Final Year Project Report Cells

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Final year project report Cells
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CH4015: Comprehensive Design Project I
Group Report
Design of a Nitric Acid Production Plant
Group members:
140573U NACJD SENARATHNA

140588U SAB SILVA
140619T PDT THATHSARA
140622V TMIP THENNAKOON
140627P HGTA THUDUWAGE
Date of submission: 13/07/2018

Supervisors: Dr. Mahinsasa Narayana
Department of Chemical and Process Engineering

University of Moratuwa

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ABSTRACT
The report is a full analysis on the feasibility and process establishment for industrial nitric
acid (HNO3) production in Sri Lanka. HNO3 acid is a valuable chemical used in production
of fertilizers and explosives and hence local production and export trade could bring in large
amounts of foreign income. This report is presented in 3 main chapters.
The first part of the report is the literature review and process selection where the market
analysis including plant location and site selection has also been carried out. Production of
Ammonium Nitrate for fertilizer production was found to be the main end use of Nitric acid
accounting for more than 80% of total production. The market analysis suggested that the in-
dustry will continue to grow at a CAGR of 4.72% until early 2020s and the projected total
production will be 6900 Kilotons/year. The local Nitric acid requirement was very low and it
was around 1300 MT/year. Out of the various processes available, Ostwald process has been
selected in this study and Hambanthota is suggested as the most suitable plant location.
Process chemistry, HSE assessment and economic feasibility evaluation of production is pre-
sented as the second part. Since Nitric acid is a dangerous & corrosive acid, many precau-
tions were suggested in the HSE assessment with regard to handling, transportation and stor-
age. Hazards involved in dispersing and handling of waste gases and by products along with
occupational and general safety concerns are also discussed. The economic evaluation sug-
gested that the production rate needs to be 200,000 MT/year for a 8 year pay back period.
The third and final section presents the material and energy balance with utility requirements
of the process in detail.
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ACKNOWLEDGEMENT
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We would like to mention and acknowledge wholeheartedly, the following people who guided
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us throughout in preparation of this report for Comprehensive Design Project. Their contribu-
of
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tions and support directly and indirectly helped makes this design project, a success.
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First, our deep gratitude goes out to our supervisor; Dr. Mahinsasa Narayana for his immense
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support given to us. He was always there to guide us through his advice and direction, from the
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start of our first Interim report to this Final report. We highly appreciate his veteran guidance
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given to us in compiling this final report in a commendable manner.
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Next, we would like to thank our module coordinator Dr. Olga Gunapala and fellow lecturers
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of Department of Chemical and Process Engineering, for their guidance by providing us with
the necessary knowledge and tools in completing this design project by means of lectures and
so forth. We would also like to thank them for this opportunity given to us which enabled us to
utilize our chemical and process engineering knowledge in a practical application.
Finally, we would like to acknowledge and extend our thanks to all the academic staff of DCPE
and our colleagues, whose names we may have failed to mention here for any and all the sup-
port they gave us in making this report a reality.
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CONTENTS
LIST OF TABLES ............................................................................................................................................... V

LIST OF FIGURES ............................................................................................................................................. V
CHAPTER 1: INTRODUCTION........................................................................................................................ 6
CHAPTER 2: LITERATURE REVIEW AND PROCESS SELECTION ...................................................... 8
2.1 NITRIC ACID.................................................................................................................................................. 8
2.1.1 Identity .................................................................................................................................................. 8
2.1.2 Physical Properties ............................................................................................................................... 8
2.1.3 Environmental Parameters & Toxicology ............................................................................................ 9
2.1.4 Applications of Nitric Acid .................................................................................................................. 10
2.2 MARKET ANALYSIS ..................................................................................................................................... 11
2.2.1 Global Market analysis ....................................................................................................................... 11
2.2.2 Global Market analysis by application ............................................................................................... 12
2.2.3 Regional demand and supply .............................................................................................................. 13
2.2.4 Global Market share ........................................................................................................................... 14
2.2.5 Local Market analysis ......................................................................................................................... 14
2.3 PROCESSES AVAILABLE ............................................................................................................................... 15
2.3.1 Nitrate Process.................................................................................................................................... 15
2.3.2 Birkeland-Eyde Process ...................................................................................................................... 16
2.3.3 Ostwald Process.................................................................................................................................. 18
2.4 PROCESS SELECTION ................................................................................................................................... 19
2.5 OSTWALD PROCESS FOR MANUFACTURE OF NITRIC ACID ........................................................................... 21
2.5.1 Block diagram for Ostwald process .................................................................................................... 21
2.5.2 Main Unit Operations of Ostwald Process ......................................................................................... 22
CHAPTER 3: FEASIBILITY STUDY AND PROCESS CHEMISTRY ESTABLISHMENT .................. 25
3.1 PRODUCTION RATE DETERMINATION ........................................................................................................... 25
3.2 PLANT LOCATION AND SITE SELECTION ...................................................................................................... 26
3.3 PROCESS CHEMISTRY .................................................................................................................................. 27
3.4 HEALTH, SAFETY AND ENVIRONMENTAL (HSE) IMPACT ASSESSMENT ....................................................... 28
3.4.1 Raw Materials and Final product ....................................................................................................... 28
3.4.2 Waste and byproducts ......................................................................................................................... 29
3.4.3 Process operating conditions .............................................................................................................. 30
3.4.4 Occupational safety and general safety concerns ............................................................................... 31
3.5 ECONOMIC EVALUATION ............................................................................................................................ 31
3.5.1 Capital cost ......................................................................................................................................... 31
3.5.2 Operating costs ................................................................................................................................... 34
3.5.3 Annual revenue and Profit calculations .............................................................................................. 36
3.5.4 Payback period and Rate of Return of the project .............................................................................. 36
CHAPTER 4: MASS AND HEAT BALANCE FOR THE PROPOSED PLANT ........................................ 37
4.1 MATERIAL BALANCE ................................................................................................................................... 37
4.2 ENERGY BALANCE ...................................................................................................................................... 41
4.3 PROCESS FLOW DIAGRAM ........................................................................................................................... 48
4.4 ENERGY REQUIREMENTS OF THE PROCESS AND UTILITY SELECTION .......................................................... 49
4.5 SITE LAYOUT ............................................................................................................................................... 51
CHAPTER 5: CONCLUSIONS ........................................................................................................................ 52
REFERENCES ...................................................................................................................................................VI
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APPENDICES...................................................................................................................................................... X
APPENDIX 1 ..................................................................................................................................................... X
APPENDIX 2 ................................................................................................................................................ XVII
APPENDIX 3 ............................................................................................................................................... XXIII
LIST OF TABLES
Table 1- Identity of Nitric Acid [4] ............................................................................................. 8

