weeks .The higher temperature and the
favorable pressure effect make possible a greater recovery of energy from the process.
[10]
The process begins with the vaporization of ammonia at 1240 kPa and 35C using
process heat "as shown in the given flow sheet, Fig. (1). Steam is then used to
superheat the ammonia to 180C, filtered air is compressed by an axial compressor to
an interstage level and then, following cooling, by a centrifugal compressor to a
discharge pressure of 1090 kPa. A portion of the air is diverted for acid bleaching; the
remainder is circulated through a jacket surrounding the tail-gas preheater and then
used for ammonia oxidation. [10]
In this process; the heated air and the ammonia vapor (10.3% ammonia by volume)
are then mixed and passed through the platinum/ rhodium gauze reactor where the
heat of reaction (producing nitric oxide) raises the temperature to be between 927C
and 937C. The reaction gas flows through a series of heat exchangers in which
energy is recovered either as high-pressure superheated steam or as shaft horsepower
from the expansion of hot tail gas. [6]
Approximately 70% of the oxidation to nitrogen dioxide occurs as the gas passes
through the energy recovery train and is cooled to 185C. After further cooling to
63C in the primary cooler/condenser, separation of approximately one third acid
product as 42% strength nitric acid is achieved. The remaining gas reaches a 43%
oxidation conversion to nitrogen dioxide, with approximately 20% dimerization. The
gas is combined with bleached air containing additional nitrogen peroxide; it then
passes through an empty oxidation vessel and the secondary cooler. [6]
In cooling to 66C, the gas provides heat to a recirculating hot water system used
for vaporizing the ammonia. The gas entering the absorber is 95% oxidized to
nitrogen peroxide. In the absorber deionized water is added to the top tray, and weak
acid from the low-pressure condenser is added to a tray corresponding to its strength.
[6], [5]
Down-flowing acid and up-flowing acid alternately mix as the chemical steps of
action formation and nitric oxide oxidation take place with the liberation of heat.
There are three operational zones in the absorber, these are the lower zone cooled
with plant cooling water, the middle zone cooled with chilled water, and the upper
zone which is essentially adiabatic. High efficiency of heat removal in the middle and
10
lower zones is particularly important due to its effect on the oxidation and
dimerization reactions. [6]
For this process, chilled water at 7C is used and the tail-gas exit temperature is
approximately 10C. Acid from the bottom of the absorber is bleached at 1010 kPa
with partially cooled compressed air. The bleach air, containing nitrogen peroxide
stripped from the acid, is then added to the main gas stream before entering the
oxidation vessel. The cold gas is warmed by heat exchange with the hot compressed
bleached air, and then heated to the expander inlet temperature of 620C by two
exchangers in the recovery train. The expander recovers 80% of the required
compressor power. Expanded tail gas at 300C flows through an economizer,
providing heat to high-pressure boiler feed water and to low-pressure de ionized
deaerator make-up water. Subsequently tail gas is exhausted to the atmosphere at
66C and less than 1000 ppm of nitrogen oxides. [9]
The chilled water (7C) for absorption refrigeration unit, using heat, supplies the
absorber recovered from the compressor and intercooler as the energy source. Heat
for ammonia vaporization, as previously noted, is available at 35C and is recovered
from the secondary gas cooler. The system uses circulating condensate as the energy
transfer medium. [7]
1.2.2 The Dual-Pressure Process

The dual-pressure process was developed to take advantage of two factors:
a) Low-pressure ammonia oxidation;
b) High-pressure absorption for acid production.
In addition to the higher conversion, the lower catalyst gauze temperature
(associated with the low-pressure ammonia oxidation) results in a much lower rate of
platinum deterioration. Both advantages are maximized at the lowest pressure. In
contrast, however, absorption is best performed at the highest pressure. [7]
The low-pressure ammonia oxidation is usually performed in the pressure range of
101.3 kPa to 344 kPa. High-pressure absorption is usually performed in the operating
range of 800 kPa up to 1010 kPa. This process begins with the vaporization of
ammonia at 550 kPa and 7C "as shown in its flow sheet of Fig. (2)" followed by
superheating to 76C using heat from the compressed bleached air. Filtered air is
compressed in an axial compressor to 350 kPa and is mixed with the superheated
ammonia vapor (1 O-l 1% ammonia by volume) prior to entering the
converter/reactor. In the converter, the gases react over the platinum/rhodium gauze
catalyst. [7]
The gases leaving the reactor at 330 kPa and 865C flow through a series of heat
exchangers for recovery of energy, either as high-pressure superheated steam or shaft
horsepower from expansion of hot tail gas. Approximately 40% of the oxidation to
nitrogen dioxide occurs in the gas as it passes through the energy recovery train and is
cooled to 135C (exit from the tail-gas preheater). After further cooling to 45C in the
medium-pressure condenser, and separation of 20% of the acid product as 30%
strength nitric acid, the gas reaches 50% oxidation to nitrogen peroxide with
approximately 20% dimerization. [7]
The gas is combined with bleach air containing additional nitrogen peroxide and is
compressed in a centrifugal nitrous-gas compressor to 1025 kPa. The exit temperature
of 224C is achieved due to the combined heat effects of the compression, the further
oxidation to 80% nitrogen peroxide, and the virtual disappearance of the dimer. The
compressed gas flows through an empty oxidation chamber, a high-pressure boiler
feed water economizer, and a low-pressure deionized water economizer, and thus is
cooled to 95C. Residence time in the system and the effect of increased pressure
result in at least 95% oxidation to nitrogen peroxide, but the dimerization is low due
to the temperature level. [10]
The gas is then cooled to the dew point (50C) for entry into the absorber. The
dimerization increases to 48%, adding significantly to the heat removed prior to the
absorber. The system uses circulating condensate as the energy transfer medium. The
absorber is essentially the same as that previously described for the single-pressure
process. [4]
Chilled water at 15C is used in the absorber and the outlet gas temperature is
18C. Refrigeration for the chilled water is provided by the ammonia vaporizer which
operates at 7C. [6]
Weak acid from the bottom of the absorber is let down to 330 kPa for bleaching
with air from the axial compressor. This air, with nitrogen peroxide stripped from the
acid, flows to the suction of the nitrous-gas compressor together with the main nitrous
gas stream from the condenser. [5]
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1.2.3 Process Selection

(Factors Favoring the Single-Pressure Process)
The single-pressure process uses a higher ammonia conversion. This higher
pressure provides advantages in terms of equipment design, e.g. smaller converter
dimensions and a single heat-exchanger-train layout. The higher temperature and the
favorable pressure both increase the energy recovery from the process. The singlepressure process provides an extra 10% high-level recoverable heat energy. Plant
capital costs in the USA have been estimated at 8 million (USS5.1 million) for the
single-pressure process and 9.1 million for the dual-pressure process.
The 1.1 million higher cost of the dual-pressure process is accounted for by the
larger vessels required at lower operating pressures. Estimates made for the two plants
in European locations show a differential of 0.8 million, also in favour of the singlepressure process A discounted cash flow (DCF) analysis based on these US figures
was performed by matching the capital cost advantage of the single pressure process
against the production cost advantage of the dual pressure process. They indicate that
it would take 21 years for the lower operating cost of the dual-pressure process. In
this project, pressure process to finally overcome its initial capital cost disadvantage
due to its smaller capital cost compared to the dual pressure process. [1] , [9] , [10]
1.2.4 Process Selection Conclusions
The single-pressure process appears to be preferred for our project. The capital
cost advantage of this process surpasses the benefits of the superior operating cost
structure of the dual-pressure process.
1.3. Main Uses of Nitric Acid

Nitric acid is predominantly used for fertilizer manufacture. It also finds use in the
manufacture of adipic acid, nitroglycerin, nitrocellulose, ammonium picrate,
trinitrotoluene, nitrobenzene, silver nitrate, and various isocyanates.
Nitric acid has enormously diverse applications in the chemical industry. It has
commercial uses as a nitrating agent, oxidizing agent, solvent, activating agent, and
catalyst and hydrolyzing agent. The most important use is undoubtedly in the
production of ammonium nitrate for the fertilizer, which accounts for approximately
65% of the world production of nitric acid. [5]
Nitric acid has a number of other industrial applications. It is used for pickling
stainless steels, steel refining, and in the manufacture of dyes, plastics and synthetic
fibres. Most of the methods used for the recovery of uranium. Such as ion exchange
and solvent extraction, use nitric acid [7].
An important point is that for most uses concerned with chemical production, the
acid must be concentrated above its azeotropic point to greater than 95%(wt).
Conversely, the commercial manufacture of ammonium nitrate uses nitric acid below
its azeotropic point in the range 50-65%(wt). If the stronger chemical grade is to be
produced, additional process equipment appropriate to super-azeotropic distillation is
required. [2] , [7] , [10]
1.4. Physical Properties

In its commonest form nitric acid is a pungent, colorless liquid and pure
(anhydrous) that boils at 86C and solidifies at -42C. Those are the most common
nitric acid properties. It is used in varying dilutions across many industries and
chemical processes from munitions thru to agriculture, cleaning and woodworking.
As a pure acid HNO3 often emits white vapor when exposed to air and as a
dissolved solution can give off a vapor that is reddy-brown leading to its common
name red fuming acid. When stored in a diluted form for some length of time the
acid can take on a yellow tinge. Nitric acid is completely soluble in water.
This mineral based acid is highly corrosive, even in dilute forms, and if splashed
on skin will cause yellow blisters to be formed this should be expunged immediately
with copious amounts of water. It is highly toxic.
Pure anhydrous nitric acid (i.e. undiluted) is not, however, stable and even at
ambient temperatures can decompose, as temperatures increase so too does the rate of
the acids decomposition and when heated vigorously it will divide into its component
form of water, oxygen and nitrogen dioxide. Care is required, therefore in its storage
and handling. [3]
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1.5. Chemical Properties

Nitric acid can be seen to have a number of properties that can be describes as
acidic, oxidizing, reactive and as passivation.
Its acidic nature means that varying degrees of corrosion can be anticipated
dependent on the levels of dilution leading to its use as a cleansing, etching and
ageing chemical in many applications. If being used as a reagent or cleanser then
care needs to be taken to use vessels made from corrosion resistant alloys or metals to
enable processes to take place.
As a strong and powerful oxidizing agent it reacts, sometimes vigorously and
violently, with numerous non-metallic substances and compounds and the resultant
reaction can be an explosive one. This holds true to most metals with the exception of
those classed as precious and it is for that reason that nitric acid is used in the
cleansing and assessing of precious metal purity. Depending on the level of dilution
used during oxidization nitrous oxide may be formed.
When used in conjunction with many metals the end result is that nitric acid will
dissolve most of them and in the process creates nitrogen oxides. If combined with
hydrochloric acid then Nitric acid can be used to dissolve what are known as noble
metals such as gold, platinum, iridium and others. [3]
1.6. Safety Properties

Nitric acid is a strong acid and a powerful oxidizing agent. The major hazard
posed by it is chemical burns as it carries out acid hydrolysis with proteins (amide)
and fats (ester), which consequently decomposes living tissue (e.g. skin and flesh).
Concentrated nitric acid stains human skin yellow due to its reaction with the keratin.
These yellow stains turn orange when neutralized. Systemic effects are unlikely,
however, and the substance is not considered a carcinogen or mutagen.
The standard first aid treatment for acid spills on the skin is, as for other corrosive
agents, irrigation with large quantities of water. Washing is continued for at least ten
to fifteen minutes to cool the tissue surrounding the acid burn and to prevent
secondary damage. Contaminated clothing is removed immediately and the
underlying skin washed thoroughly.
Being a strong oxidizing agent, reactions of nitric acid with compounds such as
cyanides, carbides, and metallic powders can be explosive and those with many
organic compounds, such as turpentine, are violent and hypergolic (i.e. self-igniting).
Hence, it should be stored away from bases and organics. [1], [3]
1.7. Market Survey
1.7.1 Economic Outlook

Nitric acid is not produced in Saudi Arabia. However, worldwide annual
production of nitric acid is at present approximately 34 million tons. The USA, UK,
Poland and France are the largest producers. The trend in the last decade has been for
growth by the larger producers, very much at the expense of the smaller ones. The
global scene is a much more stable market. This can be attributed historically to
consumption being more broadly based with a sizable consumption in chemical
production processes.
World nitric acid consumption peaked in the late 1980s before declining
significantly through 1994. That decline was related primarily to economic turmoil in
the Eastern bloc countries. Since then, the market has exhibited an upward trend. The
largest market for nitric acid consumption is the production of ammonium nitrate
(AN) and calcium ammonium nitrate (CAN). In 2010, this accounted for 80% of total
world consumption of nitric acid. The major end use of AN fertilizer is in decline as a
result of concerns about nitrate groundwater contamination and increased usage of
solid urea, which has a higher nitrogen content (46%) than AN (34%), is less costly,
and is less dangerous. Consumption of AN in explosives and blasting agent
applications continues to grow, but is much more regulated since September 11, 2001.
[9]
The following pie chart shows (Figure 1) world Produces of nitric acid
16
World Producers of Nitric Acid
%21
USA
%30
Poland
france
USSR
%10
UK
%7
%10
%4
Other
Estern Europe
%18
Figure 1 World producers of nitric acid [2]
Most nitric acid is consumed captively and the merchant portion of the market
accounts for less than 10% of the total. International trade is minor and has little
impact on the nitric acid balance. Although there has been a relatively steady increase
in capacity, the world's average operating rate increased to 76% in 2010, indicating a
much stronger market balance than previously.
It is estimated that AN (and CAN) production accounted for 80% of the world
nitric acid market in 2010. The AN market is nearly three-quarters fertilizer and onequarter industrial applications. However, other nitric acidbased products such as
nitrophosphates and potassium nitrates are also used in fertilizer applications,
accounting for an additional 2.5% of total nitric acid consumption. The remaining
17.5% of nitric acid is consumed in industrial (nonfertilizer) applications. The
combined production of organic compounds, such as nitrobenzene, toluene
diisocyanate (TDI), adipic acid, and nitrochlorobenzenes accounted for nearly 10% of
total world nitric acid consumption in 2010.
Western Europe, China, the former USSR, Central Europe and the United States
dominate the market statistics. Together, these five regions accounted for 81.4% of
capacity, 82.0% of production, and 81.9% of consumption in 2010. Since 1994, the
largest increases in capacity, production and consumption have occurred in China.
One environmental problem affecting the consumption of nitric acid concerns the
use of ammonium nitrate fertilizers. The loss of nitrogen to groundwater because of
nitrification and leaching has become a significant problem and has negatively
impacted the use of nitrogen fertilizers, particularly in Western Europe. A European
Community directive has set a target of reducing nitrate levels in groundwater to a
maximum of 50 milligrams per liter. There is also concern about nitrate levels in
groundwater in the United States.
Current world production is approximately 34 million tons per annum, and over
30% is produced in the United States. Of the remaining production, about 60% is
based in Europe. The USSR (6 million tons), United Kingdom (3.3 million tons),
Poland (2.4 million tons) and France (1.5 million tons) are the main producers.
The plant should operate on a standard 8000 hour/year basis, with approximately
330 days of production. Nitric acid market price is $400 per ton can be obtained for
the product.
Ammonia market price is $500 per ton; we need to 18687.08 tons for ammonia to
produce 100000 tons of nitric acid. [9]
Table 1: Prices of raw materials and product
Component
Price per ton
Total Price
Ammonia
$500
$9343540
Water
$0.04
$963
Nitric acid
$400
$40000000
Total Profit = 40000000 - 9343540 - 963 = $30655497
1.8 Preliminary Hazard Analysis
1.8.1 Summary of Previous Plant Accident

At about 6 a.m. on December 13, 1994, two explosions rocked the ammonium
nitrate (AN) facility at the Port Neal, U.S.A Iowa nitrogen products manufacturing
complex operated by Terra Industries. Four people were killed and 18 injured.
18
Approximately 5,700 tons of anhydrous ammonia was released, and releases of

ammonia continued for nearly six days following the explosion. Chemicals released
as a result of the blast contaminated groundwater under the facility. [10]
Figure 2 Terra's Port Neal, Iowa complex before the explosion. The ammonium nitrate plant is indicated
[2]
Figure 3 Post-explosion aerial photograph of the Port Neal plant [2]
The Port Neal plant produced an 83 percent AN solution by reacting ammonia and
nitric acid in a vessel called a neutralizer. The original neutralizer was replaced in
1980 and a major modification and upgrade of the plant occurred in 1992. A scrubber
and new control system were also added in September 1994. In the two days prior to
the explosion, the nitric acid plant was shut down for maintenance. With the nitric
acid plant not operating, the AN facility was also shut down.
The accident occurred due to unsafe plant operations including poor maintenance
and inadequate employee training. Specifically, during the shutdown period, the pH
of the neutralizer vessel contents dropped to an unusually low level and leaks in other
equipment led to the introduction of chloride ions that catalyzed the final reaction.
Unaware that the 18,000 gallon-capacity neutralizer vessel was in a highly acidic and
contaminated condition, Terra employees injected superheated steam to try to keep
the vessel contents from freezing due to the winter cold. The energy from injected
superheated steam led to the runaway chemical reaction of the sensitized ammonium
nitrate solution and resulted in the subsequent explosive detonations. [5]
1.8.2 Inherent Safety Aspects

Taking into consideration the inherent safety aspects such as substitution of
hazardous chemicals, safe location, plant layout, transportation and storage can reduce
accidents Potential consequences:
a) Hazardous Chemicals:
The following hazards may arise during nitric acid production:
Equipment/piping failure because of corrosion
Explosion hazard due to the air ammonia mixture
Explosion of nitrite/nitrate salts
(i) Equipment/Piping Failure

Corrosion protection is achieved by the well-proven use of suitable austenitic
stainless steel where condensation can occur and by regular monitoring of the
conditions.
(ii) Explosion Hazard due to the Air Ammonia Mixture
The air ammonia ratio is continuously controlled and kept below the hazardous
range. Safety is ensured by the automatic closure of the ammonia control valve and
separate shutdown trip valve when too high an air ammonia ratio is measured, either
from each individual ow meter or indirectly from the catalyst gauze temperature.
(iii) Explosion of Nitrite/Nitrate Salts
Any free ammonia present in the nitrous gas will give a deposit of nitrite/nitrate in
a cold spot. Local washing and well proven operating practices will prevent the
hazard. [1], [6]
20
b) Safe Location:
The selection of suitable location is a very important decision to make when there
is new plant to build. Some of the factors that should be consider when selecting the
location for a plant is for example the availability of raw materials used, also good
transportation network, and availability of market, weather condition suitability and
the water supply. From safety aspects, few factors should be taken in consideration
before deciding whether the location is suitable. Most important is the distance from
the residential area, availability of water and power supply. [4]
c) Plant Layout:
Another inherent safety is plant layout. After deciding on the plant location the
overall plant layout, for example the processing areas, the absorber column, control
rooms, roads and storage areas and other utilities must be planned carefully taking in
consideration the future problems that might arise. Firstly and elementary layout
developed first, these shows the fundamental relationship between the operating
equipment and the storages area. Then the second step is the primary layout base of
the flow of the material, unit operational storage, and future expansion. An efficient
arrangement and coordination is very important to reduce the risk and hazards in plant
by putting the element of health and safety into the design. [9]
d) Transportation:
Transportation to and from the plant is very important. Usually if the plant is big, it
requires inside transportation and these kinds of vehicles should be ensured that it is
safe and does not bring any hazards to the workers or the plant itself. Vehicles should
be using diesel instead of petrol, as a diesel engine does not produce sparks that might
ignite fire. For nitric acid transferring process, container should be constructed from
insulating material. [9]
e) Storage:
Most of the large accidents in chemical or petrochemicals plants happen in the

storage area. Storages room or tanks is where most plants stores whether their raw
material or their products. Chemical storage areas shall be inspected at least annually
and any unwanted or expired chemicals shall be removed. Adjusting the storage
capacity or installing safety system will definitely reduce accident occurrence. The
duration of material stored should also be taken in consideration. For example, longer
store might change the material properties, which might cause to undesired accidents.
Raw materials and products should not be stored for long period. [4]
1.8.3 Local Safety and Environmental Regulations

(Nitrogen oxides defined as nitrogen dioxide NO2)
1) Purpose:
The purpose of these standards is to prevent development of nitrogen dioxide
concentrations, which could produce adverse health effects or lead to the production
of significant concentrations of photochemical oxidants.
2) Standards:
a) During any 30 days period, one-hour average NO2 concentration shall not
exceed 660-microgram/cubic meter (0.35 ppm) more than twice at any location.
b) During any 12 months period, the annual NO2 concentration shall not exceed
100-microgram/cubic meter at any location. [11]
22
1.9 Site Feasibility

1.9.1 Selection Criteria
Several factors influence the selection of a site for the location of a chemical plant.
The following list contains a few of the important considerations, but should not be
considered exhaustive.
(a) Designation as a heavy industrial development area (light industry usually means
assembly of electronic components, small metal fabricators, etc., and a major
chemical plant would not be acceptable).
(b) Prior existence of similar chemical plants and location of other industrial centres.
(c) Existing roads and services, e.g. electricity, gas, water, etc.
(d) Appropriate terrain, sub-surface, drainage, etc.
(e) Suitable access for transportation of raw materials and chemicals, and for
construction of a chemical plant.
(f) Proximity to major transportation networks, e.g. roads, railways, airports,
waterways and ports. This is a major consideration in the location of a plant. In some
cases direct pipelines for the transportation of chemicals or utilities (e.g. water, gas,
oil) may be the most economical method. The cost of transportation by tanker (road,
rail or sea) is reduced if a return load can also be carried.
(g) Availability of a local workforce and distance from local communities.
(h) Availability of domestic water and plant cooling water.
(i) Environmental discharge regulations.
(j) Proximity to both the raw materials supply and the market for the product
chemical.
(k) Existence of services equipped to deal with a major industrial accident.
(1) Climatic conditions, e.g. humidity, maximum wind velocity and its prominent
direction, rainfall, etc.
(m) Proposed or possible government restrictions regarding industrial development or
discharge emissions.
(n) Room for expansion.
(0) Price of land.
(p) Public opinion.
(q) Possibility of earthquakes, subsidence, avalanches, etc.
(r) Availability of government regional development grants or tax incentives,

subsidies, etc. [1], [9]
1.9.2 Potential Site Location

The manufacture of nitric acid is categorized as a petrochemical project. The plant
must therefore be sited in a special zone provided by the government. After
conducting the feasibility and site survey, three existing industrial areas have been
evaluated to choose the most suitable area for the acetone plant, which are Jubail
Industrial City (JIC), Yanbu Industrial City (YIC) and Ras Alkhair Seaport.
Table 2: Information of site location
Factors
JIC
Site Location
YIC
Type of Industrial Area

Raw Materials IPA
Power
Water
Utilities
Steam
Natural
Gas
Available Area
Land Price
Space for Expansion
Cost of Living
Seaport
Transportation Railway
Roadway
Airport
Price of
Power
Utilities
Water
Existing Infrastructure
Existing Services for
Industrial Accidents
Training Centre
Government Incentives
TOTAL SCORE
PERCENTAGE (%)
RANKING
10
9
10
10
9
8
10
0
10
10
8
8
Ras Alkhair
Seaport
10
10
10
10
6
8
9
10
0
5
10
5
10
5
6
10
10
10
8
10
0
8
10
0
10
10
6
10
10
10
10
10
0
9
10
10
10
3
6
10
10
10
10
10
166
83
2
5
10
162
81
3
5
10
167
83.5
1
In these cities, there are a lot of petrochemical plants and because the raw material
(ammonia) plant is available in Ras Alkhair, we have chosen the location of our plant
to be there.
24
Chapter 2
Material Balance
2.1 Process Description

The process begins with the vaporization of ammonia at 1240 kPa and 35C using
process heat. Steam is then used to superheat the ammonia about 170C, filtered air is
compressed by a centrifugal compressor, discharge pressure of 1200 kPa.
In our process; the air and the ammonia vapor are mixed and passed through the
platinum/ rhodium gauze reactor where the heat of reaction raises the temperature to
be between 650C and 630C. The reaction gas flows of heat exchangers to cooled
down to 70 oC.
Approximately 95% of the oxidation to nitrogen dioxide occurs as the gas passes
in the Oxidation unit, after that cooled to 60C, then sent to absorber to produce nitric
acid (60%) purity.
26
2.1.1 The Flow Sheet of the Selected Process
Figure 4 Process flow sheet for nitric acid production by the single pressure process." our selected process"
28
2.1.2 Justification for the Equipment Selection

Process Units
1. Air Compressor Two stage compressors to achieve the high pressure required".
2. Ammonia Vaporizer: a shell and tube-type heat exchanger. This unit should contain internal
baffles. This exchanger is made from mild steel.
3. Ammonia Superheater: a shell and tube-type heat exchanger of similar mechanical
construction to the ammonia vaporizer. Also constructed from mild steel.
4. Mixer (usual mixing vessel).
5. Reactor: the reactor is a pressure vessel operating in the range 1050 kPa to 1100 kPa. The
vessel must be designed to ensure even passage of the feed gas mixture over the
platinum/rhodium catalyst gauze The catalyst gauze and accompanying platinum filter gauze
are fixed in position by lateral supports across the width of the reactor.
6. Cooler: this shell and tube-type heat exchanger uses deionized water as its cooling medium. It
has a design pressure of about 1200 kPa.
7. Oxidation Unit: the oxidation unit is a normal pressure vessel that takes input reaction gases
and air.
8. Secondary Cooler: the secondary cooler takes the exit gases from the oxidation unit at 140C
and cools them down to 60C, a suitable temperature for entry into the absorption column. It
is a shell and tube-type heat exchanger.
9. Absorber: the absorber is usually a sieve tray-type column. It has a design pressure of 1200
kPa, and operates at a temperature range of 60oC to 30oC.
The material balances for the all units of the plant were hand calculated. A material balance
for each unit presented below in tabulated form. The main equations used in the calculations are
shown in their relevant sections. The detailed calculations are included in Appendix (C).
The general equation for material balance is
Input Output + Generation Consumption = Accumulation
For steady state without chemical reaction
Input Output = 0
2.2 Overall Mass Balance
S1
S 12
S2
S 13
S 14
Table 3: Summery of overall mass balance
Component
O2
Input S1
(Kg/h)
9142.88
Input S2
(Kg/h)
-
Output S14
(Kg/h)
-
Output S12
(Kg/h)
799.19
Output S13
(Kg/h)
-
N2
34394.64
34490.82
NH3
2335.88
H2O
3007.51
646.00
5000.00
HNO3
7500.00
NO2
288.20
NO
156.70
Total
48880.91
48880.91
30
2.3 Reactor Mass Balance
S7
S8
R-201
Table 4: Summery of reactor mass balance
Component
NH3
Input S7
(Kg/h)
2335.88
Output S8
(Kg/h)
-
O2
9142.88
3756.58
N2
34394.64
34490.82
NO
3916.05
H2O
3709.93
Total
45873.4
45873.4
2.4 Oxidation Mass Balance
S9
S 10
R-202
Table 5: Summery of oxidation mass balance
Component
NO
Input S9
(Kg/h)
3916.05
Output S10
(Kg/h)
156.70
NO2
5764.39
O2
3756.57
1751.55
N2
34490.82
34490.82
H2O
3709.93
3709.93
Total
45873.40
45873.40
32
2.5 Absorber Mass Balance
S 12
S 14
S 11
S 13
T-201
Table 6: Summery of absorber mass balance
Component
H2O
Input S11
(Kg/h)
3709.93
Input S14
(Kg/h)
3007.51
Output S12
(Kg/h)
646.00
Output S13
(Kg/h)
5000.00
HNO3
7500.00
NO2
5764.40
288.20
NO
156.70
156.70
O2
1751.55
799.19
N2
34490.82
34490.82
Total
48880.91
48880.91
Chapter 3
Energy Balance
34
3.1 Vaporizer Energy Balance
S4
S5
E-101
For S4: NH3 at -15 oC and S5: NH3 at 35 oC
= 1.78 /
= 0
= 2902575.37 /
3.2 Compressor Energy Balance
S3
S1
C-101
For S1: Air at 101 kPa and S3: Air at 1090 kPa
= 8879734.37 /
(This is the mechanical energy required by the compressor.)
36
3.3 Superheater Energy Balance
S5
S6
E-102
For S5: NH3 at 35 oC and S6: NH3 at 177 oC
= 0
= 5.442 /
= 747758.01 /
3.4 Mixer Energy Balance
S3
S7
S6
M-101
For S3: NH3 at 177 oC, S6: Air at 262 oC and S7: NH3+Air at ?
= 0 ()
= 250
38
3.5 Reactor Energy Balance
S7
S8
R-201
For S7: NH3+Air at 250 oC and S8: Air+NO+H2O at 645 oC
Table 7: Summary of enthalpy components in reactor
Component
H (Air)
H (NH3)
H (NO)
H (H2O)
= 51820729.07 /
Input S7
(kJ/mol)
6.654
8.84
-
Output S8
(kJ/mol)
19
19.744
23
3.6 Heat Exchanger Energy Balance (1st Cooler)

S8
S9
E-201
For S8: Air+NO+H2O at 645 oC and S9: Air+NO+H2O at 70 oC

= 0
For air: = 17.693 /
For NO: = 18.400 /
For H2O: = 21.173 /
= 30,084,503.19 /
40
3.7 Oxidation Energy Balance
S9
R-202
S 10
For S9: Air+NO+H2O at 70 oC and S10: Air+NO+H2O+NO2 at 140 oC
Table 8: Summary of enthalpy components in oxidation
Component
Input S9
(kJ/mol)
Output S10
(kJ/mol)
H (H2O) (g)
1.521
3.919
H (Air)
1.312
3.37
H (NO)
1.345
3.47
H (NO2)
4.5
= 3707006.24 /
3.8 Heat Exchanger Energy Balance (2nd cooler)
S 10
S 11
E-202
For S10: Air+NO+H2O+NO2 at 140 oC and S11: Air+NO+H2O+NO2 at 60 oC

= 0
For H2O: = 2.737 /
For air: = 2.350 /
For NO: = 2.4230 /
For NO2: = 3.1796 /
= 3911927.94 /
42
3.9 Absorber Energy Balance
S 12
S 14
T-201
S 11
S 13
Basis: Tref = 25oC

For S11: Air+NO+H2O+NO2 at 60 oC, S14: H2O at 20 oC, S12: Air+NO+H2O at 30 oC and S13:
HNO3+H2O at 30 oC
Table 9: Summary of enthalpy components in absorber
Component
Input S11
Input S14
Output S12
Output S13
(kJ/mol)
(kJ/mol)
(kJ/mol)
(kJ/mol)
H (H2O) (g)
1.18
0.166
H (H2O) (L)
-0.375
0.375
H (Air)
1.02
0.145
H (NO)
1.044
0.149
H (NO2)
1.32
H (HNO3)
0.55
Q= -29876241 KJ/h
Chapter 4
Design and Sizing

Equipment
44
4.1 Sizing of Pump [7]

Pump Specification Data
Ammonia
Flow rate = 2335.88 kg/h
Temperature = -15C
Density at -15C = 656.67 kg/m3
Estimating the pump diameter required
Mass flowrate (G) =
2335.88
= 0.6488 Kg/s
3600
G = 0.6488 kg/s
() =
0.6488
656.67
Q = 0.001 m3/s
Piping Specification
Atypical velocity for fluid flow is 2 m/s.
Determination of the pipe area:
Area of pipe (A) =
Area =

Velocity
0.001
2
Area= 0.0005 m2
4 0.5
Diameter of pipe (D) = [
]
=[
4 0.0005 0.5
]
D = 25 mm
This value is compared with the result achieved by applying the Economic pipe diameter
formula for stainless steel from
Optimum diameter = 226 G0.5 -0.35
Optimum diameter = 226 (0.6488)0.5 (656.67)-0.35
Optimum diameter = 19mm
Accept the larger value as a conservative estimate
4.2 Design of Heat Exchanger (Vaporizer)

The objective is to design a heat exchanger (vaporizer) (shell and tube) to heat Ammonia of flow
rate 2335.88 kg/h from -15oC to 35 oC using saturated steam entering at 1 atm.
Table 10: Data of ammonia
Component
Mwt
NH3
Kg/Kmol
17
Kmol/h
137.404
Kg/h
2335.88
Mole fraction
Y
Mass fraction
X
Table 11: Physical properties of ammonia at Tave = 10oC and Pave = 1240 kPa
Component
Pa.s
1.531 x 10-4
Cp
KJ/kg.K
5.02
NH3
K
W/m.K
0.5135
Kg/m3
623.6318
Table 12: Physical properties of standard steam at 1 atm and T ave = 100oC = 373 K
Cpl
Cpv
KJ/Kg.K
4.24
1.888
l
0.27 x
10-3
v
Pa.s
1.295 x
10-5
v
3
Kg/m
953
0.596
kl
kv
W/ m.K
0.681
0.0251
KJ/Kg
2256.9
Heat duty (Q) needed to be added to gas mixture:

Q = m Cpmix T
[7]
Q = 163 kJ/s (kw)
For steam:
Qlost = Qgain = m
[7]
msteam = 163/2256.9
msteam = 0.0722 kg/s
46
Finding Tlm:
T1 = 100 oC
T2 = 100 oC
VAPORIZER
t2 = 35 oC
t1 = -15 oC
Tout = T1 t 2 = (100 35) = 65 oC

= 2 1 = (100 (15)) = 115
[7]
= 87.63
The heat exchanger will consist of one shell pass and one tube passes:
Tm = 87.63 oC
According to Table A in Appendix E, Cold fluid is Ammonia and hot fluid is condensing steam.
The following value of overall heat transfer coefficient U can be estimated:
U= 500 W/ m2.oC
Required Area for Heat transfer:

= = / [7]
= 3.72 2
Choosing 25 mm OD, 21 mm ID stainless steel tubes to resist corrosion problems. Placing

condensing steam in the shell side. Take Tube length L=2 m [7]
Calculation of Number of tubes:
3.72
=
25 103 2
= 24
Since the steam in the shell side is always clean, we will use triangular pitch arrangement with
Pt= 1.25do:
Calculation of bundle diameter Db:

1
1
= [ ]
1
[7]
K1, n1 are constants given in Table C:

K1 = 0.319
n1 = 2.142
1
159 2.142
= 25 [
]
0.319
[7]
Db = 187.9 mm
Calculating the shell diameter Ds:
= + [7]
From Figure A in Appendix E and for split-ring floated heat type of heat exchanger we get,
clearance= 48 mm
= 187.9 + 48 = 235.64 [7]
48
Calculating the heat transfer coefficients for tube side (hi):
= 2 = (21)2 = 346.36 2
4
4
= (
) 2 = 0.008312 2 [7]
.
4
0.64885
=
= 78.06
2 . [7]
0.008312
78.06
( ) =
=
= 0.125 [7]
623.6318
( ) =
To calculated hi use the equation

0.14
= 0.33 ( )
[7]
hi = inside heat transfer coefficient

di = tube diameter = 21x10-3 m
Kf = thermal conductivity of water fluid = 0. 5135
W/m.oC
Jh = factor for heat transfer given form Figure B in Appendix E in Appendix E by (Re)
() =
623.6318 0.125 21 103

=
= 10692.57
1.531 104
(Turbulent Flow)
() =
5.02 103 1.531 104

=
= 1.49
0.5125
From Figure B in Appendix E at Re= 10692.57

Jh = 4 x10-3
From (eq. hi) and neglecting (
0.14
) and assume it approximately 1
w
Then:
(21 103 )
= (4 103 )(10692.57)(1.49)0.33
0.5135
hi = 1192.93 W/m2.oC
[7]
[7]
Calculate heat transfer coefficients for shell side (ho):

Area for cross flow of the shell side As, using Kern Method:
= [
[7]
Pt = tube pitch
Pt
do = tube outside diameter

Ds = shell inside diameter
LB = Buffle spacing (usually one fifth of shell diameter)
do
do = 25 mm
Pt = 1.25 do mm = 31.25 mm
235.9
=
= 47.18
5
5

31.25 25
= [
] = [
] (235.9)(47.18) = 2226 2
31.25
=
As = 0.002226 m2
Mass velocity (Gs) and liner velocity (vs):

mshell = mass flow rate of steam = 0.0722 kg/sec
= [
0.0722
]=[
] = 32.43 2 .
0.002226
32.43
= [ ] = [
] = 54.42
0.596
[7]
[7]
The equivalent (Hydraulic) diameter de:

=
1.10 2
( 0.9172 )
1.10
[(31.25)2 0.917(25)2 ] = 17.75 = 0.01775
25
[7]
Re & Pr for shell side:

=
0.0722
=
= 1.5 103 .
24 2
[7]
50
(32.43)(0.01775)
=
= 45721.4 [7]
1.259 105
187.9
=
= 6.01
31.25
[7]
The shell side coefficient ( hs or ho )

1
1
(953)(953 0.596)(9.8) 3
6
= (0.95)(0.681) [
]
6.01
(0.27 103 )(1.5 103 )
hs = 13441.08 W/m2.oC
Calculating the overall heat transfer coefficient (U):
ln ( ) 1
1
1
1
1
=
+
+
+ ( )+
( )

2

[7]
Uo = overall coefficient based on outside area of the tubes

ho = outside fluid film coefficient
hi = inside fluid film coefficient
di = tube inside diameter
Kw = thermal conductivity of tube wall material = 16 (W/m.oC) for "stainless steel"
hod = outside dirt " fouling " coefficient = 3000 (W/m2.oC) (From Table B)
hid = inside dirt " fouling " coefficient = 3000 (W/m2.oC) (From Table B)
25 103 ln(2521)
1
1
1
1
25
1 25
=
+
+
+
( )+
( )
13441.08 3000
2 16
1192.93 21
3000 21
Uo = 516 W/ .oC
The value of 516 W/m2.oC is well above the estimated value of 500 W/m2.oC.
Hence, the present design satisfactory. (ok)
52
Calculating the pressure drop (P) for side tube and shell tube:
1.The tube side Pt
L
m
vt2
Pt = NP [8jf ( ) ( ) + 2.5] [
]
di w
2
[7]
Pt = tube side pressure drop (N/m2)

Np = Number of tube passes
jf = fraction factor ' depending on Re ' Found from Figure 12.30 in the text book assuming
baffle cut of 0.25
L = length of one tube = 2 m
vt = flow velocity inside the tube =0.125 m/sec
m = exponent value depending on type of flow
For laminar (Re<2100) m = 0.25
For Turblent (R>10000) m = 0.14
Now, assuming viscosity ratio =1 and finding jf corresponding to Re= 5594.35, we get;
Pt = [8(5 10
3 )
2
623.6318 0.1252
(
) + 2.5] [
]
21 103
2
Pt =30.74Pa = 0.0307 kpa (Acceptable)
2. The shell side Ps

Ds L
vs2
0.14
Ps = 8jf ( ) ( ) (
)( )
De LB
2
w
[7]
Ps = shell side pressure drop (N/m2)

jf = fraction factor ' depending on Re , Found from Figure 12.30 in the text book assuming
baffle cut of 0.25
Ds = shell diameter = 235.9 mm
De = equivalent diameter for shell side = 17.75 mm
Re= 45721.4
vs = flow velocity in shell = 54.42 m/sec
LB = Baffle spacing = 47.18 mm
shell = 0.596 kg/m3
Neglecting viscosity correction, we get:
Ps = 8(3.9 10
2 )
235.9 2 103 0.596 4.422

(
)(
)(
)
17.75
47.18
2
Ps = 155.12 kpa (acceptable)
54
Finally, we summarize our present design as follows

1. The selected heat exchanger has one shell pass and one tube passes, in which
ammonia flow inside the tube and condensing steam flows inside the shell .
2. The selected tubes are made of stainless steel with 25 mm outside diameter, 21 mm
inside diameter, the total number of tube is 24, while the tube length is 2 m, and the
triangular pitch applied for this tube distribution is 31.25 mm.
3. The shell diameter Ds is 235.9 mm. and the baffles used are 25% cut, while the baffle
spacing is 48 mm.
4. The first estimated value for overall heat transfer coefficient Uo is 500 W/m2.oC,
while the final calculated value is 516 (W/m2. oC).
5. The pressure drop (Pt) for the tube side is 0.0307 kPa , while the shell side (Ps) is
155.12 kPa .
4.3 Sizing of Compressor [7]
101 1000 28.9
=
= 1.15 3
298 8314
1
3
1 = = 0.8733
V = 12.693/1.145 = 10 .562 m3/s = 38023.2 m3 / h

From Figure C in Appendix E and for volumetric flow 38023.2 and discharge pressure 11 bars
the recommended compressor is centrifugal compressor
Calculation the polytropic coefficient (n)
From Figure D in Appendix E and suction flow 10.562 m3/s
Ep = 0.74
Average heat capacity of mixture at T = 30 oC
= = 29.099 .
= = 29.099 8.314 = 20.785
= 1.4
( 1)
=
= 0.386
( )
=
1
= 1.62
1
The polytropic work:
2
= 1 1
[( )
1 1
(1)
1]
Wpoly =376366.4 J/kg

Actual work required:
Wpoly/Ep = 508731.6 J/kg
Power required
Pac = W m = 12.693 508731.6 = 6068.531 KW
Electric power:
From table the approximate electrical efficiency, Ee is 0.97
Pe = Pac /Ee = 6068.531 /0.97 = 6256.2 KW
4.4 Design of Heat Exchanger (Superheater)

56
The objective is to design a heat exchanger (superheater) (shell and tube) to heat Ammonia of
flow rate 2335.88 kg/hr from 350C to 177 0C using saturated steam entering at 40 bars.
Table 13: Data of ammonia
Component
Mwti
kg/kmol
17
NH3
Ni
kmol/h
137.404
Mi
Kg/h
2335.88
Mole fraction
Yi
1
Mass fraction
Xi
1
Table 14: Physical properties at Tave = 106oC and P = 1240 kPa
Component
Cp
kJ/kg.K
2.38
NH3
i
Pa.s
1.32 x 10-4
K
W/m.K
0.0364
kg/m3
7.04
Table 15: Physical properties of standard steam at 40 bars and Tave = 250.3oC = 523.45 K
Cpv
kJ/kg.K
1.958
v
Pa.s
1.84 x 10-5
v
kg/m3
20.12
Heat duty (Q) needed to be added to gas mixture:

= [7]
= 219.28 / ()
For steam:
= = [7]
= 219.28/1712.9
= 0.128 /
Finding Tlm:
kv
W/ m.K
0.0388
kJ/kg
1712.9
T1 = 250.3 oC
t2 = 177 oC
T2 = 250.3 oC
SUPERHEATER
t1 = 25oC
= 1 2 = (250.3 177) = 73.3 C

= 2 1 = (250.3 35) = 215.3 C

[7]
= 131.79 C
The heat exchanger will consist of one shell pass and one tube passes.
According to Table A in Appendix E, Cold fluid is Ammonia and hot fluid is condensing steam.
The following value of overall heat transfer coefficient U can be estimated:
U= 160 W/ m2.oC
58
= =
[7]
= 10.39 2
Choosing 25 mm O.D, 21 mm I.D stainless steel tubes to resist corrosion problems. Placing
condensing steam in the shell side. Take Tube length L = 5 m
[7]
Calculation of Number of tubes:

=
10.39
=
25 103 5
[7]
= 27
Since the gas mixture in the shell side is always clean, we will use triangular pitch arrangement
with Pt= 1.25do [7]
Calculation of bundle diameter Db:

1
1
= [ ]
1
[7]

K1 = 0.319
n1 = 2.142
1
27 2.142
= 25 [
]
0.319
[7]
Db = 198.5 mm
Calculating the shell diameter Ds:
= + [7]
clearance= 49.5 mm
= 198.5 + 49.5 = 248
Calculating the heat transfer coefficients for tube side (hi):
= 2 = (21)2 = 346.36 2 [7]

4
4
= (
) 2 = 0.009351 2 [7]
.
4
0.64885
=
= 69.39
2 .
0.009351
78.06
( ) =
=
= 9.85 [7]
623.6318
( ) =
[7]

0.14
= 0.33 ( )
[7]

Kf = thermal conductivity of water fluid = 0.0364 W/m.oC
Jh = factor for heat transfer given form Figure B in Appendix E by (Re)
() =
7.04 9.85 21 103

=
= 110320
1.32 105
[7]
(Turbulent Flow)
2.38 103 1.32 105
() =
=
= 0.863
0.0364
[7]
From Figure B in Appendix E at Re = 110320

Jh = 2.8 x10-3 [7]
From (eq. hi) and neglecting ( )
0.14
and assume it approximately 1
Then:
(21 103 )
= (2.8 103 )(110320)(0.863)0.33
0.0364
hi = 510 W/m2.oC
60

= [
[7]
Pt = tube pitch
Pt

do = 25 mm
Pt = 1.25 do mm = 31.25 mm
248
=
= 49.5
5
5

31.25 25
= [
] = [
] (248)(49.5) = 2455.2 2
31.25
=
As = 0.0024552 m2
mshell = mass flow rate of steam = 0.128 kg/sec
= [
0.128
] = [0.0024552] = 52.13
2 . [7]
52.13
= [ ] =
= 2.59 [7]
20.12
=
1.10 2
( 0.9172 ) [7]
1.10
[(31.25)2 0.917(25)2 ] = 17.75 = 0.01775
25
Re & Pr for shell side:
20.12 2.59 0.01775

=
= 50269.92 [7]
1.84 105
do
1.958 103 1.84 105

=
=
= 0.928

0.0388
[7]
The shell side coefficient ( hs or ho )

1

0.14
= 3 ( )

[7]
From Figure B in Appendix E at Re= 50269.92

Jh = 3.2 x10-3
[7]
From (eq. hs) and neglecting (
0.14
w
(25 103 )
= (3.2 103 )(50269.92)(0.928)0.33
0.0388
hs = 343 W/m2.oC
62

ln ( ) 1
1
1
1
1
=
+
+
+ ( )+
( )

2

[7]

hi = outside fluid film coefficient
Kw = thermal conductivity of tube wall material = 16 (W/m.oC) for '' stainless steel''
hod = outside dirt " fouling " coefficient = 3000(W/m2.oC) (From Table B in Appendix E)
hid = inside dirt " fouling " coefficient = 3000 (W/m2.oC) (From Table B in Appendix E)
25 103 ln(2521)
1
1
1
1 25
1 25
=
+
+
+
( )+
( )
343 3000
2 16
510 21
2000 21
Uo = 163.5 W/2 .oC
The value of 163.5 W/m2.oC is well above the estimated value of 160 W/m2.oC.
Hence, the present design satisfactory. (Ok)
Calculating the pressure drop (P) for side tube and shell tube:
1. The tube side Pt:

L
m
vt2
Pt = NP [8jf ( ) ( ) + 2.5] [
]
di w
2
[7]

baffle cut of 0.25
vt = flow velocity inside the tube
at laminar (Re<2100) m = 0.25
at Turblent (R>10000) m = 0.14
Now:
Pt = [8(2.7 103 ) (
5
7.04 9.852
)
+
2.5]
[
]
21 103
2
Pt = 2154.82 Pa =2.154 kPa (Acceptable)
2. The shell side Ps:
64
Ds L
vs2
0.14
Ps = 8jf ( ) ( ) (
)( )
De LB
2
w
baffle cut of 0.25
Ds = shell diameter = 248 mm
shell = 20.12 kg/m3
248
5 103 20.12 2.592
Ps = 8(2.8 102 ) (
)(
)(
)
17.75
49.5
2
Ps = 22.39 kPa (Acceptable)
Finally, we summarize our present design as follows:
[7]
1. The selected heat exchanger has one shell pass and one tube passes, in which ammonia flow
inside the tube and condensing steam flows inside the shell .
2. The selected tubes are made of stainless steel with 25 mm outside diameter, 21 mm inside
diameter, the total number of tube is 27, while the tube length is 5 m, and the triangular pitch
applied for this tube distribution is 31.25 mm.
3. The shell diameter Ds is 248 mm. and the baffles used are 25% cut, while the baffle spacing is
(49.5 mm).
4. The first estimated value for overall heat transfer coefficient Uo is 160(W/m2 . oC) , while the
final calculated value is 163.5 (W/m2. oC).
5. The pressure drop ( Pt ) for the tube side is 2.154 kPa , while the shell side ( Ps ) is 22.39
kPa .
4.5 Sizing of Mixer

66
= 1.15
Volumetric flow rate:

3
= / = 12.7 / 1.15 = 11
Volume of mixture:
Residence time in the mixture drum: = 1s
= 11 1 = 11 3
/ = 4
= ( ) 3
4
1
3
=( )
= 1.6
= 6.1
4.6 Design of Reactor

Introduction
The direct oxidation of ammonia over platinum 10% odrhodium catalyst is the major step in
the production of nitric acid. This oxidation at temperature about 700 oC and pressure range of 59 atm. At this temperature platinum oxides are formed on the surface and some portion of it are
vaporized and carried away in the gas stream.
A suitable shape for the reactor has been found to be in the form of two frustrated square
pyramids, between the large cross-sections of which are placed the catalyst gauze. This shape
allows the walls of reactor to be kept as cool as possible.
A major issue in the design of this type of reactor is the arrangement of catalyst layer in the
form of screen supported in a manner that will ensure good distribution of flow. Because poor
distribution could cause hot spot in this exothermic reaction leading to volatilization of the
catalyst metal, and a direct reduction is also reduce the plant capacity.
Kinetic of reaction
The catalyst of ammonia oxidation is so rapid that the amount of catalyst required is very
small and heat transfer is not feasible. Typically configuration of this system is the woven wire
gauze. This reaction completely by mass transfer, and the design of screen packs has been based
on pilot plant studies and plant experience, and the reactor type is known as the shallow-bedadiabatic one. [5]
Assumption:
68
1. The reactions are mainly controlled by diffusion.