Table 2– Physical Properties of Nitric Acid [4] .......................................................................... 8
Table 3– Environmental Parameters of Nitric Acid [4] .............................................................. 9
Table 4-Toxicology Data of Nitric Acid [4].............................................................................. 10
Table 5-Comparison between processes available for HNO3 production ............................... 19
Table 6-Yields of NO vs Temperature used in electric arc ..................................................... 20
Table 7-Operating parameters of production modes [11] ........................................................ 21
Table 8-Local Demand for nitric acid by volume and value ................................................... 25
Table 9-Kinetic and Process condition data applicable for the process ................................... 28
Table 10-Direct Capital costs of the project ............................................................................ 33
Table 11-Indirect Capital costs of the project .......................................................................... 33
Table 12-Operating costs of the project ................................................................................... 35
LIST OF FIGURES
Figure 1-Applications of Nitric Acid ....................................................................................... 11

Figure 2-Global Nitric Acid Market Size (USD Billions) ....................................................... 12
Figure 3-Global Nitric acid Market by application and growth rates ...................................... 13
Figure 4-Global nitric acid Market share by region................................................................. 14
Figure 5-Sri Lanka Nitric acid Import trend ............................................................................ 15
Figure 6-Nitrate process ........................................................................................................... 16
Figure 7-Birkeland-Eyde process ............................................................................................ 17
Figure 8-Block Diagram of the Ostwald Process .................................................................... 21

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CHAPTER 1: INTRODUCTION
Acid Production quantity was the main indicator to measure the development of a country in
the past. Which means acid production is extremely important. Nitric acid production plays a
huge role in the industry as one of the major acids taken as a raw material.
Around 60,000,000 tonnes of nitric acid are produced in the world. And The largest demand of
nitric acid is for the Ammonium nitrate production in the world market, it is roughly 76%. And
About 9% of nitric acid demand is for adipic acid, which is used for resins nylon 6,6 and pol-
ymers, polyester polyols for polyurethane resins, and other related fibres and resins. 6% of
nitric acid demand is acquired by the Toluene di-isocyanate (TDI) and nitrobenzene, and the
remaining 3% of nitric acid demand is for the metal nitrate and other miscellaneous applica-
tions [1]
In the Sri Lankan view, Sri Lanka is an agricultural country. This means our country needs
fertilizers. Currently, fertilizers are largely imported, if we can produce HNO3 inside the coun-
try, one of the main raw material for the fertilizer production can be supplied economically. In
Sir Lanka we have rock phosphate in Eppawela. Currently we can use those for the long-term
crops. But it cannot be used for the other crops due to lack of insolubility. By using HNO3 and
rock phosphate we can produce NPK-Fertilizers [2]. Therefore Construction of the HNO3 plant
in Sri Lanka will rapid lead to prosperity of Agriculture sector and GDP (gross domestic prod-
uct) value.
Design Constraints:
In the aspect of design constraints, the government regulations over the possible environmental,
health and safety impacts related with the activities of an acid production plant are important
to consider. The engineering design, facility development and implementation of the process
should be done according to the prevailing standards issued by the Central Environmental Au-
thority and Factory Ordinance Act of Sri Lanka.
The other main factor to be concerned here is the market constraints. Currently Demand for the
Nitric acid in Sri Lanka is low due to limited local applications. Hence, designing a plant of

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low production rate result in low profit of the plant due to economies of scale therefore we have
to export the surplus of the production.
Further the procurement of main raw material; ammonia should be imported. Therefore, higher
transportation costs, demurrages and relevant tax expenditures should be paid.
Objectives:
- To design a plant with a production rate of 200,000 MT of Nitric acid plant.

- To retain and earn foreign exchange to the country by substituting the current imports
and acquiring the Nitric acid export market while creating new direct and indirect job
opportunities.
In line with these objectives a literature review with process selection, a feasibility study with
process chemistry establishment and material and energy balance for the proposed plant will
be presented.

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CHAPTER 2: LITERATURE REVIEW AND PROCESS SELECTION
2.1 Nitric Acid
Nitric Acid is an inorganic acid. It is both extremely corrosive and toxic. Pure nitric acid is
colourless but has a yellowish appearance when it is old due to the collection of nitrogen ox-
ides. Nitric acid is a strong oxidizing agent. In solution, it is a good conductor of electricity
because it ionizes easily. It forms nitrate salts, reacts with metals, oxides and hydroxides. It is
used in a wide range of industries including fertilizer industry and polymer industry and has a
variety of domestic applications. The treatment of sodium nitrate with sulfuric acid is used to
produce Nitric acid in the laboratory. It is produced industrially by oxidation of ammonia
through the Ostwald process. [3]
2.1.1 Identity
IUPAC Name Nitric Acid
Chemical Formula HNO3
CAS No. 7697-37-2
Molecular Weight 63.12
Table 1- Identity of Nitric Acid [4]
2.1.2 Physical Properties
Appearance Pale yellow to reddish brown liquid
Melting point -42 0C
Boiling point 83 0C
Density 1.5129 g/cm3(at 20 0C)
Solubility in water Completely miscible
Vapor pressure 48 mmHg (at 20 0C)
Dissociation Constants (pKa) -1.38
Table 2– Physical Properties of Nitric Acid [4]

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2.1.3 Environmental Parameters & Toxicology
Acute Eco toxicity 24 – hour 40mmol/l (Human) (Inhibitor Con-

centration )
2– hour 300mg/m3 (cat) (low toxicity)
500 mg/ m3 (cat) (Lowest published lethal con-

centration)
Chronic Eco toxicity 48 hr, saltwater: 100-330 mg/L Agonus cata-

phractus (Hooknose or pogge)
48 hr ,renewal, /aerated water/ :100-300 mg/L

Asterias rubens (Starfish)
Mobility Nitric acid reduced the amount of carbon min-

eralized soil amended with 1% glucose than
did hydrogen sulfate.
Abiotic Degradation Nitric acid will be neutralized by hardness min-

erals (Ca and Mg) in water. The nitrate ion may
persist longer but will ultimately be consumed
as a plant nutrient
Biotic Degradation Aerobic / Anaerobic: Not applicable (inorganic

compound )
Potential for Bioaccumulation Not applicable (ionizable inorganic compound)
Table 3– Environmental Parameters of Nitric Acid [4]
Eye Redness. Pain. Burns.
Skin Serious skin burns. Pain. Yellow discoloura-

tion.