2. The partial pressure of ammonia on the catalyst surface is negligible.
3. The design model is developed as plug flow.
4. Typical reported data are used.
5. Ratio of mass of ammonia /hr.: mass of catalyst =85.
6. Cross sectional area = 0.256 10-3 m2 / ton HNO3, daily.
Let: [5]
Nw = 80 inch mesh size
Aw = area /ton HNO3 = 0.256 m2/ton HNO3
dw = wire diameter = 0.003 inch =76 x10-4 cm
fw = wire area per gauza cross sectional area
Awr = surface area of screen / volume of one screen
The density of catalyst = 0.0214 kg / cm3
ns = number of screen per gauza
X= 0.95
Vg = volume of one screen = 110 cm3
YNH3 = 0.09
=
1 2
[( ) + 2 ]
0.2
= 122.6 1 = 294.39 1 [5]
= 2 = 294.39 2 0.003 = 1.77

aw dw
122.6 76 104
=1
= 0.8 [5]
4
4
(3063) 2000
= =
=

24 3600 0.96 0.09 0.027547
= 4.63 2 . = 2.1 2 .
= Porcity = 1
Superficial velocity
[5]
= 2.1
1
82.06 1209
= 2.1
= 890 = 28.3
[5]
7.8 30
(1 ) 0.352 0.648 0.648 0.0190

=
[5]
(5.81761 105 ) 0.333 (28.85 + 11.82 ) 0.667
= 19
Ratio
mass amonia
= 85 [5]
mass catalyst
The mass of ammonia / 85 = mass of catalyst

=
17 137.4
= 27.5
85
= = 0.256 300 = 76.8 2

= /
= 27.5 / 0.0214 = 1284 3
= =
= 50 [5]
(1 )
= 0.5 50 + 1 + 1 = 27
=
76.8
= 1
27
70
4.7 Design of Heat Exchanger (1st Cooler):

The objective is to design a heat exchanger (shell and tube) to cool vapor mixture of flow rate
45873.40 kg/h from 645 0C to 70 0C. Cooling water will be used as the coolant fluid entering at
200C and exiting at 600C.
Table 16: Data of mixture
Component
Mwt
Mixture
Kg/Kmol
28.27
Kmol/h
1622.88
Kg/h
45873.40
Mole fraction
Y
Mass fraction
X
Table 17: Physical properties of mixture at Tave = 630.5 K and Pave = 12.4 bars
Component
Mixture
Pa.s
3.03 x 10-5
Cp
KJ/kg.K
1.1538
K
W/m.K
0.0484
Kg/m3
6.4106
Table 18: Physical Properties of cooling water at Tave = 40oC = 313 K
Component
H2O
Cp
KJ/kg.K
4.181
Pa.s
0.656 x 10-3
K
W/m.K
0.571
Heat duty (Q) needed to be remove from gas mixture:

Q = mCpmix T [7]
= 12.7426 1.1538 (645 70)
Q = 8453.887 KJ/s
For cooling water:

Qlost = Qgain = m1 Cpmix T + m2
[7]
m1: mass flow rate of mixture without water = 42163.34 kg/h

= 11.71 kg/s
m2: mass flow rate of water which is condensing
Calculating the remaining water in vapor pressure after 1st cooler:
Kg/m3
992.25
H2 O vapor exit at 70 oC (yH2 O ) =
P vap
[7]
P total
By Antoine Equation, we find Pvap of water

ln P vap = A
B
T+C
A =16.3872. B =3885.70. C =230.170

P vap = 31.256 kPa
yH2 O =
31.256
1064
yH2 O = 0.029
m2 =
yH2 O
(mass flow rate of mixture without H2 O)
1 y H2 O
0.029
(42163.45)
1 0.029
kg
kg
m2 = 1259.25 h = 0.35 s
m2 =
The remaining water in the exit liquid stream = H2O entering 1st cooler in stream 7 H2O exiting
vapor stream in stream 8
The remaining water = 1.03 0.35 = 0.68 kg/s
Qlost = Qgain = m1 Cpmix T + m2
[7]
= 1954.79 kJ/kg
mass of water = mwater =
Q
8453.887
kg
=
= 50.55 s
CpT 4.181 40
Finding :
T1 = 645 oC
T2 = 70 oC
COOLER
t2 = 60 oC
72
t1 = 20 oC
Tout = T1 t 2 = (645 60) = 585 oC

Tin = T2 t1 = (70 20) = 50 oC
Tlm =
Tout Tin
T
ln Toutt
in
[7]
Tlm = 217.52 C
The heat exchanger will consist of one shell pass and two tubes pass.
So we need a correction factor for Tlm:
Tm = Ft (Tlm)
=
1 2
= 14.375
2 1
2 1
= 0.064
1 1
[7]
[7]
From given Figure (12.19) in textbook for Ft as function of (R, S)

Ft = 0.97 [7]
Tm = (0.97)(217.52) = 210.99 oC
According to Table A in Appendix E, Cold fluid is water and hot fluid is gas. The following
value of overall heat transfer coefficient U can be estimated:
U=300 W/m2.oC
Q = U A Tm A = Q / U Tm
A= 133.56 m2
Choosing 25 mm OD, 21 mm ID Cupro-Nickel tubes to resist corrosion problems. Placing

cooling water in the tube side since it is more corrosive. Take Tube length L=5 m
Calculation of number of tubes (Nt):
Nt =
A
133.56
=
d L 25 103 5
[7]
Nt = 341 tubes
with Pt= 1.25do [7]
Calculation of bundle diameter (Db):

1
Nt n1
Db = do [ ]
K1
[7]

K1 = 0.249
n1 = 2.207
1
341 2.207
Db = 25 [
]
0.249
Db = 659.36 mm
Calculating the shell diameter (Ds):
Ds = Db + clearance
[7]
clearance= 66 mm
[7]
Ds = 659.36 + 63 = 722.36 mm
Calculating the heat transfer coefficients for tube side (hi): [7]
= 2 = (21)2 = 346.36 2
4
4
74
341
=
= 170.5
.
2
= (
) 2 = 0.059 2
.
4
50.55
=
= 856.78
2 .
0.059
856.78
( ) =
=
= 1.374
623.6318
( ) =

hi di
0.14
0.33
= Jh Re Pr
( )
Kf
w
992.25 1.374 21 103
() =
=
= 43643.872
0.656 103
(Turbulent Flow)
() =
4.181 103 0.656 103

=
= 4.803
0.571
From Figure B in Appendix E at Re = 43643.872

Jh = 2.9 x10 -3
From (eq. hi) and neglecting ( )

w
0.14
and assume it approximately 1
Then:
hi (21 103 )
= (2.9 103 ) (43643.872) (4.803)0.33
0.571
hi = 5776.13 W/m2.oC
[7]
As = [
Pt do
] Ds LB
Pt
Pt = tube pitch
Pt

do
do = 25 mm
Pt = 1.25 do mm = 31.25 mm
Ds 722.36
=
= 144.47 mm
5
5

31.25 25
= [
] = [
] (722.36)(144.47) = 20871.87 2
31.25
LB =
As = 0.02087187 m2
mshell = mass flow rate of mixture = 12.7426 kg/sec
= [
12.7426
]=[
] = 610.52 2 .
0.02087187
610.52
= [ ] =
= 95.24
6.4106
de =
1.10 2
(P 0.917d2o )
do t
1.10
[(31.25)2 0.917(25)2 ] = 17.75 = 0.01775
25
For shell side:

Physical properties of liquid water at Tave:
L = 60.03
kg
m3
L = 0.083 103 Pa. s

k L = 0.47 Wm. K
kg
v = 0.34 m3
76
h =
Ws
12.7426
=
= 4.98 103
Nt L 511 5
Number of tubes in centre row Nr =

Nr =
Db 659.36
=
= 21
Pt
31.25
2
21 = 14
3
1
3
L (L v )g
hc = 0.95 k L [
]
L h
Nr
1
6
1
3
60.03(60.03 0.34) 9.8

hc = 0.95 0.47 [
]
0.083 103 4.98 103
14
1
6
hc = 1264.34 W/m2 . oC
[7]

ln ( ) 1
1
1
1
1
=
+
+
+ ( )+
( )

2

Kw = thermal conductivity of tube wall material = 50 (W/m.oC) for ''Cupro -Nickel alloys''
hod = outside dirt " fouling " coefficient = 3000(W/m2.oC) (From Table B in Appendix E)
hid = inside dirt " fouling " coefficient = 3000 (W/m2.oC) (From Table B in Appendix E)
25 103 ln(2521)
1
1
1
1
25
1 25
=
+
+
+
( )+
( )
5776.13 3000
2 50
1264.34 21
3000 21
Uo = 529.53 W/m2 .oC
The value of 529.53 W/m2.oC is well above the estimated value of 300 W/m2.oC. Hence, the
present design satisfactory OK
Calculating the pressure drop (P) for side tube and shell tube: [7]
1.The tube side Pt
78
L
m
vt2
Pt = NP [8jf ( ) ( ) + 2.5] [
]
di w
2
baffle cut of 0.25
Now,
5
992.25 0.7582
Pt = 2 [8(3.5 103 ) (
)
+
2.5]
[
]
21 103
2
Pt = 5226.02 Pa = 5.22602 kPa (Acceptable)
Ds L
vs2
0.14
Ps = 8jf ( ) ( ) (
)( )
De LB
2
w
baffle cut of 0.25 = 2.8 x 10-2
shell = 11.56 kg/m3
857.99 5 103 6.4106 67.512
Ps = 8(2.8 102 ) (
)(
)(
)
17.75
171.59
2
Ps = 4609.086 kPa (Too high!)
This value for Ps is high, so we will decrease vs by quadrupling the baffle spacing, which will
reduce the velocity in the shell by a factor of (1/3)
i.e. new vs new = 0.333 vs old
Ps vs2
Ps new (0.333)2 Ps old
Ps new = (0.333)2 (4609.086) = 511.09 kPa
But this effect of using half vs old will affect the hs as follows
hs Re0.8
hs now = ( 0.333 )0.8 hs old
hs now = ( 0.333)0.8 (5776.13) = 2396.58 W/m2.oC
The new value for the overall heat transfer coefficient will be Uo = 468.91 W/m2.oC which is still
above the initial estimated value of 300 W/m2.oC then this trial for reducing Ps is satisfactory.

80
1. The selected heat exchanger has one shell pass and two tubes pass, in which cooling
water flow inside the tube and mixture flows inside the shell .
2. The selected tubes are made of Capper - Nickel alloy with 25 mm outside diameter, 21
mm inside diameter, the total number of tube is 341, while the tube length is 5 m, and the
triangular pitch applied for this tube distribution is 31.25 mm.
spacing is (63 mm).
4. The first estimated value for overall heat transfer coefficient Uo is 529.53 (W/m2. oC) ,
while the final calculated value is 468.91 (W/m2. oC).
5. The pressure drop ( Pt ) for the tube side is 6.20309 kPa , while the shell side ( Ps ) is
511.09 kPa .
4.8 Design of The Oxidation Unit
Partial pressure of O2 = 0.714 atm

Partial pressure of NO = 0.70 atm
=
=
2993
11.323 = 2.529 103 1 [14]
(2 () (2 ))
[14]
2.529 103
=
((80.047)2 (71.94))
8.314(343)
= 0.408
130 1000
3600
5.2 1000
=
3600
=

= 84.8 3
4.9 Design of Heat Exchanger (2nd Cooler):
82
The objective is to design a heat exchanger (shell and tube) to cool vapor mixture of flow rate
45873.40 kg/h from 140 0C to 60 0C. Cooling water will be used as the coolant fluid entering at
250C and exiting at 400C.
Table 19: Data of mixture
Component
Mwt
Mixture
Kg/Kmol
28.27
Kmol/h
1622.88
Kg/h
45873.40
Mole fraction
Y
Mass fraction
X
Table 20: Physical properties of mixture at Tave = 373 K and Pave = 12.4 bars
Component
Mixture
Cp
KJ/kg.K
1.1085
Pa.s
2.051 x 10-5
K
W/m.K
0.0603
Kg/m3
11.56
Table 21: Physical properties of cooling water at Tave = 32.5oC = 305 K
Component
H2O
Cp
KJ/kg.K
4.183
Pa.s
0.771 x 10-3
Heat duty (Q) needed to be remove from gas mixture:

= [7]
= 12.7426 1.1085 (140 60)
= 1130.0138 /
For cooling water:
= = [7]
= 1130.0138 / (4.183 (40 25))
= 18.01 /
Finding :
K
W/m.K
0.616
Kg/m3
995.5
T1 = 140 oC
T2 = 60 oC
COOLER
t2 = 40 oC
t1 = 25 oC
= 1 2 = (140 40) = 100

= 2 1 = (60 25) = 35
[7]
= 61.92
The heat exchanger will consist of one shell pass and two tubes pass.
So we need a correction factor for Tlm:
Tm = Ft (Tlm) [7]
=
1 2
= 5.333 [7]
2 1
2 1
= 0.130 [7]
1 1
From given Figure (12.19) for Ft as function of (R, S)

Ft = 0.98 [7]
Tm = (0.98)(61.92) = 60.68 oC
According to A in Appendix E, Cold fluid is water and hot fluid is gas. The following value of
overall heat transfer coefficient U can be estimated:
84
U= 300 W/m2.oC
Q = U A Tm A = Q / U Tm [7]
A= 62.08 m2
Choosing 25 mm OD, 21 mm ID Cupro-Nickel tubes to resist corrosion problems. Placing
cooling water in the tube side since it is more corrosive. Take Tube length L=5 m
Calculation of number of tubes:
=
62.08
=
25 103 5
= 159
with Pt= 1.25do [7]
Calculation of bundle diameter Db: [7]
1
1
= [ ]
1
K1, n1 are constants given in Table C: [7]
K1 = 0.249
n1 = 2.207
1
159 2.207
= 25 [
]
0.249
Db = 466.64 mm
Calculating the shell diameter Ds: [7]
= +
clearance= 56 mm [7]
= 466.64 + 56 = 522.64
Calculating the heat transfer coefficients for tube side (hi): [7]
= 2 = (21)2 = 346.36 2
4
4
159
=
= 79.5
.
2
= (
) 2 = 0.028 2
.
4
18.01
=
= 643.21
2 .
0.028
643.21
( ) =
=
= 0.646
995.5
( ) =

0.14
0.33
=
( )

() =
995.5 0.646 21 103

=
= 17516.15
0.771 103
(Turbulent Flow)
4.181 103 0.771 103
() =
=
= 5.233
0.616
From Figure B in Appendix E at Re=17516.15
Jh = 3.8 x10-3
From (eq. hi) and neglecting (
0.14
w
Then:
hi (21 103 )
= (3.8 103 ) (17516.15 ) (5.233)0.33
0.616
hi = 3371.09 W/m2.oC
Calculate heat transfer coefficients for shell side (ho): [7]

86
= [
Pt = tube pitch
Pt

do = 25 mm
Pt = 1.25 do mm = 31.25 mm
522.64
=
= 104.53
5
5

31.25 25
= [
] = [
] (522.64)(104.53) = 10926.31 2
31.25
=
As = 0.01092631 m2
mshell = mass flow rate of mixture = 12.7426 kg/sec
= [
12.7426
]=[
] = 1166.23 2 .
0.01092631
1166.23
= [ ] =
= 100.88
11.56
=
1.10 2
( 0.9172 )
1.10
[(31.25)2 0.917(25)2 ] = 17.75 = 0.01775
25
Re & Pr for shell side

=
11.56 100.88 0.01775

=
= 1009242.67
2.051 105
1.1085 103 2.051 105

=
=
= 0.377

0.0603
The shell side coefficient (hs or ho):
do
1

0.14
= 3 ( )

From Figure B in Appendix E at 25% assumed design value for baffle cut and Re:
Jh = 6.2x10-4
0.14
)
Assumed to be approximately 1. We get
w
(25 103 )
= 6.2 104 1009242.67 0.3770.33
0.0603
hs = 1093.85 W/m2.oC
Calculating the overall heat transfer coefficient (U): [7]