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Ingestion Sore throat. Abdominal pain. Burning sensa-

tion in the throat and chest. Shock or col-
lapse. Vomiting.
Inhalation Burning sensation. Cough. Laboured breath-

ing. Shortness of breath. Sore throat. Symp-
toms may be delayed
Carcinogenicity In IARC classified strong inorganic acid

mists as carcinogenic to humans. It should
be noted that this classification concerns
mists of strong inorganic acids that may in-
clude nitric acid but are not limited to nitric
acid.
Table 4-Toxicology Data of Nitric Acid [4]
2.1.4 Applications of Nitric Acid
Nitric Acid is available in different grades.
• White fuming nitric acid is that it include 2% water and 0.5% dissolved NO2. And
white fuming nitric acid also called 100% nitric acid or WFNA and it is very close to
the anhydrous nitric acid product.
• In red fuming nitric acid or RFNA include substantial amount of dissolved nitrogen
dioxide leaving the solution with a reddish-brown color. One formulation of red fum-
ing nitric specifies a minimum of 13% NO2, another specifies 17% NO2.
• In commercial grade nitric acid are included 52% and 68% nitric acid.
Industrial Uses of ammonia include: [4]
• Production of ammonium nitrate –Nitric acid is used in the production of ammonium

nitrate for fertilizers, making plastics, and in the manufacture of dyes. It is also used
for making explosives such as nitroglycerin and TNT. But nitric acid 80% used for
manufacture of fertilizers.
• Chemical industry – Nitric Acid is combined with hydrochloric acid, an element
called aqua regia is formed. This is a reagent that is capable of dissolving gold and
platinum.
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• In Medicine –Nitric acid is used in its pure state as a caustic to remove chancres and
warts. Diluted solutions are used in the treatment of dyspepsia.
• Water treatment –Nitric acid used for cleaning process of muddy water samples, solid
sludge samples, and other types of identical samples that require elemental analysis
through ICP-MS, ICP-OES, ICP-AES, GFAA and flame atomic absorption spectros-
copy.
• woodworking industry –Nitric acid is used to changed artificially age maple and pine
in woodworking industry. The color produced is a graygold, very much like very old
wax or oil-finished wood. In a low concentration nitric acid used for it.
In addition there are several other industrial applications of Nitric Acid, including polymer
industry, science laboratories etc.
Figure 1-Applications of Nitric Acid
2.2 Market Analysis
2.2.1 Global Market analysis

Global Nitric acid market was valued at US$14.114 billion in 2017 and will expand at a pro-
jected compound annual growth rate (CAGR) of 4.72% over the period from 2018-2023. The
current global production quantity of Nitric Acid is approximately 6130 kilotons and it is ex-
pected to grow to 6900 kilotons by 2021 with a CAGR of 3%. Although 90% of world’s Nitric
acid production is for onsite consumption and hence this value represents only 10% of the
global Nitric acid production. [5]
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Nitric acid is a useful industrial intermediary chemical used to manufacture various end prod-
ucts in the agriculture and military industries and many other organic and inorganic chemical
industries. Projected Growth in end user industries such as above and increasing production of
elastomers, lacquers, foam plastics, polyurethane foams and polyurethane foam coated fabrics
will supplement this forecast growth of Nitric acid market.
The fertilizer industry is a major driver for this projected CAGR for Nitric acid market. Am-
monium nitrate is heavily used in the agriculture industry with surging demand and the growing
need for high yields in production to cater to the requirements of the increasing world popula-
tion is further estimated to propel the market. [6]
Figure 2-Global Nitric Acid Market Size (USD Billions)

As Nitric acid is an intermediary good for many industries, the manufacturers can be found in
various stages of the value chain. The demand for the product is mainly dependant on the suc-
cess and market growths of previously mentioned end products.
With growth of industries, comes environmental pollution. Especially usage of nitrate fertiliz-
ers results in loss of Nitrogen in underground water due to nitrification and leaching and hence
various environmental restrictions are in place to control the concerns associated with usage of
Nitric acid and this is restraining the growth of the market. For instance, the regulatory frame-
works implemented by the European Union and EPA to limit nitrogen levels in groundwater
are expected to affect the growth of the nitric acid market in North America and Europe.
2.2.2 Global Market analysis by application

Agriculture industry is the leading consumer of Nitric acid related products. Fertilizer manu-
facturing dominated the global Nitric acid market accounting to 80% of total market in 2014.
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This is expected to continue to early 2020s as well. The agricultural and population growth in
India, Brazil and China is expected to boost the requirements of nitrate fertilizers and this will
result in increased Nitric acid market.
Then comes the production of Adipic acid which is heavily used to produce polymer compo-
sites such as Nylon 6,6 to be used in the automotive industry as a replacement for metal parts.
This also represents a small share of the nitric acid market followed by nitrobenzene and nitro-
chlorobenzene production [7]
Figure 3-Global Nitric acid Market by application and growth rates
2.2.3 Regional demand and supply

Europe and China are the largest consumers of Nitric acid in the world. They account for 60%
of total consumption due to the presence of large agricultural and industrial markets. Specially,
the growth of agriculture and industries in the Asia pacific region is expected to boost the
growth of global nitric acid consumption. It is predicted that the environment regulations in the
European region regarding nitrate consumption will create a shift in Nitric acid demand to the
AP region.
The United States dominates the Nitric acid market in the North American region accounting
for staggering 69% revenue from sales with their prominent chemical, electronics and automo-
tive industries.
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Figure 4-Global nitric acid Market share by region

When considering the Western Europe region, Germany leads the market share with the pres-
ence of industry leaders such as BASF, Bayer and Henkel who have established manufacturing
units catering to bulk chemical production and specialty polymers. Russia is also contributing
to the market share in Europe with their fertilizer manufacturing facilities. [8]
2.2.4 Global Market share

The Global Nitric acid market is dominated by a few industry players including DuPont, BASF,
The Dow chemical company, Agrium Inc; Omnia holdings, Apache Nitrogen Products etc. But
there are various other manufactures who contribute to the fragmentation of the market as well.
[6]
2.2.5 Local Market analysis

Local Nitric acid market is mainly dependant on imports from the AP region. The below figures
depict the major trade countries with a comparison of import values. South Korea has been the
major supplier of Nitric acid during the past few years and now Malaysia is slowly replacing
South Korea. Most of these acid imports are used for Laboratory usage in both industrial and
academic applications including a few applications in manufacturing industry [9]
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Figure 5-Sri Lanka Nitric acid Import trend
2.3 Processes available
Although different methods are used to produce Nitric acid (HNO3) at the lab scale, industrial
HNO3 manufacture is done by two chemical routes; reaction of a nitrate with concentrated sul-
phuric acid (H2SO4) and oxidation of NO to NO2 with subsequent reaction of latter in water.
Three distinct processes are available for this purpose [10] [11]:
1. Nitrate Process
2. Birkeland-Eyde Process
3. Ostwald Process
2.3.1 Nitrate Process
This was the first industrial process used to manufacture HNO3 in large scale. Its origins can
be traced back to work of Glauber in 1698. It was used for centuries, prior to the development
of other processes in the early 20th century [11]. Although this method is now almost obsolete
in large scale processes, it is still used in lab scale to produce HNO3.
It consists of distillation of a nitrate; Potassium Nitrate (KNO3) or Sodium Nitrate (NaNO3)

with concentrated H2SO4. Chile saltpeter was used as the source of nitrates extensively.
The process can be detailed as below [12]
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Chile saltpeter ore contains NaNO3, KNO3 & NaCl. It is concentrated by use of crystallization
as the first step in order to get 90-95% NaNO3 purity.
Next the refined Chile saltpeter is mixed with excess concentrated H2SO4 in a cast iron retort
and heated using coal/fuel fire to over 200 oC. This result in formation of HNO3 vapors along
with other compounds as below:
2NaNO3 + H2SO4 → Na2SO4 + 2HNO3
NaNO3 + H2SO4 → NaHSO4 + HNO3
2NaHSO4 → Na2S2O7 + H2O
The vapor is distilled off while the other salts remain in the retort. Silica pipes with water
circulation are used to cool down the hot vapors which will be collected in an acid resistant
collector vessel. The forerun will contain HCl and NOCl formed from other impurities in the
Chile saltpeter ore and is discarded. A packed bed tower is used to treat the uncondensed gases
that leave the collecting vessel from which further HNO3 in dilute format is collected.
Figure 6-Nitrate process

2.3.2 Birkeland-Eyde Process
Birkeland-Eyde process was developed by the Norwegian scientist; Kristian Birkeland in 1903,
along with his business partner, Samuel Eyde. It is also known as the Arc process and was
based on the work of British scientist; Henry Cavendish performed in the 18 th century. This
method involved fixation of atmospheric Nitrogen (N2) into HNO3 by use of an electric arc.
Due to its inefficient energy consumption, this method was phased out by Ostwald process in
the 1910s and 1920s.
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The Arc process required only dust free atmospheric air (N2 & O2) as raw materials and a large
source of electricity as utility requirements. The manufacturing plant usually requires a power
station close-by to be present in order to facilitate this.
Birkeland-Eyde process can divided into 3 main steps:
1. Fixation of atmospheric N2 to form NO

2. Oxidation of NO to NO2
3. Absorption of NO2 in water to form diluted acid
Detailed description of the process is as follows [13]
The process involved an Arc furnace setup where an electrical arc is formed between two co-
axial electrodes where temperatures exceeding 3000 oC are achieved. Inlet air is allowed to
pass through this electric arc. Here, some of the N2 to react with O2 to form Nitric Oxide (NO).
N2 + O2 → 2NO
Hot exit gases from the furnace are cooled down to 50 oC by passing through a series of alu-
minum tubes and a water-cooled boiler. This cool gas mixture combines with more atmospheric
O2 in an oxidizing tower to form Nitrogen Dioxide (NO2)
2NO + O2 → 2NO2
Produced NO2 gas mixture is passed through the bottom of an absorption tower containing
water. NO2 dissolves in the water to form dilute acid which is obtained from the bottom of the
tower. NO produced in this step is used as recycle to form more NO2.
3NO2 + H2O → 2HNO3 + NO
Fractional distillation of the bottom product is done to increase the purity and concentration of
the product.
Figure 7-Birkeland-Eyde process
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2.3.3 Ostwald Process

Ostwald process was patented and put into industrial scale use by the German chemist; W.
Ostwald in 1906. It was based on the work of French chemist; Kuhlmann back in 1838. It is
one of the key chemical processes in the modern chemical industry and is used to produce
almost all HNO3 worldwide.
The process requires Ammonia (NH3) as the principal raw material and thus closely linked to
the Haber-Bosch process from which it is cheaply sourced.
Ostwald process can be divided into 3 main steps:
1. Oxidation of atmospheric NH3 to form NO

2. Oxidation of NO to NO2
3. Absorption of NO2 in water to form diluted acid
HNO3 production in this method occurs as detailed below [14]
Liquefied NH3 is vaporized and preheated from its storage units at first. This is mixed with
preheated air, resulting in a gas mixture of 10.5-12% ammonia by volume at about 300 oC. This
stream is sent into a catalyst chamber where it passes through Platinum/Rhodium (10/90%)
gauze. In here, NH3 undergoes the below rapid exothermic reaction on the catalyst surface to
form NO.
4NH3 + 5O2 → 4NO + 6H2O
Hot exit gas from the catalytic converter, rich in NO is cooled down to 50 oC using a heat
exchanger and a cooler. Then it is compressed using an air compressor to increase the pressure
before feeding in to the adsorption tower.
Oxidation of this NO into NO2 and absorption of NO2 or its dimer N2O4 to form nitric acid is
performed in this absorption column. Both these reactions are favoured by high pressures and
low temperatures. Secondary air is used to ensure this further oxidation of NO into NO2. By
reaction of NO2 with water, NO is reformed which will be oxidized with more oxygen inside
the column to create more NO2.
2 NO+ O2→ 2NO2
3 NO2+ H2O→ 2 HNO3+ NO
To obtain higher concentrated acid, HNO3 vapour is passed over concentrated H2SO4 which is
a dehydrating agent.
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2.4 Process Selection
From the processes available for Nitric acid production explained in the previous section, we
can arrive at a comparison considering following key areas:
Ostwald Process Arc Process Nitrate Process
Capital cost Moderate High Moderate
Technical complexity Moderate High Moderate
Energy consumption Moderate Very High High
Product Yield High Very Low Low
Raw materials required Ammonia Atmospheric air Chile saltpeter

conc. H2SO4
Raw material availability Yes (Imported) Yes Yes (Imported)
Heat recovery opportuni- Available within the No No

ties process itself
Buyers & technical Widely available Very limited Very limited

know-how availability
Operational/Environ- Low High Moderate

mental hazards
Table 5-Comparison between processes available for HNO3 production

The manufacture of nitric acid using Nitrate process is no longer executed, as the high temper-
atures necessary for the reaction to occur causes high fuel consumption, plant equipment de-
preciation, and furthermore it can lead to the decomposition of nitric acid into nitrous acid and
other nitrogen products [10]
In addition, sourcing Chile saltpetre into Sri Lanka will bear extra cost because it is not a readily
imported item. Acquiring the manufacturing technology and equipment required will be an
issue as well since the process is obsolete at present. Therefore, Nitrate process is not a suitable
option for our plant.
The arc process is obsolete in terms of production of nitric acid commercially due to the high
energy requirements of the process. It has been recorded that about 14-17 MWh of electricity
is utilized for the process per ton of nitric acid produced [11]. This leads to higher production
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and running costs. Capital cost of such a plant is high as well since special equipment is re-
quired to handle such extreme temperatures and voltages.
Product yields in nitrogen fixation is limited to 1- 4 % as well, even under carefully adjusted
process conditions [11]. Since Arc process is obsolete at the industrial scale, it would be diffi-
cult to procure the technology required to manufacture HNO3 in this method as well. Therefore,
Arc process is not a suitable option for our plant.
Table 6-Yields of NO vs Temperature used in electric arc
When considering the Ostwald process, by adjusting process temperatures and pressures (600-
800 oC & 4-10 atm) in the NH3 oxidation step, yields of up to 98% can be achieved. This
coupled with the availability of cheap synthetic NH3 from Haber process, reaction temperatures
being low due to use of efficient catalysts make the HNO3 production very economical using
this method.
Technology and equipment are readily available with a variety of global suppliers with decades
of operational and design experience for Ostwald process HNO3 manufacturing plant commis-
sioning and maintenance. The process design has heat recovery opportunities incorporated and
doesn’t pose significant operational or environmental hazards as well. Therefore, Ostwald pro-
cess will be selected as the most suitable process option for our plant.
When considering HNO3 manufacture using Ostwald process, 3 types of production modes are
available; medium pressure (1.7-6.5 bar), high pressure (6.5-13 bar) and dual pressure pro-
cesses. Process descriptions are similar in all these modes, only difference being the difference
in working pressure of the process [11]
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Table 7-Operating parameters of production modes [11]