88

ln ( ) 1
1
1
1
1
=
+
+
+ ( )+
( )

2

Kw = thermal conductivity of tube wall material = 50 (W/m.oC) for ''Cupro -Nickel alloys''
hod = outside dirt " fouling " coefficient = 3000(W/m2.oC) (From Table B)
hid = inside dirt " fouling " coefficient = 3000 (W/m2.oC) (From Table B)
25 103 ln(2521)
1
1
1
1
25
1 25
=
+
+
+
( )+
( )
3371.09 3000
2(50)
1093.85 21
3000 21
Uo = 463.24 W/2 .oC
The value of 463.24 W/m2.oC is well above the estimated value of 300 W/m2.oC. Hence, the
present design satisfactory OK
Calculating the pressure drop (P) for side tube and shell tube: [7]
1.The tube side Pt
L
m
vt2
Pt = NP [8jf ( ) ( ) + 2.5] [
]
di w
2
baffle cut of 0.25
Now,
5
995.5 0.6462
Pt = 2 [8(4.2 103 ) (
)
+
2.5]
[
]
21 103
2
Pt = 4362.09 Pa =4.36209 kPa (Acceptable)
90
Ds L
vs2
0.14
Ps = 8jf ( ) ( ) (
)( )
De LB
2
w
baffle cut of 0.25 = 2.5 x 10-2
shell = 11.56 kg/m3
522.64 5 103 11.56 100.882
Ps = 8(2.5 102 ) (
)(
)(
)
17.75
104.53
2
Ps = 16569.19 kPa (Too high!)
This value for Ps is high, so we will decrease vs by quadrupling the baffle spacing, which will
reduce the velocity in the shell by a factor of (1/3)
i.e. new vs new = 0.333 vs old
Ps vs2
Ps new (0.333)2 Ps old
Ps new = (0.333)2 (16569.19) = 1837.34 kPa
But this effect of using half vs old will affect the hs as follows
hs Re0.8
hs now = ( 0.333 )0.8 hs old
hs now = ( 0.333)0.8 (3371.09) = 1398.70 W/m2.oC
The new value for the overall heat transfer coefficient will be Uo = 388.04 W/m2.oC which is still
above the initial estimated value of 300 W/m2.oC then this trial for reducing Ps is satisfactory.
1. The selected heat exchanger has one shell pass and two tubes pass, in which cooling
water flow inside the tube and mixture flows inside the shell .
2. The selected tubes are made of Capper - Nickel alloy with 25 mm outside diameter, 21
mm inside diameter, the total number of tube is 159, while the tube length is 5 m, and
the triangular pitch applied for this tube distribution is 31.25 mm.
spacing is (56 mm).
4. The first estimated value for overall heat transfer coefficient Uo is 463.24 (W/m2 . oC) ,
while the final calculated value is 388.04 (W/m2. oC).
5. The pressure drop ( Pt ) for the tube side is 4.36209 kPa , while the shell side ( Ps ) is
1837.34 kPa .
4.10 Design of Absorber

92
Introduction
The most important step of manufacturing nitric acid is Absorption of NOx When it is compared
to other absorptions operation. Absorption of NOx is the most complex. This is for several
reasons:
1. NOx is a mixture of several components of NO,NO2,N2O3 and N2O4.

2. In absorption tower many reversible and irreversible reactions.
3. Simultaneous absorption of many gases occurs followed be chemical reaction.
4. Heat Generated from the reactions, which affect the absorption.
2NO2 + H2O + O2 2HNO3
Figure 1 Nitric acid column
The objective
To design an absorption tower to absorb NO2 from the mixer gas stream using water to form
nitric acid with 60% weight.
Absorber design calculation
Tail Gases 30 C
Y2 = 0.0048
Water 20 C
X2 = 0
Gases 60 C
Y1 = 0.0884
Nitric Acid 30 C
X1 = 0.3
Figure 2 Stream temperature and NO2 molar composition
Number of Gases moles entered the absorber= Gm= 1417.09 Kmol/hr

Number of water moles entered the absorber=Lm=373.19 Kmol/hr
Table 22: Compositions of income gases
Component
NO2
NO
O2
N2
Mole fraction
0.0884
0.0037
0.0386
0.869
Molecular weight
46
30
32
28
94
()
= (46 0.0884) + (30 0.0037) + (32 0.0386) + (0.869 28)
= 29.74
( ) = =
1200000 29.74
=
8314.34 333
= 12.89 /3
T=60 C = 333 K
P= 1200000 Pa
R= 8314.34 3 /
Density of water at 20 C, 1200 kPa = = 998.23 Kg/m3 [3]

Diameter Calculation
= (0.171 2 + 0.21 0.047) (
0.5
[7]
Lt=plat spacing=0.9 m
= (0.171
(0.9)2
998.23 12.89 0.5

+ 0.21 0.9 0.047) (
) = 0.51 /
12.89
Taking 60% Uv =0.3 m/s

4
[7]
4 11.71
= 1.96 2
3.14 12.98 0.3
Design 1
Assumptions
1. N2O4 (2NO2) is the only species, which dissolved in the Liquid.
2. Neglect the reactions occurs in the column.
3. Isothermal Operation and the temperature is 45oC.
4. The design of the column is trays absorption column.
Height of Absorber
Equilibrium line can be specified:
=
From Raoult's law

[18]
Psat for NO2 at 45oC:

From Antoine Equation:
=
[7]
From appendix C page. 1123 [7]

A=20.5324
B= 4141.29
C=3.65
T= 45oC= 318 k
= 20.5324
4141.29
= 7.6572
318 + 45
Psat = 2115.944 mmHg = 282.01 kPa

So, the slope of the equilibrium line
=
282.01
= 0.234
1200
96
ln[(1 ) (1 2 ) + ]
2
2
= =
ln( )

[19]
m = 0.235
Gm = 1417.09 kmol/hr
Lm = 373.191 Kmol/hr
Y1 = 0.0048
Y2 = 0.0884
X2 = 0
0.0884 0
ln [(1 0.893) (0.0048 0) + 0.893]
1
ln (0.893)
= 9.3 10
= = = 10 0.9 = 9
Design 2:
Assumptions:
1. N2O4 (2NO2) is the only species, which dissolved in the Liquid.
2. The reaction occurs in the column.
3. 2NO2 + H2O + O2 2HNO3
4. Isothermal Operation and the temperature is 45oC.
5. The design of the column is trays absorption column.
Height of Absorber:
From fuller equation, the diffusivity of N2O4 in water:
A = N2O4
B= H2O
VA= 33.5
VB=14.7
MA= 92
MB=18
T=45 C =318 K
P=1200 Kpa = 11.843 atm
1
1 0.5
1 107 1.75 ( + )
=
[17]
0.33
0.33 )2
( +
1
1 0.5
1 107 3181.75 (92 + 18)
11.843(33.50.33 + 14.70.33 )2
= 1.6535 106 2 /
Mass transfer Coefficient can be calculated from the following Equation:
0.33
( )
0.42 0.5
=
[
]
2
= =
[17]
2.3 105
=
= 13.3

1 1.6535 106
[3]
= 2 4 = 2.2 105 /.
= 12.89 /3
= 998.23 /3
= 1.0 /3
= 13.3
= = 9.8 / 2
3
R= = 8.2 102
98
[(998.23 12.89) 2.2 105 9.8]0.33

0.42 13.30.5
=
8.2 102 318

12
= 2.6484 103 /2 . .
Determine the rate reaction

=
2 4
1
1
+ 1
[4]
Kg= mass transfer coefficient, kmol/m2.atm.sec

PN2O4= partial pressure of N2O4 at interface, atm
H= solubility of N2O4 in liquid = 0.352 kmol/m3.atm [19, page.275]
K1= reaction rate constant= 1340 sec-1 [19, page.275]
= , /2 . .
1 = 0.0166
3
= 700 2
1 700
=
= 1.6
1
1
+
2.6484 103 0.0166
1
() =
[7]

+
3
3
0.0019
3
=
=
2.05
10
3
3

0.0019 + 0.91
G = molar velocity of gas based on the area of the absorber

= 0.3936 /. 2
=
0.3936
=
= 0.1253 2
2
2
4
2 4 = 0.7
2 4 = 1.3 101
0.1253
0.7
ln (
) = 27.7 28
3
11.843 2.05 10 1.6
1.3 104
100
4.11 Design of Nitric Acid Tank
( 0.5 1)
0.5
= ( ) ( 1) = ( ) [
]
2
2
0.5
[7]
Where:
t = wall thickness (mm)
Di = tank inside diameter (mm)
D0 = tank outside diameter (mm)
Z = (FE + P)/ (FE - P)
F = design tensile strength of material (MPa)
E = joint efficiency
P = internal pressure (MPa)
The internal pressure is equivalent to the head of liquid inside the tank. This maximum head of
10.7 m represents a pressure of 142 kPa. The recommended wall thickness is:
=
=
( + )
[7]
( )
[(108 0.8) + 0.142]
[(108 0.8) 0.142]
= 1.003
15200
= (
) (1 .0030.5 1) = 11
Adding a corrosion allowance of 5 mm, the final recommendation is for 16 mm plating for the
tank shell based on circumferential stress. Minimum thickness based upon longitudinal stress
(circumferential joints) Formula as given above for circumferential stress, except that:
= [
] + 1 [7]
With the internal pressure at 140 kPa, the calculation is:
] + 1
0.140
= [
] + 1
108 0.8
= [
= 1.0016
= (
15200
) (1.00160.5 1) = 6
2
This indicates that circumferential stresses are more important, and they determine the minimum
shell thickness for this tank. The BHP steel plate available and closest to this specification is 16
mm thickness.
Checking Calculations for Other Stresses

Dead- weight stress
= +

= [{15.2 + (2 0.016)} 0.016 10.71
+ 1.3 [( ) 15.2 2 0.0161]] [7]

4
= 12 3
Density of SS304L = 7.8 tones/m3
= = 12 7.8 = 93.6
Considering the stresses:
Weight stress =

Weight stress =
93.6 x 9.8
(15.2 + (2 x 0.016)) 0.016
Weight stress = 1200 kPa

Weight stress = 1.2 MPa
=
Axial stress =
4
0.140 {15.2 + (2 0.016)}
4 1 0.016
Axial stress = 33 MPa

Hoop stress = 2 Axial Stress = 66 MPa
Wind stresses are disregarded because of the high ratio of tank diameter to tank height.
Analysis of Stresses:
Upwind Total stress = Axial stress - Radial stress = 33 - 1.2 = 31.8 MPa
Downwind Total stress = Hoop stress - Radial stress = 66 - 1.2 = 64.8 MPa
Radial Radial stress = 0.5 P = 70 kPa
102
Maximum stress = 70 MPa

The maximum stress is approximately 35% below the design stress of 108 MPa, and therefore
the shell thickness used in this design is considered acceptable. Inlet/Outlet Line Diameters The
inlet and outlet line diameters are sized for a recommended liquid flowrate of 2 m/s.
The inlet line sizing is determined by allowing 20% above the normal product flowrate of 11 700
kg/h. This corresponds to a volumetric flowrate of 2.9 10-3 m3/s.
Area of pipe = Volumetric flowrate/Velocity
2.9 103
=
= 1.44 103 2
2
4 0.5
Diameter of pipe = [
]
0.5
1.44 103 4
[
]
= 40mm
The nearest commercial pipe size is a nominal pipe size of 1.5, schedule number 40s (with inside
diameter of 41 mm and a wall thickness of 4 mm).
The outlet flowrate is calculated based upon the need to fill a standard 30 tonne tanker in 15
minutes. This corresponds to a volumetric flowrate of 2.5 x 10-2 m3/s
Area of pipe = Volumetric flowrate/Velocity
= 2.5 10-2/ 2
= 1.23 10-2
Diameter of pipe = [
4 0.5
]
0.5
1.44 103 4
[
]
= 40mm
The nearest commercial pipe size is a nominal pipe size of 6, schedule number 120 (with an
inside diameter of 140 mm and a wall thickness of 14 mm).
Figure 7 Tank of nitric acid [5]
104
Chapter 5
Control Loop
5.1 Introduction
Control is crucial because it provides a proper control of the process variables so that the whole
plant operation is within the specification limit for safety purposes. Besides, it has direct impacts
on the plant economics, environment and the product specifications. According to Seborg
(2004), without process control, it is impossible to operate most modern processes safely and
profitably, while satisfying plant quality standards.
The three most important considerations that make plant control necessary are:
1. Safe Plant Operation
To keep the process variables within known safe operation limits
To make sure the temperature and pressure at the desired level for reactor and columns
To detect danger as they develop and to provide alarms and automatic shutdown systems
To provide interlocks and alarms to prevent dangerous operating conditions
2. Production Rate and Quality
To achieve the design product output composition specification for outlet stream of
reactor according to the literature specification
To maintain the desired purity especially for ethyl acetate and acetic acid
3. Cost Operation
To operate at the lowest production cost, commensurate with the other Objectives
To minimize the usage of heating and cooling utility, and thus reducing the utility cost
The types of basic control strategies that is implemented under the scope of this project are:
Feedback control
Feedforward control
Cascade control
Ratio control
106
The simplest control loops requires:

1- Identifying the controlled variable.
2- Setting the required value of the controlled variable.
3- Measuring the controlled variable
4- Identifying the magnitude of deviation (set value measured value).
5- Sending the deviation to the controller.
6- Adjusting the value of manipulated variable to offset the deviation.
Table 23: Symbols used in control loops
Symbol
Definition
Control Valve
Normally Closed Gate Valve
LC
Level Control
TC
Temperature Control
FC
Flow Control
TT
Temperature Transmitter
AC
Analyzer Control
PC
Pressure Control
PT
Pressure Transmitter
Figure 8 Process control loop for nitric acid production
108
5.2 Control of Vaporizer

Table 24: Control specification of vaporizer
Control Strategy Selected
Feedback control
Control Objective
To set the output temperature to 35 C
Controlled Variables
Output temperature
Measured Variables
Output temperature
Manipulated Variables
The flowrate of steam inside the vaporizer
The flowrate of ammonia inside the

vaporizer
Disturbances
The Temperature of ammonia inside the

vaporizer
Set Points
35C inlet temperature to Superheater.
5.3 Control of Reactor

Table 25: Control specification of reactor
Feedback control
Control Objective
To set the reactor pressure to 1060 kPa
Output temperature
Reactor pressure
Output temperature
Reactor pressure
The flow rate of Cooling water in the
Measured Variables
reactor
The flow rate of vented gas
The flow rate of air and ammonia
The Temperature of air and ammonia
Disturbances
Set Points
inside the reactor
645 C inlet temperature to cooler.
110
5.4 Control of Absorber

Table 26: Control specification of absorber
Feedback control
Control Objective
To set the reactor pressure to 1200 kPa
Output temperature
Absorber pressure
Output temperature
Absorber pressure
The flow rate of Cooling water in the
Measured Variables
Absorber
The flow rate of vented tail gas
The flow rate of multi gases
The Temperature of multi gases inside the
Disturbances
Set Points
absorber
30 C product temperature
Chapter 6
Economic Analysis
112
6.1 Estimation of capital investment items based on delivered equipment [16]

ITEM
*DIRECT COSTS
Purchased equipment cost (PEC)
PEC
Purchased equipment Installation
0.47 PEC
Instrumentation and controlled
0.18 PEC
Piping (Installed)
0.66 PEC
Electrical (Installed)
0.11 PEC
Buildings (including services)
0.18 PEC
Yard improvements
0.10 PEC
Land
*TOTAL DIRECT PLANT COST
3.4 PEC
*INDIRECT COSTS
Engineering and supervision
0.33 PEC
Construction expenses
0.41 PEC
TOTAL DIRECT AND DIRECT

PLANT COSTS
4.14 PEC
Contractor fee
0.207 PEC
Contingency
0.414 PEC
Fixed capital investment (FCI)
4.761 PEC
Working capital investment (Wc)
0.84 PEC
Total capital investment (TCI)
5.601 PEC
6.2 Equipment Cost (at 2011) [16]

Equipment
Material
Purchase Cost $
Compressor
SS
1,700,000
Vaporizer
SS
38,760
Superheater
SS
78,702
Reactor
SS
227,587
Cooler 1
Cuppro-Nickel
286,868
Oxidation
SS
115,838
Cooler 2
Cuppro-Nickel
212,937
Absorption Column
SS
187,384
Nitric Acid Tank
SS
1,396,861
Cost $
I0 (Index at 2011) = 586.5
4,244,937
I (Index at 2013) = 636
Cost (in 2013) = Cost (in 2011) (I / I0)