All the gaseous phase reactions encountered in Ostwald process are reversible and the ammo-
nia oxidation step favors lower pressures while the next two steps favor higher pressure.
Thus, use of dual pressure levels by use of a compressor in the NO outlet from catalytic reac-
tor allows further improvements in HNO3 yield. Utility requirements, catalyst losses, pollu-
tion levels caused by a dual pressure Ostwald process plant is significantly lower. Thus, we
would select Dual Pressure mode for our Ostwald Process HNO3 manufacturing plant
2.5 Ostwald Process for manufacture of Nitric Acid
2.5.1 Block diagram for Ostwald process
Figure 8-Block Diagram of the Ostwald Process

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2.5.2 Main Unit Operations of Ostwald Process

The main unit operations involved in nitric acid production using Ostwald method in sequential
order are as follows;
Air/ammonia filtration
Both air and ammonia feeds are filtered before the production process because presence of
impurities not only could reduce the yield but also damage the equipment’s. Since air is taken
from atmosphere it could contain impurities such as solid particles (dust, pollen, mould) and
water vapour. So, it is filtered at the very beginning before the air compression unit. For am-
monia, it is first evaporated and then filtered before mixing with compressed air.
Air compression
Air compressor is used to compress the feed air. Feed air is mixed with ammonia in the volu-
metric ratio of 9:1 [15]. Thus, air is compressed prior to the mixer.
Air and ammonia mixing
Air and ammonia feeds are mixed in the mixer-1 in the volumetric ratio of 9:1 before entering
to the catalytic reactor. In the mixer-2 ammonia is mixed with tail gas from adsorption tower
before entering to the selective catalytic reduction unit. Tail gas is mixed with ammonia so that
NOX present in the tail gas could be converted in to N2 and H2O.
Ammonia oxidation in the catalytic reactor
Oxidation of ammonia in the above inlet gas mix is carried out in a catalytic reactor. The tem-
perature of chamber is about 600 oC. This chamber contains a Platinum/Rhodium gauze which
serves as catalyst.
Oxidization of ammonia is reversible and exothermic process. Therefore, according to Le-

Chatelier’s principle, a decrease in temperature and pressure favours reaction in forward direc-
tion. Thus, a low pressure is maintained inside the chamber. In primary oxidization 95-96 per
cent of ammonia is converted into nitric oxide (NO) [16].
4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)
Simultaneously nitrous oxide, nitrogen and water are formed as well, in accordance with the
following equations: -
4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(g)
4NH3(g) + 4O2(g) → 2N2O(g) + 6H2O(g)
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The catalyst typically consists of several woven or knitted gauzes formed from wire containing
about 90% platinum alloyed with rhodium for greater strength and sometimes containing pal-
ladium [17]Selectivity to the ammonia oxidation to NO by catalyst action is however strong
and will take place with excellent yield.
Energy recovery by steam generation and gas reheating
Ammonia oxidation is a highly exothermic reaction thus it releases excessive amount of heat.
Water is used to cool down the reactor thus producing steam in the process. Steam produced
then is used to generate power using a steam turbine. This recovered energy is then used to
power up the compressors making process more energy efficient.
In parallel to that tail gas from the adsorption tower is reheated using heat exchangers. Heat is
extracted from the high temperature output gas stream from catalytic reactor.
Cooling and condensation of reactor outlet gases
Reactor outlet gases cooled up to 150 0C by the heat exchanger is further cooled to 50 0C in a
cooler condenser. Here partial oxidation of NO and formation of weak HNO3 acid occurs. Both
these liquid and gas product streams are directed to the absorber.
Gas compression, energy recovery and cooling
In air compressor, feed air is compressed prior to the mixing unit. Another air compressor is
used to compress the NO rich gas mix produced by cooler condenser. This is done to increase
the adsorption tower pressure. NO oxidation to NO2 happens inside the adsorption tower. Ac-
cording to Le Chatelier’s principle, an increase in pressure favours reaction in forward direc-
tion. Thus, a high pressure is maintained inside the adsorption tower.
Absorption with the production of nitric acid
Oxidation of residual NO into NO2 and absorption of NO2 are performed in an absorption col-
umn. These reactions are favoured by high pressures and low temperatures. Secondary air is
used to ensure a further conversion of NO into NO2. Secondary air is cooled before is being
send to the bleacher where dissolved gases in raw nitric acid are stripped off. Acid condensate
from cooler condenser and additional water is provided to the absorber to produce the nitric
acid. Complex reactions occur at the formation of nitric acid. On a whole, nitric acid is gener-
ated by absorption of nitrogen dioxide in water. By reaction of NO2 with water, nitrogen mon-
oxide is reformed, which prevents complete absorption of the inlet gases. The following overall
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reactions could be supposed for absorption and oxidation which take place at the absorption
column [16]
2 NO(g) + O2(g) → 2NO2(g)
3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g)
Absorption columns are equipped with sieve plates which are cooled with inside water-cooled
cooling coils to remove heat of reaction. Oxidation of NO into NO2 proceeds rather slowly
when the NOX concentration is low. Thus, spacing between the sieve plates increase with fall-
ing NOX concentration. Waste heat particularly arises from the formation of acid and must be
eliminated to get high absorption yields.
Selective catalytic reduction
Waste gases from adsorption tower contains considerable amount of NOX. So before releas-
ing it to the environment it is treated in a selective catalytic reduction unit. Before entering to
the SCR unit waste gas is mixed with NH3, which act as the reducing agent. Titanium oxide
or base metal oxides (such as vanadium, tungsten and molybdenum) are used as catalysts.
NOx reduces to N2 as follows;
4NO + 4NH3 + O2 → 4N2 + 6H2O
2NO2 + 4NH3 + O2 → 3N2 + 6H2O
2N2O → 2N2 + O2
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CHAPTER 3: FEASIBILITY STUDY AND PROCESS CHEMISTRY

ESTABLISHMENT
3.1 Production rate determination
There are several factors which affect the output obtainable from the plant.
Factors affecting maximum production rate
• Raw material supply- Ammonia is the principal raw material. To produce nitric acid,
ammonia must be imported.
• Storage facilities availability - If proposed plant has excess nitic acid production we
need large storage tanks and large production equipment.
• Capital availability
Factors affecting minimum production rate
• Equipment restrictions
• Economic benefit of process – Designing a plant of low production rate result in low
profit of the plant due to economies of scale
• Future Trends – trends of increasing demand and related industry development
The main target is to establish production flowrates to satisfy the Sri Lankan demand for ni-
tric acids. [18]which is as follows for the past years (2015-2017). [19] [20]
Year Annual FOB Average price Yearly Average Ex- Average HNO3 Quan-
USD (RMB/MT) change Rate (RMB TO price tity
USD) (USD) (Ton/yr.)
2015 81,707 1200 1/6.489 184.928 442
2016 218,159 1159.60 1/6.910 167.815 1300
2017 267422 1441.41 1/7.030 205.037 1304
Table 8-Local Demand for nitric acid by volume and value

From above it is evident that the current nitric acid demand is small compared to global num-
bers. As of now it’s being imported for a limited application like as a reagent in processes and
laboratory use only. However, the demand is increasing. Currently, Sri Lanka does not pro-
duce fertilizers locally. Annual nitrate fertilizer requirement for Sri Lankan arable land ex-
ceeds 40 million tonnes [21] [22]. There is huge potential of implementation of fertilizer
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production industry because of raw material availability (Rock phosphate is available in Ep-
pawela) if nitric acid is available freely in the country.
Although the local demand is less, a huge demand for quality nitric acid exceeding 250,000
MT/year in Asian markets like China, India, Bangladesh exists. Export of nitric acid is thus
possible to cater this demand as well.
Considering all the above factors and economies of scale, an annual production of 200,000
MT/year of nitric acid is proposed.
Daily nitric acid production rate = 200,000/365 =550 MT/day = 25,000 kg/h
3.2 Plant Location and site selection

The location of the plant can have a crucial effect on the proﬁtability of a project and the scope
for future expansion. Many factors must be considered as below: [21]
Raw materials
NH3 is the main raw material which is used to manufacturing nitric acid by using Ostwald
process. Currently Sri Lanka doesn’t produce any ammonia and total requirement is imported.
So, if we are planning to construct nitric acid plant, we have to select the most suitable geo-
graphical location with a harbour close by so that required raw material can be sourced easily.
Hambantota and Trincomalee would be good candidates because there is plenty of land closer
to the harbour unlike the case in Colombo. However, Trincomalee may not suitable for com-
mercial level activity in this scale.
Marketing Area and Transport
The plant should be located close to the primary market and other industries which use nitric
acid as raw material. There are main roads and proposed railway and highways available in
Hambantota which would connect the plant to many locations island wide and the capital.
Utilities
Water requirement for the cooling can be taken from the sea. Electricity can be supplied from
the national grid if required. But most of the utility requirement is catered from the process
itself by energy recovery methods.
Climate
There are no adverse climate conditions in Hambantota region such as high winds, earthquakes
etc.
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Political and Strategic Considerations
There are many relevant industrial standards under the National Environmental Act No. 47 of
1980 and raw material should be handled under the Chemical Weapons Convention Act No.
58 of 2007 [22]
Local Community Considerations
There is limited community density in the Hambantota region. This provides additional benefit
from safety aspects.
According to these factors Hambantota is the most suitable place for the construction of the
Nitric acid production plant.
3.3 Process Chemistry
The modern nitric acid process proceeds essentially in three stages [23]
1) Oxidation of Ammonia
2) Oxidation of NO
3) Absorption of NO2
Reactions and kinetics of above stages as follows; [24] [25] [26] [27]
Unit Operation Reaction Involved Kinetic Data Process Condition
(Rate Constant K and Re- (Temperature T

action Energy) and Pressure P)
E= +216.7 kcal/mol T=600C
Oxidation of Ammo- 4NH3(g) +5O2(g) → K=0.723 × 1076 P=4.6 bar

nia 4NO(g) +6H2O(g)
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E= -4.41KJ/mol T=50-25 oC
Oxidation of NO 2NO(g) +O2(g) → K=6.5×103 L2mol-2S-1 P=4.6 bar

2NO2(g)
Absorption of NO2 3 NO2(g) + H2O(l) → K=1.0 x 108 mol-1S-1 T=25 oC
2 HNO3(aq) + NO(g) P=12 bar
Table 9-Kinetic and Process condition data applicable for the process
3.4 Health, Safety and Environmental (HSE) impact assessment
Let us look at how few different components and aspects of nitric acid production impact
HSE.
3.4.1 Raw Materials and Final product

Ammonia is the main raw material in nitric acid manufacturing process and it is a cause for
many health hazards. Eye exposure can cause to severe eye irritation. Ammonia is irritating
to nose, throat, and lungs. Respiratory exposure symptoms may include coughing, burning
sensations, and shortness of breath, wheezing, headache and nausea. High exposure may also
cause nervous system effects such as unconsciousness. Skin contact with the vapor may cause
irritation and burns. Contact with ammonia liquid may cause freezing of the tissue, frostbite,
or severe injury [30] [31].
In order to mitigate the above risks and hazards below procedures are practiced in plants:
• Ammonia tanks are to be located outside of buildings, or in a building or section of a

building specially provided for that purpose.
• Storage areas are to be kept free of easily ignitable materials such as waste or weeds.
• Ammonia tanks and fittings are to be protected against tampering and physical damage.
• Personnel handling ammonia are recommended to wear rubber gloves, chemical-type

safety goggle, and impervious clothing.
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Nitric acid is a dangerous substance which is highly corrosive. Due to its high oxidizing capa-
bility, it causes fire when in contact with other materials. Primary routes of health hazards for
Nitric acid are skin contact, eye contact, inhalation and ingestion. Eye contact can cause per-
manent vision damage and skin contact will lead to deep penetrating ulcers. Ingestion causes
severe damage to the digestive tract and kidneys which will lead to death. Effects of inhala-
tion maybe delayed but chemical pneumonitis, bronchitis and possible death is certainly in
range.
Immediate medical attention needs to be provided to anyone exposed to nitric acid and proper
PPE must be worn in order to prevent any possible accident. Also plant conditions must be
within the limits specified for exposure control and personal protection. Accidental release,
handling and storage and disposal methods are regulated and the policies and release limits
need to be followed as specified by the government.
3.4.2 Waste and byproducts