Cost $ (at 2013) = 4603206
The Location Factor = 1.3
PEC = cost (at 2013) 1.3
PEC = $5,984,168
114
6.3 Total Production Cost (TPC) [16]

TPC = Manufacturing Cost + General Cost
1) Manufacturing Cost
A) Direct Production Cost
1) Raw Material
$9343520
2) Operating labor
0.1TPC
3) Direct Supervisory
0.11TPC
4) Utilities
0.1 TPC
5) Maintenance
0.05FCI
6) Operating Supplies
0.005FCI
7) Liberty Charges
0.1TPC
8) Patients & Royalties
B) Fixed Charges
1) Deprecation
0.1FCI
2) Taxes
3) Insurance
0.005FCI
4) Rent
C) Plant Overhead Cost
0.05TPC
2) General Costs
a) Administration
0.02TPC
b) Distribution
0.05TPC
c) Research & Development Costs
0.05TPC
d) Financing
Fixed Capital Investment (FCI)

FCI = 4.761 PEC
FCI = 28490624$
Working Capital Investment (WC)
WC = 0.84 PEC
WC = $5026702
Total Capital Investment (TCI)

TCI = 5.601 PEC
TCI = $33,517,325
Total Production Cost (TPC)
TPC = Manufacturing Cost + General Cost
TPC = 0.58TPC + 0.16FCI + 9,343,520
TPC = $33,100,048
Revenue (total income)
Revenue = Price of Nitric Acid (per ton) Capacity
Revenue = 400 100,000
Revenue = $40,000,000
Net Profit
Net Profit = Revenue - TPC
Net Profit = 400,00,000 33,100,048
Net Profit = $6,899,953
Return on Investment (ROI)
ROI = ((Net Profit)/TCI) 100
ROI = 20.5%
Depreciation = 0.1 FCI = $2,849,062.40

ACF = Annual Profit + Depreciation = 6,899,953 + 2,849,062.40 = $9,749,015.40
Pay Back Period (PBP)

PBP = TCI/ACF = 3.43 years
116
Chapter 7
Process Integration
INTRODUCTION TO PROCESS INTEGRATION

The process industrial is among the most important manufacturing facilities. They span a
wide range of industries including chemical, petroleum, gas, petrochemical, food,
pharmaceutical, microelectronics, metal, textile, and forestry product. The performance of these
industries is strongly dependent on their engineering and engineers. So, what are primary
responsibilities of process engineers in the process industries? Many process engineers would
indicate that their role in the process industries is to design and operate industrial processes and
make them work faster, better, cheaper, safer, and greener. All of these tasks lead to more
competitive processes with desirable profit margins and market share. Specifically, these
responsibilities may be expressed through the following specific objectives: process innovation,
profitability enhancement, Yield improvement, capital productivity increase, Quality control,
assurance
and
enhancement
Resource
conservation,
Pollution
prevention,
safety,
Debottlenecking.
Heat Integration Objectives

Heat integration, as a part of process integration aims at:
Designing a process in such a way that it makes optimum use of energy that is available
within the process itself
Optimizing the quality level of the utilities required
Optimizing energy exchange with neighboring plants and energy recovery with the view
to optimize energy and capital cost
However, our aim was to use the steam, which occurred when the reactor cooled down by water,
which leaded us to use the steam to vaporize the ammonia.
Stripping
Based on our project, we avoid using the stripping due to the problems, which can be caused,
by stripping such as increasing the purity of nitric acid, which can be ended up by killing the
plant. Also, this project had designed to use the nitric acid (60% purity) under specific conditions
on other words. If we use the nitric acid more than 60% purity we can use it as bombs, and if we
use it as 60% purity we can use it as fertilizer.
118
Chapter 8
Safety and Loss

Prevention
120
8.1 Plant Layout

There are several plant layout considerations relevant to the Bunbury site. First, the prevailing
winds direction, shown with a dark arrow in Figure 9. This would indicate that the tank farm is
best placed on the seaside of the site to avoid vapors drifting back across the plant area. The
second major consideration is the need for road access to the ammonium nitrate dispatch/storage
area.
A suggested layout for the overall complex is shown in Figure 9.It features the three chemical
processes flowing approximately one to the other. The joint administration and workshop
facilities are located in the southwestern corner of the plant. There is a central control room for
all operations, and the roadway is extended into the dispatch area.
The nitric acid plant is relatively small and should not occupy more than 1 hectare. Even this
small area should leave plenty of room for expansion. The plant layout includes space for a
parallel production trucks should the market expand sufficiently in the future such that a second
plant is required. The layout also offers plenty of room around each unit for maintenance work,
with units remaining closes enough for process streams to be transferred easily. The main
objectives of the plant layout are:
To maximize safety
To prevent spread of fire
To facilitate easy operation and maintenance
To consider future expansion
To minimize the construction cost
Figure 9 Nitric acid plant layout
122
8.2 Safety of Materials

Ammonia
Both gaseous and liquid ammonia pose moderate health hazards to those who come into
contact with them. For example, farmers who handle liquid ammonia risk the possibility of
painful blistering of the skin or damage to the mucous membranes if they come into contact with
the fertilizer. Ammonia fumes can irritate the mouth, nose, and throat, causing coughing and
gagging responses. Higher levels of exposure may irritate the lungs, resulting in shortness of
breath and producing headaches, nausea, and vomiting. Very high exposures can cause a buildup
of fluid in the lungs that can result in death. Since ammonia is a common ingredient of many
household products, everyone should be aware of its health risks, although the threat posed by
such products is, in fact, very small. [15]
Nitric oxide
Nitric oxide is considered an environmental pollutant. It oxidizes readily to form nitrogen
dioxide, which, in turn, reacts with moisture in the air to form nitric acid, a component of acid
rain. Acid rain is thought to be responsible for a number of environmental problems, including
damage to buildings, destruction of trees, and the death of aquatic life. The nitrogen dioxide
produced from nitric oxide is also a primary component of photochemical smog, a hazardous
haze created by a mixture of pollutants in the presence of sunlight.
Even though it is toxic in the environment, nitric oxide plays several important roles in the
human body. Nitric oxide is involved in the process by which messages are transmitted from one
nerve cell to the next. It also regulates blood flow by triggering the smooth muscles surrounding
blood vessels to relax. This action increases blood flow and lowers blood pressure. Nitric oxide
also prevents the formation of blood clots, which can break off and travel to the heart or brain,
increasing the risk of heart attack or stroke.
Finally, nitric oxide plays a role in memory and learning. A deficiency of the compound
appears to be related to the development of learning problems. On the other hand, an excess of
nitric oxide has been implicated in the development of certain diseases, such as Huntingtons
chorea, an inherited disorder characterized by unusual body movements and memory loss, and
Alzheimers disease, a progressive disorder that results in memory loss.
When used to treat a medical condition, nitric oxide is usually administered in the form of a
solid or liquid medicine that decomposes in the body, releasing the compound. For example, the
drug nitroglycerin is used to treat heart problems. When it enters the bloodstream, nitroglycerin
begins to break down, releasing nitric oxide. The nitric oxide causes smooth muscle cells in the
heart to relax, relieving the symptoms of angina, chest pain caused by an inadequate flow of
blood to the heart. Other types of drugs produce nitric oxide to inhibit the buildup of fatty
deposits in blood vessels, which can lead to heart attack and stroke. Patients with pulmonary
hypertension, a condition in which the vessels that supply blood to the lungs are constricted,
preventing normal oxygen flow, are sometimes given an inhaler with a mixture of nitric oxide
and air to open blood vessels to the lungs.
In spite of its many benefits, nitric oxide may also be a health hazard. If inhaled in excessive
amounts, it may replace oxygen in the lungs, leading to asphyxia, suffocation resulting from an
insufficient supply of oxygen. Research suggests that exposure to low concentrations of the gas
over long periods of time may result in lung disease, emphysema, and chronic bronchitis. [15]
Nitrogen dioxide
Nitrogen dioxide poses both safety and health hazards. As a strong oxidizing agent, it reacts
readily with combustible materials, such as paper, cloth, and other organic matter to produce
fires or explosions. It is also a toxic material, producing some biological effects at relatively low
concentrations in the air. These effects include irritation of the eyes, nose, and throat; coughing;
congestion; chest pain; and breathing difficulties. The gas is sometimes referred to as an
insidious agent because its effects may go unnoticed for several hours or days, during which time
more serious damage may have occurred. This damage may include pulmonary edema, a
condition in which the lungs begin to fill with fluid; cyanosis, a condition in which the lips and
mucous membranes turn blue because of lack of oxygen; and a variety of heart problems. Longterm exposure to nitrogen dioxide may result in chronic health problems, such as hemorrhaging
(blood loss), lung damage, emphysema, chronic bronchitis, and eventually death. [15]
124
Nitric acid
Nitric acid is a highly toxic material. It attacks and destroys skin and other tissues, leaving a
distinctive yellow scar caused by the destruction of proteins in the skin or tissue. If swallowed,
inhaled, or spilled on the skin, it can cause a number of effects, including severe corrosive burns
to the mouth, throat, and stomach; severe irritation or burning of the upper respiratory system,
including nose, mouth, and throat; damage to the lungs; severe breathing problems; and burns to
the eye surface, conjunctivitis, and blindness. In the most severe cases, the acid can cause death.
[15] (For more information, see appendix A)
8.3 Hazard and Operability Studies
Figure 10 the three nodes chosen for HAZOP study
126
Node 1:
Node No. 1:
Intention:
Inlet to the Oxidation Unit (R-202)

Start from the Cooler (E-201) to the Oxidation Unit (R-202)
To transport the multi gases to the Oxidation Unit
Guide
word
Deviation
None No flow
Less
Causes
Flow control valve failure
(closed, seat of plug broken,
electrical signal fails)
Pipeline rupture
Partial plug or large leak in pipe

Valve not fully open
Less
Temperature
Less Pressure
Cold weather
Temperature controller
malfunctioning
Pressure controller
malfunctioning
Pipe leakage
Less Flow
Consequences
No flow into the
Oxidation unit
No reaction
Explosion
Process stops
Product not according to

the desire specifications
Reduced production
Action requires
Install low flow alarm
Install flow indicator and flow control
valve
Plant emergency shutdown procedure
Check regularly (maintain), check
signal of control valve, operates bypass line
Install temperature indicator

Install low temperature alarm
May cause change in the

gas phase
Install pressure control

Install low pressure alarm
Contd Node 1
Guide
word
More
Deviation
More Flow
Causes
Consequences
Valve opened at full rate
More
Temperature
More
Pressure
Hold weather
malfunctioning
Pressure controller
malfunctioning
Partial blockage of line due to
partially closed valve
Relief valve fails closed
Action requires
Change in product
quality
Some of gas exit without
reaction
Install high level alarm

valve

the desired specification
Reaction fail or run
away
Install high Temperature alarm
Increase pressure
upstream
Excess pressure (may
cause explosion)
Install pressure relief valve with

automatic
feed from temperature control system
Install high pressure alarm
128
Node 2:
Node No. 2:
Intention:
Inlet to Cooler (E-202)

Start from the Oxidation Unit (R-202) to Cooler (E-202)
To transport the multi gases to Cooler
Guide
word
Deviation
None No flow
Less
Less Flow
Less
Temperature
Causes
Pipeline rupture
Partial plug or large leak in pipe

Valve not fully open
Cold weather
malfunctioning
Less flow temperature from
oxidation unit
Pressure controller
malfunctioning
Pipe leakage
Less Pressure
Consequences
No product
Process stops
Action requires
valve
Check regularly (maintain), check
signal of control valve, operates bypass line

Reduced production
Overheated flow

cooler outlet
temperature less than the
desired

May cause reverse in

flow

Contd Node 2
Guide
word
Deviation
More Flow
Causes
Process rate changes
More
Temperature
Consequences
Reduce Heat transfer
efficiency
Process fails
Action requires
valve

automatic feed from temperature
control system
Hot weather
Fire near the stream
malfunctioning
High flow temperature from the
oxidation unit
The output flow has

high temperature than
desired
Fails process
Pressure controller
malfunctioning
Partial blockage of line due to
partially closed valve
Increase pressure
upstream
Excess pressure (may

cause explosion)
cooler fails
More
More
Pressure
130
Node 3:
Node No. 3:
Intention:
Inlet to Absorber (T-201)

Start from the Cooler (E-202) to Absorber (T-201)
To transport the multi gases to Absorber (T-201)
Guide
word
Deviation
None No flow
Less
Less Flow
Less
Temperature
Causes
Pipeline rupture
Partial plug or large leak in pipe.

Valve not fully open.
Reaction gas temperature in

oxidation unit lower
Less Pressure
Gas Release (line rupture)
Consequences
No Absorption in the
column
Entire process stops as
tail-gas row stops
Action requires
Plant emergency shutdown procedure.
Check signal of control valve, operates
by-pass line
The production of Nitric

acid will be less
Decreased absorption
Increased dissolved
NOx
Concentration of the
product will be higher
Less efficiency of NOx
absorbed


Contd Node 3
Guide
word
Deviation
More More Flow
Causes
Valve opened at full rate
More
Temperature
More
Pressure
Higher feed rates causing larger

heat of reaction
Pressure controller
malfunctioning
Flooding
Consequences
Possible reduction in
absorption efficiency
May cause flooding
Reduce absorption
efficiency
Higher NOx emission