Waste gas [32] [33]
Waste gas in nitric acid process consist of NOx like NO, NO2 & N2O along with water vapor
and air. Environmental regulations exist to control the levels of NOx permissible in this waste
streams because of their environmental detrimental effects. During the plant start-up and
shut-down process periods will generally increase the NOx gas content of the waste gas at the
stack. Therefore during this time extra care is taken in monitoring tail gas conditions and sta-
bilise it. SCR reduces the NOx levels during normal operation.
Liquid wastes [33]
• Boiler blow-down- The boiler blow-down may be cooled and neutralized before re-
lease if it any adverse condition is detected.
• Lubricating oil- Lubricating oil from the turbo-set machine can be centrifuged to min-
imize waste and used oils can be reprocessed by specialist firms if required.
• Ammonia vaporizer blow-down- The ammonia vaporizer blow-down may have the
ammonia vaporized and recovered from it into the process for safety and economic
purposes.
Solid wastes [33]
• Ammonia oxidation catalyst and catalyst in SCR- These are fully reprocessed by the
gauze manufacturer with recovered special metals are used for new gauzes. Else they
are disposed of under strict procedural guidelines.
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• Filter cartridges- Periodical replacement of the filter cartridges with proper disposal of
them is carried out. Reuse is often carried out.
3.4.3 Process operating conditions
As it is common in almost every chemical and process plant, nitric acid production also carries
many hazardous operating conditions. While it is impossible to get rid of those conditions, we
could mitigate the risk and the likelihood of loss that might occur due to those conditions.
Commonly found hazardous operating conditions are discussed below [33]:
Extreme temperature
Since the reaction in the catalytic reactor is highly exothermic temperature in the cham-
ber rises to 900 0C. This causes rise to two problems, safety and environmental impact.
Later, the effect on the environment is minimized by recovering that heat and reusing
the recovered heat to both generate power using steam generators and to preheat process
streams where it is necessary. In the aspect of safety, to avoid the thermal runway which
could occur due to failure in the heat exchanger system a process control system is used
to shut down the reaction. Explosion dampers and pressure release valves are to be
installed and maintained properly in case of emergency. To prevent unwanted situation
from happening a proper low risk operating routine is to be practiced. To prevent health
issues of employees due to exposure to hot environment proper ventilation and air cool-
ing methods can be used. Furthermore, proper personal protective equipment should be
worn wherever it is necessary.
High pressure
Air compressor and a nitrous gas compressor are used to generate high pressure gas to
be used in reactor and adsorption tower. Using high pressure gas causes safety problems
as even a slight mishandle could cause damage to air compressor itself, connected
equipment’s and nearby employees. Thus, all pipes, hoses, and fittings must have a
rating of the maximum pressure of the compressor. Compressed air pipelines should be
identified as to maximum working pressure. Air supply shutoff valves and pressure
releasing valves should be installed where it is necessary. Compressed air must not be
used under any circumstances to clean dirt and dust from clothing or off a person’s skin.
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Loud noises
Noise emissions would typically occur from compressors, pumps, electric motors, air cool-
ers, and moving equipment’s. To reduce the degree of noise pollution noise prevention and
mitigation measures should be applied. For stationary sources such as equipment that emit
high levels of noise during operation, it is wise to implement noise control measures at the
source itself. When selecting equipment, the sound power levels emitted should be a con-
sideration. In equipment casing radiating noise, acoustic enclosures could be installed.
Sound insulation to constructed buildings could be applied if it is necessary or otherwise
could use ear plugs.
3.4.4 Occupational safety and general safety concerns
Safety and health concerns are inevitable in the operation of a chemical process plant. There-
fore, it is of paramount importance to facilitate a safe working environment for the benefit of
employees and the general public as well as to minimize losses. Thus, standard operating pro-
cedure must be in place for the safe operation of day to day plant activities [33]. And it is very
important to make employees identify the importance of safe work practices. Following of
standard work procedures during routine activities, job safety analysis during special tasks,
hazard identification studies, etc. should be monitored by the plant’s OH&S department. Per-
sonal protective equipment’s should be provided to the employees wherever it is necessary.
With the involvement of employees in all sectors and levels along with third party individuals
for enhanced perspective, HAZOP studies must be carried out within reasonable time periods
to analyze long term occupational health and safety hazards in a professional manner.
3.5 Economic Evaluation
3.5.1 Capital cost

It is the one-off cost that must be incurred before production activities could commence in a
plant. This is of two types:
1. Fixed capital - Total construction and commissioning cost of the plant

2. Working capital - Additional investment required to start up the plant and operate
it till the first stock of products is produced
Since the nature of the production process and its unit operations have already been decided,
Step counting method will be used to obtain an estimate of the Total Capital Cost (TCC).
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Below equation for chemical plants that deal with gas phase processes can be used to deter-
mine TCC required for the proposed nitric acid plant [34]:
C = 14,000NQ0.615
Where,
C = Total capital cost of the plant in US Dollars (for the year 1998)
N = Number of significant functional units in the plant
Q = Plant capacity in tons/year
Substituting the values,
• N = 8 (evaporator unit, gas compression units, catalytic reactor, heat exchanger net-
work, absorption column, SCR unit, bleacher, filtration and mixing units)
• Q = 200,000 tons/year
C (as estimated for the year 1998) = 14,000 × 8 × 2000000.615 ≈ $ 203.7 million
The Chemical Engineering Plant Cost Index (CEPCI) for year 1998 and 2017 are 389.5
[35]and 567.5 [36] respectively.
Therefore, TCC adjusted to 2017:

567.5
TCC in USD = $203.7 million × = $297 million
389.5
Exchange rate of Sri Lankan Rupees to US Dollars as of 2018.06.08 is LKR 158.82/ $1.00
Therefore, TCC in local currency would be;

Rs. 158.8
Total capital cost of proposed plant = $297 million × = Rs. 47,169 million
$1.00
Generally Fixed capital cost to Working capital cost ratio is about 85%:15% of TCC. There-
fore:
Fixed capital cost = Rs. 47169 million × 85% = Rs. 40,094 million
Working capital cost = Rs. 47169 million × 15% = Rs. 7,075 million
Capital required for the purchase of the equipment required for the plant can be estimated by
Lang’s equation:
Cf = Lf x Ce
Where,
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Cf = Fixed capital cost
Ce = Equipment cost
Lf = Lang factor (4.7 for fluid processing plants)
Therefore,
40094
Equipment cost = = Rs. 8531 million
4.7
Similarly, rest of the key capital costs can be estimated as below as per the guidelines set out
in “Coulson & Richardson’s Chemical Engineering Volume 6”:
Direct costs Basis Value (Rs. mn)
Equipment cost Lang’s equation 8531
Equipment erection 0.4 times equipment cost 3412
Piping 0.7 times equipment cost 5972
Instrumentation 0.2 times equipment cost 1706
Electrical 0.1 times equipment cost 853
Buildings, process 0.15 times equipment cost 1280
Utilities 0.5 times equipment cost 4266
Storages 0.15 times equipment cost 1280
Site development 0.05 times equipment cost 427
Ancillary buildings 0.15 times equipment cost 1280
Total direct capital costs 29,007
Table 10-Direct Capital costs of the project
Indirect costs Basis Value (Rs. mn)
Design and engineering 0.3 times direct cost 8702
Contractors fee 0.05 times direct cost 1450
Contingency 0.1 times direct cost 2901
Total indirect capital costs 13,053
Table 11-Indirect Capital costs of the project
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3.5.2 Operating costs