due to lower absorption
More NOx absorebed
Action requires
valve

automatic feed from temperature
control system
132
Chapter 9
Waste Treatment
What Is NOx?
Most of the worlds nitrogen occurs naturally in the atmosphere as an inert gas
contained in air, which consists of approximately 78% N2 by volume. NOx refers to
oxides of nitrogen. These generally include nitrogen monoxide, also known as nitric
oxide (NO), and nitrogen dioxide (NO2). They may also include nitrous oxide (N2O),
also known as laughing gas, as well as other less common combinations of nitrogen and
oxygen, such as nitrogen tetroxide (N2O4) and nitrogen pent oxide (N2O5).
The EPA defines nitrogen oxides as all oxides of nitrogen except nitrous oxide.1
In most high-temperature heating applications; the majority of the NOx exiting the
exhaust stack is in the form of nitric oxide (NO).
What is Wrong with NOx?
Health hazards: NO is poisonous to humans and can cause irritation of the eyes and
throat, tightness of the chest, nausea, headache, and gradual loss of strength. Prolonged
exposure to NO can cause violent coughing, difficulty in breathing, and cyanosis; it
could be fatal. NO2 is a reddish-brown, highly reactive gas that has a suffocating odor
and is a strong oxidizing agent. It is highly toxic and hazardous because of its ability to
cause delayed chemical pneumonitis and pulmonary edema. NO2 vapors are a strong
irritant to the pulmonary tract.
Ground level ozone: Ozone (O3) is present in the upper atmosphere and is desirable as
it shields the earth against high-intensity ultraviolet rays from the sun. However, ozone
in the lower atmosphere is undesirable. There, NO reacts with oxygen to form ozone, in
addition to NO2:
NO + HC + O2 + sunlight NO2 + O3
Ozone is also a health hazard that can cause respiratory problems in humans. It is an
irritant to the eye, nose, and throat. Ozone can cause damage to plants including crops
and deterioration of textiles and other materials.
Acid rain: Rain is effective at removing NO2 from the atmosphere. However, NO2
decomposes on contact with water to produce nitrous acid (HNO2) and nitric acid
(HNO3), which are highly corrosive . NO is the predominant form of NOx produced in
industrial combustion processes. It reacts with O2 in the atmosphere to form NO2.
When NO2 forms in the atmosphere and comes into contact with water in the form of
134
rain, nitric acid is formed. Acid rain is destructive to anything it contacts, including
plants, trees, and man-made structures like buildings, bridges, and the like.
Smog: Another problem with NO2 is its contribution to smog. Smog is the combination
of smoke and fog and occurs where there are high concentrations of pollutants
combined with fog. Smog impairs visibility through the atmosphere. When sunlight
contacts a mixture of NO2 and unburned hydrocarbons in the atmosphere,
photochemical smog is produced.
Figure L: Acid rain
Figure K: Smog
Nitrogen Oxide Pollution
The nitrogen oxides NO and NO2 which make up NOx have long been known as
precursors of acid rain and smog. While ever more stringent emission limits apply in
many countries there are still a large number of nitric acid plants, which have no NOx
abatement equipment installed. Nitrous oxide (N2O) is a powerful greenhouse gas being
about 300 times more potent than carbon dioxide. Even though nitric acid plants
represent the largest single industrial process source of this gas, most countries have not
yet imposed emission limits on N2O, although steps in this direction are being made, for
example, in the European Union. As nitric acid plants are point sources for N2O and
NOx emissions they make good candidates for the implementation of cost effective
greenhouse gas and NOx emission reduction technologies.
Uhde Technologies for NOx and N2O Abatement
1. Uhde DeNOx process: NOx reduction with ammonia:
It was found that one of the iron zeolites materials tested was a very efficient catalyst
for the selective reduction of NOx (NO and NO2) with ammonia. This catalyst has the
advantage that it can be used over a large range of temperatures, from ~200C to over
500C, while classical vanadium-pent oxide-based SCR catalysts for nitric acid plants
generally cannot be used at temperatures much above ~400C. A further advantage is
that it generates no N2O, again in contrast to vanadium pent oxide, which is reported to
produced N2O at temperatures above 350C (Jouannic etal.1984).
This is the basis of the Uhde DeNOx process, which has a similar ammonia
consumption to classical SCR/DeNOx processes, is applicable over a wider range of
temperatures and, in contrast to frequently used classical SRC/DeNOx catalyst
materials, contains no environmentally hazardous substances, thus simplifying handling
and disposal. The Uhde DeNOx process can be very conveniently combined with N2O
abatement as described below
2. EnviNOx process variant 1: N2O decomposition with NOX reduction:
The iron zeolite catalysts investigated decompose N2O into its elements. An
important phenomenon is that the rate of decomposition is greatly enhanced when NOx
is present in the waste gas stream. This fact, combined with the NOx reducing
136
properties of the iron zeolite catalysts, is exploited in the EnviNOx process variant 1,
which is illustrated in Figure 13.
The EnviNOx reactor is typically located in the tail gas stream on the inlet side of
the tail gas turbine where the tail gas temperature is at its highest. Because of the high
NOx concentration in the tail gas entering the reactor, a very large proportion of the
incoming N2O is catalytically decomposed to nitrogen and oxygen in the first bed.
Ammonia is mixed with the tail gas between the beds, the ammonia distribution and
mixing equipment being incorporated into the reactor. In the second bed the NOX is
reduced to the level required for emission to atmosphere and some further
decomposition of N2O also takes place.
Figure 13 EnviNOx process variant 1: Combined N2O and NOX abatement for nitric acid plants
using N2O decomposition and NOX reduction with ammonia
EnviNOx process variant 1 is currently suitable for tail gas temperatures between
about 425C and 520C. High rates of N2O removal are possible with 98% typically
achieved in commercial installations and NOX emissions can be reduced to low levels
depending on the amount of ammonia supplied, with 5 40 ppmv being usual. As with
the Uhde DeNOx process ammonia consumption is similar to that of classical
SCR/DeNOx processes.
3. EnviNOx process variant 2: N2O & NOX reduction by hydrocarbons & NH3
There are, of course, a great many nitric acid plants with tail gas temperatures below
425C. The solution for a large number of these plants is the EnviNOx process variant
2, which relies on another significant phenomenon, which was intensively investigated
during development work. While N2O in nitric acid tail gas can be reduced by reaction
with a hydrocarbon over certain iron zeolite catalysts, the effectiveness of the reduction
is greatly enhanced if the NOx is removed almost entirely from the tail gas. Even a few
ppm of NOx is sufficient to cause strong inhibition of the reactions of hydrocarbons
with N2O. This property combined with the NOX reducing properties of the iron zeolite
catalysts with ammonia leads to the EnviNOx process variant 2, depicted in Figure 14.
Figure 14 EnviNOx process variant 2: Combined N2O and NOX abatement for nitricacid plants
using N2O reduction with hydrocarbons and NOX reduction with ammonia
Ammonia is mixed with the tail gas entering the EnviNOx reactor in such an
amount that NOx is completely reduced in the first DeNOx bed. The virtually NOx free
tail gas is then mixed with a hydrocarbon and passed over the second catalyst bed where
the N2O is reduced to a very low level by reaction with the hydrocarbon. Tail gas with
nearly no NOx and a very low concentration of N2O leaves the reactor. It is important to
recognize that the hydrocarbon acts as a chemical reagent and is not used as a fuel to
138
raise the temperature of the catalyst to a level at which high rates of N 2O decomposition
can occur. Because of their favourable costs and availability the hydrocarbons of choice
are natural gas or propane. Consumptions of both ammonia and hydrocarbon are quite
moderate. The EnviNOx process variant 2 works best at temperatures between about
340C and ~520C.
4. Uhde DeN2O process: N2O decomposition without NOX abatement
If there is no requirement to lower NOx emissions, the N2O decomposition catalyst

described above can be used on its own. The catalyst achieves high N2O abatement
performance up to temperatures of about 600C, substantially increasing the range of
nitric acid plants which can be equipped with N2O abatement. In such plants a NOx
abatement unit can also be installed if necessary, provided an appropriate tail gas
temperature level between about 200C and 500C is available.
Conclusion
The EnviNOx process for the combined abatement of NOx and N2O emissions
from nitric acid plants has proven itself in installations around the world which are now
operating at temperatures between 340C and 510C. Typically, N2O emissions are
reduced by ~98% 99% while NOX emission levels of 1 to ~25 ppmv are achieved,
depending on the process variant.
The EnviNOx process can be applied in nitric acid plants with tail gas temperatures
between about 340C and 600C covering an estimated 70% 80% of all nitric acid
production worldwide. For many of the nitric acid plants with tail gas temperatures
outside this range, relatively simple plant modifications are possible to enable a nitrous
oxide abatement system to be installed.
The EnviNOx process can thus make a useful contribution to lowering greenhouse gas
emissions.
EnviNOx is an operator friendly technology since the EnviNOx catalysts are easy
to handle, environmentally uncontroversial materials with a long operating lifetime.
Furthermore as an end-of-pipe process EnviNOx does not interact in any way with the
plant product or its precursors.
Conclusion
In conclusion, setting up 100000 tons per year of nitric acid production plant in
Saudi Arabia is very feasible and attractive in order to meet high demand of ammonia in
this region. Ras Alkhair industrial city is identified as the most ideal location for the
new petrochemical plant. All the desired criteria for the construction of the plant in Ras
Alkhair are met and the necessary facilities for plant expansion are also available.
In order to produce the required capacity 100000 tons per year of nitric acid while
the amount of ammonia required 2335.88 kg/hr while the amount of air needed
43537.52 kg/hr.
Designing and sizing for equipment used are prepared in Equipment Specification
Sheet which provide the design and size estimation for chosen equipment.
A highly integrated process control system is also included to the proposed plant.
Control systems are essential to ensure the plant operates in safe manner and achieves
the desired production. The control system proposed are all feedback and cascade
model, which can correct the error continuously to serve better control objectives. All
equipment has been covered and proper control strategy and design have been proposed.
In designing the proposed plant, various safety factors and procedures such as
Hazard and Operability Studies (HAZOP), plant start up and shut down procedures,
maintenance and inspection of each equipment as well as control system design were
taken into consideration. However, it is recommended that further studies in this area is
needed unceasingly to ensure operational safety of the plant. Safety aspects are also
been considered in recommending the plant layout.
In responding to the environmental obligation, the plant has been designed to achieve
the target of waste minimization while achieving cost minimization at the same time.
From our economic and cost estimation analysis, the expected payback period is
(3.43) years. The economic analysis of the process flowsheet indicated that the ROI is
about 20.5%. The project is worth investing.
140
Finally, it can be concluded that the construction of a 100,000 tons per year of nitric
acid production plant in Ras Alkhair is technically feasible and economically attractive.
Encouragement from the Saudi government investment with various incentives offered
serves as another factor that contribute to the feasibility of the plant.
References
1- Krick Othmer, "Encyclopedia of Chemical Technology", VoL.15, 3th Edition, Jonh Wiley,1982
2- George Charles Lowrison,"Fertilizer Technology",Eillis Horwood Limited,1989
3- R. Perry and C. Chilton,"Perry's Chemical Engineer's Hand Book", 7th Ed.,Mcgra W-Hill, 1997
4- Vincent Sauchelli, "Fertilizer Nitrogen its Chemistry and Technology", Rinhold Publishing
Corporation", 1964.
5- Howard F. Rase, "Chemical Reactor Design For Process Plants",Vol. one & two, John Wiley, 1977
6- Octave Leven Spiel," Chemical Reaction Engineering", 2nd Ed.,John Wiley, 1972
7- J. M. Coulson J. Richardson, "Chemical Engineering Design", Vol.6, 3rd Ed., Pergamon Press,1983
8- P.J.C. Kaasenbrood, "Chemical Reaction Engineering", Pergamon Press, 1968
9- Richard Turton, Richard C. Bailie, Wallace B. Whiting, Joseph A. Shaeiwitz, " Analysis, Synthesis,
and Design of Chemical Processes ",3rd Edition, Prentice-Hall, 2009
10- W. Dekker, E. Snoeck and H. Kramers, "Chemical Engineering Science", 1959
11- (2012, january 15). Retrieved december 1, 2013, from Saudi Presidency of Meteorology and
Enviroment: Http://www.pme.gov.sa
12- (2009, may 27). Retrieved December 1, 2013, from Vermont Safty Information Resources, Inc. :
Http://www.siri.org
13- Richard M. Felder, Ronald W. Rousseau, " Elementary Principles of Chemical Processes ", Third
edition,2005
14- Fritz Ullmann, Ullmanns Encyclopedia of Industrial Chemistry ,John Wiley and Sons, 1999
15- Neil S. Chlager, Jayne Weisblatt, and David E. Newton, Chemical Compounds, 2001
16- Max. S. Peters, Klans D. Timmerhans, "Plan Design and Econmics for chemical Engineering 3-rd
Ed, McGraw-Hill, 1990.
17- Christie J. Geankoplis, Transport Processes and Separation Process Principles , 5th Edition,
Prentice Hall, 2003
18- J. M. Smith, H. C. Van Ness, M. M. Abbott, "Introduction to Chemical Engineering
Thermodynamics", 7th Edition, McCraw-Hill,2005
19- W. S. Norman, "Absorption, Distillation and Cooling Tower", Longmans,1962
142
Appendix A (12)
(Material Safety Data)
144
146
148
150
Appendix B
(13)
(Physical Properties Data)
152
154
156
158
160
Appendix C
(Detailed Mass Balance Calculation)
162
Overall Material Balance

NH3 + 2O2 HNO3 + H2O
Conversion: 95%
HNO3:
=
7500
= 119.048 /
63
NH3:
= 137.405
1
(119.048) = 18.357 /
1
O2:
0 = 2 (119.048) => 238.096 =
Excess 20 %
= 285.715 /
= 285.715 238.096 = 47.619/
N2:
=
285.715 32 0.79
= 1228.38 /
28 0.21
H2O:
1
0.05 + 277.778 = + (119.048)
1
= 167.084 /
Reactor Material Balance

1) 4NH3 + 5O2 4NO + 6H2O
Conversion: 95%
1 = 0.95 137.405 = 130.535
2) 4NH3 + 3O2 2N2 + 6H2O
Conversion: 5%
2 = 0.05 137.405 = 6.87
NH3:
4
4
= 137.405 (130.535) (6.87) = 0
4
4
O2:
5
3
= 285.715 (130.535) (6.87) = 117.393 /
4
4
N2:
2
= 1228.38 + (6.87) = 1231.815 /
4
NO:
4
= 0 + (130.535) = 130.535 /
4
H2O:
6
6
= 0 + (130.535) + (6.87) = 206.107 /
4
4
164
Oxidation Material Balance

2NO + O2 2NO2
Conversion: 96%
= 0.96 130.535 = 125.313
NO:
2
= 130.535 (125.313) = 5.222 /
2
NO2:
= 0 + 125.313 = 125.313 /
O2:
1
= 117.393 (125.313) = 54.736 /
2
H2O:
= 206.107 /
N2:
= 1231.815 /
Absorber Material Balance

2NO2 + H2O + O2 2HNO3
Conversion = 95%
= 0.95 125.313 = 119.048 /
No2:
= 125.313 22 (119.048) = 6.265 /
HNO3:
= 0 + 119.0475 = 119.0475 /
H2O:
= 373.191 12 (119.0475) = 313.667 /
NO:
= 5.222 /
O2:
= 54.736 0.52 (119.0475) = 24.974 /
N2:
= 1231.815 /
166
Appendix D
(Detailed Energy Balance Calculation)
Energy Balance
Vaporizer Energy Balance
S4
S5
E-101
For S4: NH3 at -15 oC and S5: NH3 at 35 oC
Tref = -15 oC
=
= 0
= [
+ +
= (2 1 ) + (22 12 ) + (23 13 ) + (24 14 )

2
3
4
1
= 1000 137.405[1.78 + (
1133.642
17) + 0.07232]
1000
= = 2902575.37 /
15
= 0
15
168
Compressor Energy Balance
S3
S1
C-101
For S1: Air at 101 kPa and S3: Air at 1090 kPa
= 1 1 ln
2
1
2
1
36000
1090
= 101 (
) ln
1.178
101
= 1 () ln
= 8879734.37 kJ/h
= 8879734.37 kJ/h (This is the mechanical energy required by the compressor)
Superheater Energy Balance
S5
S6
E-102
For S5: NH3 at 35 oC and S6: NH3 at 177 oC
=
2
=
1
2
= (2 1 ) + (22 12 ) + (23 13 ) + (24 14 )

2
3
4
1
Tref = 35 C
=
= 137.405 1000 5.442 = 747758.01 /
= = 747758.01 /
170
Mixer Energy Balance
S3
S7
S6
M-101
For S3: NH3 at 177 oC, S6: Air at 262 oC and S7: NH3+Air at ?
= 0 ()
Energy required to heat ammonia = Energy lost by air
( ) = ( )
(3 ) = 2.38 /.
() = 1.05 /.
2335.88 2.38 ( 177) = 43537.52 1.05 (262 )
= 250
Reactor Energy Balance
S7
S8
R-201
For S7: NH3+Air at 250 oC and S8: Air+NO+H2O at 645 oC
= + (1) 1 + (2) 2
1) 4NH3+5O2 4NO+6H2O (1)

Conversion=95%
2) 4NH3+3O2 2N2+6H2O (2)
Conversion=5%
= () ()
1 = 904.74 /
Based on (NO):
1 = 904.74/4 = 226.185 /
2 = 1266.22 /
Based on (H2O):
2 = 1266.22/6 = 211 /
= () () +
2
=
1
= (2 1 ) + (22 12 ) + (23 13 ) + (24 14 )

2
3
4
1
172
Tref = 25oC
Component
H (Air)
H (NH3)
H (NO)
H (H2O)
Input S7
(kJ/mol)
6.654
8.84
-
= 21192906.91 + (). 1 + (2 ). 2
= 51820729.07 /
Output S8
(kJ/mol)
19
19.744
23
Heat Exchanger Energy Balance (1st Cooler)
S8
S9
E-201
For S8: Air+NO+H2O at 645 oC and S9: Air+NO+H2O at 70 oC

= () ()
Tref = 70
() =
Input:
645
= (2 1 ) +
70
(2 12 ) + (23 13 ) + (24 14 )
2
3
4
For air
645
= cp dt = 28.94 103 (645 70) + (

70
0.4147 105
)(6452 702 )
2
0.3191 108
1.965 1012
(6453 703 )
(6454 704 ) = 17.693
3
4
For No:
645
= = 18.400
70
For H2O:
645
= = 21.173
70
= [(1318 1000 17.963) + (130.535 1000 18.4) + (206.107 1000 21.17)]

= 30084503.19 /
174
Oxidation Energy Balance
S9
R-202
S 10
For S9: Air+NO+H2O at 70 oC and S10: Air+NO+H2O+NO2 at 140 oC

2NO+O2 2NO2
Conversion=96%
= () ()
= 113.14 /
Based on (NO2):
= 113.14/2 = 56.57 /
= () () +
2
=
1
2
= (2 1 ) + (22 12 ) + (23 13 ) + (24 14 )

2
3
4
1
Tref = 25oC
Component
Input S9
(kJ/mol)
Output S10
(kJ/mol)
H (H2O) (g)
1.521
3.919
H (Air)
1.312
3.37
H (NO)
1.345
3.47
H (NO2)
4.5
= 3707006.24 /
Heat Exchanger Energy Balance (2nd cooler)
S 10
S 11
E-202
For S10: Air+NO+H2O+NO2 at 140 oC and S11: Air+NO+H2O+NO2 at 60 oC
Tref =60oC
= () ()
2
=
1
2
= (2 1 ) + (22 12 ) + (23 13 ) + (24 14 )

2
3
4
1
() =
Input:
For H2O
140
= = 2.737 kJ/mol
60
For air
140
= = 2.350 kJ/mol
60
176
For NO
140
= 2.4230/
60
For NO2
140
= = 3.1796 kJ/mol
60
= 3911927.94 /
Absorber Energy Balance
S 12
S 14
T-201
S 11
S 13
Basis: Tref = 25oC

For S11: Air+NO+H2O+NO2 at 60 oC, S14: H2O at 20 oC, S12: Air+NO+H2O at 30 oC and S13:
HNO3+H2O at 30 oC
1
3NO2+H2O + 2 O2 2HNO3
Conversion =95%
= () ()
= 435.6 /
Based on (HNO3):
= 435.6/2 = 217.8 /
= () () +
2
=
1
= + 2 + 3 + 4
2
3
4
178
Tref = 25oC
Component
Input S11
Input S14
Output S12
Output S13
(kJ/mol)
(kJ/mol)
(kJ/mol)
(kJ/mol)
H (H2O) (g)
1.18
0.166
H (H2O) (L)
-0.375
0.375
H (Air)
1.02
0.145
H (NO)
1.044
0.149
H (NO2)
1.32
H (HNO3)
0.55
= 29876241 /
Appendix E
(Equipment Design References)
180
Table A: Typical overall coefficients
Hot fluid
Heat exchanger
Water
Organic solvents
Light oils
Heavy oils
Gases
Coolers
Organic solvents
Light oils
Heavy oils
Gases
Organic solvents
Water
Gases
Heaters
Steam
Steam
Steam
Steam
Steam
Dowtherm
Dowtherm
Flue gases
Flue
Condensers
Aqueous vapors
Organic vapors
Organic (some noncondensable)
Vacuum condensers
Vaporizers
Steam
Steam
Steam
Shell and tube exchangers

Cold fluid
U (W/m2.oC)
Water
Organic solvents
Light oils
Heavy oils
Gases
800-1500
100-300
100-400
50-300
10-50
Water
Water
Water
Water
Brine
Brine
Brine
250-750
350-900
60-300
20-300
150-500
600-1200
15-250
Water
Organic solvents
Light oils
Heavy oils
Gases
Heavy oils
Gases
Steam
Hydrocarbon vapor
1500-4000
500-1000
300-900
60-450
30-300
50-300
20-300
30-100
30-100
Water
Water
1000-1500
700-1000
Water
Water
500-700
200-500
Aqueous solutions
Light organics
Heavy organics
1000-1500
900-1200
600-900
Table B: Fouling factors (coefficients), Typical values
Fluid
River water
Sea water
Cooling water (towers)
Towns water (soft)
Towns water (hard)
Steam condensate
Steam (oil free)
Steam (oil traces)
Refrigerated brine
Air and industrial gases
Flue gases
Organic vapors
Organic liquids
Light hydrocarbons
Heavy hydrocarbons
Boiling organics
Condensing organics
Heat transfer fluids
Aqueous salt solutions
Coefficient (W/m2.oC)
3000-12000
1000-3000
3000-6000
3000-5000
1000-2000
1500-5000
4000-10000
2000-5000
3000-5000
5000-10000
2000-5000
5000
5000
5000
2000
2500
5000
5000
3000-5000
Table C: Triangular pitch constants for use
No.
Passes
K1
n1
1
0.319
2.142
Triangular pitch pt = 1.25do

2
4
0.249
2.207
0.175
2.285
0.0743
2.499
0.0365
2.675
182
Figure A: Shell-bundle clearance
Figure B: Shell side heat transfer factors, segmental baffles
Figure C: Compressor operating ranges
Figure D: Approximate polytrophic efficiency of centrifugal and axial compressor
184
Appendix F
(Computer Simulation by CHEMCAD)
Note: No Absorber column in CHEMECAD. So, we choose Reactor & Distillation

186
CHEMCAD 5.1.3
Job Name: nitric acid
Stream No.
Name
- - Overall - Molar flow kmol/h
Mass flow kg/h
Temp C
Pres kPa
Vapor mole fraction
Enth kcal/h
Tc C
Pc kPa
Std. sp gr. wtr = 1
Std. sp gr. air = 1
Degree API
Average mol wt
Actual dens kg/m3
Actual vol m3/h
Std liq m3/h
Std vap 0 C m3/h
- - Vapor only - Molar flow kmol/h
Mass flow kg/h
Average mol wt
Actual dens kg/m3
Actual vol m3/h
Std liq m3/h
Std vap 0 C m3/h
Cp kcal/kmol-C
Z factor
Visc Pa-sec
Th cond kcal/h-m-C
Page 1
Date: 12/21/2013
Time: 17:03:43
1513.4900
43537.5214
25.0000
101.3000
1.000
-2407.9
-142.3629
3580.9491
0.860
0.993
33.0631
28.7663
1.1758
37026.8361
50.6795
33922.8318
1513.4900
43537.5214
426.6417
1240.0000
1.000
4.3619E+006
-142.3629
3580.9491
0.860
0.993
33.0631
28.7663
6.1004
7136.8696
50.6795
33922.8318
137.1546
2335.8798
177.0000
1240.0000
1.000
-1.3266E+006
132.5000
11278.4833
0.619
0.588
96.9616
17.0310
5.7967
402.9700
3.7749
3074.1346
1650.6446
45873.3981
397.9546
1060.0000
1.000
3.0352E+006
-122.8054
3657.0015
0.843
0.960
36.3168
27.7912
5.2582
8724.1045
54.4544
36996.9653
1513.4900
43537.5214
28.7663
1.1758
37026.8361
50.6795
33922.8318
7.0023
0.9999
1.826e-005
0.0219
1513.4900
43537.5214
28.7663
6.1004
7136.8696
50.6795
33922.8318
7.4548
1.0051
3.386e-005
0.0447
137.1546
2335.8798
17.0310
5.7967
402.9700
3.7749
3074.1346
9.9937
0.9735
1.580e-005
0.0398
1650.6446
45873.3981
27.7912
5.2582
8724.1045
54.4544
36996.9653
7.7200
1.0042
3.227e-005
0.0460
CHEMCAD 5.1.3
Stream No.
Name
Mass flow kg/h
Temp C
Pres kPa
Vapor mole fraction
Enth kcal/h
Tc C
Pc kPa
Std. sp gr. wtr = 1
Std. sp gr. air = 1
Degree API
Average mol wt
Actual dens kg/m3
Actual vol m3/h
Std liq m3/h
Std vap 0 C m3/h
Mass flow kg/h
Average mol wt
Actual dens kg/m3
Actual vol m3/h
Std liq m3/h
Std vap 0 C m3/h
Cp kcal/kmol-C
Z factor
Visc Pa-sec
Th cond kcal/h-m-C
- - Liquid only - Molar flow kmol/h
Mass flow kg/h
Average mol wt
Actual dens kg/m3
Actual vol m3/h
Std liq m3/h
Std vap 0 C m3/h
Cp kcal/kmol-C
Z factor
Visc Pa-sec
Th cond kcal/h-m-C
Surf tens N/m
Page 2
Date: 12/21/2013
Time: 17:03:43
1684.9333
45873.2316
957.1419
1060.0000
1.000
3.0352E+006
-93.0223
2905.8708
0.847
0.940
35.5966
27.2255
2.8143
16299.9875
54.2205
37765.5022
1684.9333
45873.2316
70.0000
1060.0000
0.9050
-1.0178E+007
-93.0223
2905.8708
0.847
0.940
35.5966
27.2255
11.1596
4110.6495
54.2205
37765.5022
1622.3906
45873.1642
104.1766
1060.0000
0.9819
-1.0178E+007
-73.2175
3100.2549
0.882
0.976
28.9246
28.2750
9.7690
4695.7688
52.0554
36363.6909
1622.3907
45873.1678
60.0000
1060.0000
0.8902
-1.2225E+007
-73.2175
3100.2545
0.882
0.976
28.9247
28.2750
12.1854
3764.5903
52.0554
36363.6944
1684.9333
45873.2316
27.2255
2.8143
16299.9875
54.2205
37765.5022
8.3271
1.0026
4.840e-005
0.0745
1524.9087
42990.3889
28.1921
10.4658
4107.7002
51.3372
34178.7630
7.1471
1.0009
1.986e-005
0.0250
1593.0640
45344.8463
28.4639
9.6577
4695.2154
51.5270
35706.3755
7.5261
0.9960
2.043e-005
0.0523
1444.2333
42654.5080
29.5344
11.3403
3761.3197
48.8410
32370.5377
7.3563
0.9968
1.911e-005
0.0406
160.0246
2882.8427
18.0150
977.4477
2.9494
2.8833
3586.7355
18.0725
0.0091
0.0004115
0.5648
0.0642
29.3266
528.3180
18.0150
954.7504
0.5534
0.5284
657.3158
18.2167
0.0086
0.0002687
0.5833
0.0578
178.1574
3218.6598
18.0664
984.0946
3.2707
3.2144
3993.1563
18.0877
0.0094
0.0004782
0.5542
0.0657
188
CHEMCAD 5.1.3
Page 3
Date: 12/21/2013
Stream No.
9
Name
1533.2676
Mass flow kg/h
45873.2493
Temp C
83.4790
Pres kPa
1060.0000
Vapor mole fraction
0.9504
Enth kcal/h
-1.2225E+007
Tc C
-61.2340
Pc kPa
6126.5270
Std. sp gr. wtr = 1
0.894
Std. sp gr. air = 1
1.033
Degree API
26.6962
Average mol wt
29.9186
Actual dens kg/m3
11.3094
Actual vol m3/h
4056.2009
Std liq m3/h
51.3324
Std vap 0 C m3/h
34366.1179
1457.2828
Mass flow kg/h
44273.8775
Average mol wt
30.3810
Actual dens kg/m3
10.9193
Actual vol m3/h
4054.6525
Std liq m3/h
49.8439
Std vap 0 C m3/h
32663.1003
Cp kcal/kmol-C
7.7917
Z factor
0.9948
Visc Pa-sec
1.851e-005
Th cond kcal/h-m-C
0.0249
75.9847
Mass flow kg/h
1599.3718
Average mol wt
21.0496
Actual dens kg/m3
1032.9471
Actual vol m3/h
1.5484
Std liq m3/h
1.4886
Std vap 0 C m3/h
1703.0165
Cp kcal/kmol-C
19.3733
Z factor
0.0099
Visc Pa-sec
0.0003485
Th cond kcal/h-m-C
0.5132
Surf tens N/m
0.0560
Time: 17:03:43
10
11
12
166.9448
3007.5101
25.0000
101.3000
0.0000
-1.1412E+007
374.2000
22118.2302
1.001
0.622
9.8949
18.0150
996.7087
3.0174
3.0080
3741.8412
1700.2124
48880.7581
81.9617
1060.0000
0.8481
-2.3638E+007
-30.2339
5555.8245
0.900
0.993
25.6625
28.7498
12.2125
4002.5238
54.3404
38107.9591
1274.8711
35693.1056
-168.2483
1060.0000
0.0000
-4.0263E+006
-142.3805
3356.5915
0.815
0.967
42.0561
27.9974
665.4294
53.6392
43.8188
28574.5104
1442.0068
43542.4315
30.1956
10.8929
3997.3251
49.3320
32320.7496
7.7344
0.9953
1.858e-005
0.0249
166.9448
3007.5101
18.0150
996.7087
3.0174
3.0080
3741.8412
18.0248
0.0010
0.0009227
0.5215
0.0721
258.2056
5338.3266
20.6751
1026.8606
5.1987
5.0084
5787.2082
19.2078
0.0098
0.0003542
0.5190
0.0569
1274.8711
35693.1056
27.9974
665.4294
53.6392
43.8188
28574.5104
18.6700
0.0511
0.0001005
0.0777
0.0033
CHEMCAD 5.1.3
Page 4
Date: 12/21/2013
Stream No.
13
Name
425.3410
Mass flow kg/h
13187.6533
Temp C
95.7593
Pres kPa
1060.0000
Vapor mole fraction
0.0000
Enth kcal/h
-2.4990E+007
Tc C
311.1441
Pc kPa
12082.3953
Std. sp gr. wtr = 1
1.255
Std. sp gr. air = 1
1.071
Degree API
-18.7077
Average mol wt
31.0049
Actual dens kg/m3
1164.9129
Actual vol m3/h
11.3207
Std liq m3/h
10.5216
Std vap 0 C m3/h
9533.4425
Mass flow kg/h
Average mol wt
Actual dens kg/m3
Actual vol m3/h
Std liq m3/h
Std vap 0 C m3/h
Cp kcal/kmol-C
Z factor
Visc Pa-sec
Th cond kcal/h-m-C
425.3410
Mass flow kg/h
13187.6533
Average mol wt
31.0049
Actual dens kg/m3
1164.9129
Actual vol m3/h
11.3207
Std liq m3/h
10.5216
Std vap 0 C m3/h
9533.4425
Cp kcal/kmol-C
23.8315
Z factor
0.0131
Visc Pa-sec
0.0003193
Th cond kcal/h-m-C
0.3885
Surf tens N/m
0.0415
Time: 17:03:43
14
15
137.1546
2335.8798
-15.0000
1240.0000
0.0000
-2.3156E+006
132.5000
11278.4833
0.619
0.588
96.9616
17.0310
656.6747
3.5571
3.7749
3074.1346
137.1546
2335.8798
35.0000
1240.0000
1.000
-1.5163E+006
132.5000
11278.4833
0.619
0.588
96.9616
17.0310
9.1153
256.2590
3.7749
3074.1346
137.1546
2335.8798
17.0310
9.1153
256.2590
3.7749
3074.1346
9.6843
0.9044
1.072e-005
0.0240
137.1546
2335.8798
17.0310
656.6747
3.5571
3.7749
3074.1346
19.5609
0.0190
0.0002027
0.4913
0.0299
190

Nitric Acid Project - Final

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Nitric Acid Project - Final

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Production of Nitric Acid for Fertilizer

Submitted in partial Fulfillment of the Requirement for the Degree of Bachelor

The initial design problem is to determine whether: it is both economically and

1.1 Backgrounds and History

1.2 The Nitric Acid Production Processes:

These two main Processes are:

1.2.1 The Single-Pressure Process

temperature results in an increased consumption of platinum and rhodium and the

1.2.2 The Dual-Pressure Process

1.2.3 Process Selection

1.2.4 Process Selection Conclusions

1.3. Main Uses of Nitric Acid

1.4. Physical Properties

1.5. Chemical Properties

1.6. Safety Properties

1.7. Market Survey

1.7.1 Economic Outlook

World Producers of Nitric Acid

Figure 1 World producers of nitric acid [2]

Table 1: Prices of raw materials and product

Price per ton

Total Profit = 40000000 - 9343540 - 963 = $30655497

1.8 Preliminary Hazard Analysis

1.8.1 Summary of Previous Plant Accident

Approximately 5,700 tons of anhydrous ammonia was released, and releases of

Figure 3 Post-explosion aerial photograph of the Port Neal plant [2]

1.8.2 Inherent Safety Aspects

The following hazards may arise during nitric acid production:

Equipment/piping failure because of corrosion

Explosion hazard due to the air ammonia mixture

Explosion of nitrite/nitrate salts

(i) Equipment/Piping Failure

Most of the large accidents in chemical or petrochemicals plants happen in the

1.8.3 Local Safety and Environmental Regulations

1.9 Site Feasibility

(r) Availability of government regional development grants or tax incentives,

1.9.2 Potential Site Location

Table 2: Information of site location

Type of Industrial Area

2.1 Process Description

2.1.1 The Flow Sheet of the Selected Process

2.1.2 Justification for the Equipment Selection

2.2 Overall Mass Balance

Table 3: Summery of overall mass balance

2.3 Reactor Mass Balance

Table 4: Summery of reactor mass balance

2.4 Oxidation Mass Balance

Table 5: Summery of oxidation mass balance

2.5 Absorber Mass Balance

Table 6: Summery of absorber mass balance

3.1 Vaporizer Energy Balance

For S4: NH3 at -15 oC and S5: NH3 at 35 oC

3.2 Compressor Energy Balance

3.3 Superheater Energy Balance

3.4 Mixer Energy Balance

3.5 Reactor Energy Balance

Table 7: Summary of enthalpy components in reactor

3.6 Heat Exchanger Energy Balance (1st Cooler)

For S8: Air+NO+H2O at 645 oC and S9: Air+NO+H2O at 70 oC

3.7 Oxidation Energy Balance

For S9: Air+NO+H2O at 70 oC and S10: Air+NO+H2O+NO2 at 140 oC

Table 8: Summary of enthalpy components in oxidation

3.8 Heat Exchanger Energy Balance (2nd cooler)