This refers to the costs encountered during the operation of the manufacturing process. De-
tailed analysis of operating cost components will be performed as per the guidelines in “Coul-
son & Richardson’s Chemical Engineering Volume 6” to arrive at the economic viability of
the project.
Operating Costs = Direct Production Cost + Periodical cost
Direct production costs are cost components that directly relate to the production process. It
may be further elaborated as fixed costs and variable costs. Most of these cost components
are calculated in proportion to raw material, operating labor and fixed capital costs.
Periodical costs are costs incurred during a period that aren’t directly relatable to the produc-
tion process like R&D costs, general overheads, sales expenses etc.
Raw material Costs
Ammonia is the primary raw material required for the process. Considering a 282kg ammonia
usage per ton of nitric acid production [37], annual production of 200,000 tons of nitric acid
and average price of ammonia per ton as $210 [36]
282
Raw material cost/ year = x200000x210x158.8 = Rs. 1881 million
1000
Utility Costs
Plant will have electricity, steam, cooling water and fuel as utility requirements. Generally
8.5kWh of electricity is used for each ton of acid produced [37]. Let’s assume an equivalent
energy figure of 25kWh considering all the other utilities as well. Average industrial electric-
ity unit cost is Rs. 11.2 per kWh [38].
Utility cost per year = 25x200000x11.2 = Rs. 56 million
Operating Labour Costs
We will assume that the plant will be in continuous operation throughout the year working on
8-hour shift basis with a workforce of 60 persons for each shift. Additional two shift teams
are suitable to allow for better scheduling. Thus, we’d have a total of 300 employees. Consid-
ering an average monthly salary of Rs.40000;
Operating labour cost = Rs. 40,000 × 12 × 300 = Rs. 144 million
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Therefore, Total Operating cost of the plant can be calculated as below:
Operating Cost Basis Value (Rs. mn)
Variable costs
Raw material Typical dual pressure Ostwald process 1881

operational data
Utilities Typical dual pressure Ostwald process 56

operational data
Miscellaneous material 10% of maintenance cost 200
Fixed costs
Maintenance 5% of fixed capital cost 2005
Operating labour Manning estimates 144
Laboratory costs 20% of operating labour cost 29
Supervision 15% of operating labour cost 22
Plant overheads 50% of operating labour cost 72
Capital charges 8% of fixed capital cost 3208
Local taxes 1% of fixed capital cost 401
Insurance 1% of fixed capital cost 401
Royalties 1% of fixed capital cost 401
Total direct production costs 8819
Sales expense
General overheads
10% of direct operating cost 882
Research and develop-
ment
Total operating cost 9701
Table 12-Operating costs of the project
Therefore, the total operating cost of the plant is around Rs.9701 million per annum.
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3.5.3 Annual revenue and Profit calculations
Annual Production of Nitric acid=200,000MT/year
Assuming Average Nitric acid price in 2018 [39]as $400 per MT,
• Annual Revenue = 400 x 200,000 x 158.8 = Rs.12704 Million
• Operating profit= Revenue - Annual operating cost = 12704 - 9701 = Rs. 3003 million
Let us assume depreciation to be 8% per annum based on a plant life of 12.5 years which is
the typical age of a nitric acid plant. This has been calculated as capital charges in the operat-
ing cost calculations accordingly.
• Depreciation=Rs.3208 million
• Profit before tax=Rs.3003 million
Tax rate applicable to manufacturing industries that engages in export [40]is 10%
• Tax =10%*Profit before tax=0.1*3003= Rs.300.3 million
• Profit after tax= Profit before tax-Tax=3003-300.3= Rs. 2702.7 million
Therefore, Net profit per annum is Rs. 2702.7 million
3.5.4 Payback period and Rate of Return of the project
• Payback period = Total capital cost / (Net profit + Depreciation)
=47169 / (2702.7+3208)
=8 years
Average Investment = (Initial investment+ scrap value)/2
= (47169+0)/2 = Rs. 23584.5 million
• Accounting Rate of Return (ARR) = (Net profit/average investment)*100%
= (2702.7/23584.5)*100%
=11.45%
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CHAPTER 4: MASS AND HEAT BALANCE FOR THE PROPOSED PLANT
4.1 Material balance
Material balance for the process is carried out to size the equipment to handle required pro-
duction capacity and the raw material quantities required for the process. The stream data ob-
tained will be used to determine the energy requirements of the process later as well.
Production rate of HNO3 was set at 200,000 MT/yr. Since this was the only known flow rate,
a preliminary calculation was performed using an assumed basis; input ammonia flow rate of
100kmol/h. Here mass balances for key equipment in the process where changes in stream
compositions occur were done, to arrive at comprehensive actual material balance later using
a scale-up factor. [16] [41]
Basis of flow sheet calculations were as below:
1. 8000 operating hours per year
2. Oxidizer chemical yield of 96%
3. Weak acid concentration condensed in the cooler is 45% w/w
4. Acid concentration produced 68% w/w HNO3
5. Tail gas compositions NO - 0.15%, NO2 – 0.1% v/v
6. Air to ammonia ratio fed in to the mixer 1 is 9:1
7. Bleacher stripping functionality at 100%
8. No change in stream compositions when flow is through equipment such as heat ex-
changers, filters, mixers, splitters and compressors
Then the stream compositions about these key equipment were adjusted using the scale-up
factor of 4.4 to arrive at actual values.
Preliminary calculations and scale up factor determination used to determine the actual flow
rates are attached as Appendix 1
Material balance for actual production rate
Based on the above preliminary calculations and scale up factor, material balances for key
equipment are expressed as shown. Material flow in all the streams and other equipment like
filters, mixers, splitters, compressors and heat exchangers will be shown in the PFD attached
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next where simply the Inflow will be equal to the Outflow of material without any change.
[42] [43] [34]
Catalytic Reactor
Cooler-condenser
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Absorber
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SCR
Bleacher
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4.2 Energy Balance
Energy balance enables the identification of energy demands of the process and the energy
flow and conditions (temperature variation) of the process.
Based on the flow rates determined above and taking 1 hour of operation as basis, energy bal-
ance for key equipment was carried out using Aspen Plus software and manual calculations
when required to arrive at following results. (Appendix 2) [44] [34]
Air Compressor
Compressor
Net Work Required 8.273 MW
Compressor Outlet
Compressor Inlet Pressure(bar) 4.6
Pressure(bar) 1 Temperature (C) 247.5
Temperature (C) 30 Mass Enthalpy (kJ/kg) 227.5
Ammonia Vaporizer
Mass Enthalpy (kJ/kg) 4.84 Total Mass Enthalpy(GJ) 30.4
Total Mass Enthalpy(GJ) 0.6
Ammonia evaporator
Evaporator
Heat Required to vaporize 11258.4 MJ/h
Evaporator Outlet
Evaporator Inlet Pressure(bar) 4.6
Pressure(bar) 4.6 Temperature (C) 30
Temperature (C) 1.8 Mass Enthalpy (kJ/kg) 2700
Mass Enthalpy (kJ/kg) 4070 Total Mass Enthalpy(GJ) 21
Ammonia air mixer#
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Ammonia Mixer
Ammonia Inlet
Pressure(bar) 4.6
Temperature (C) 30
Mass Enthalpy (kJ/kg) 2700
Air Inlet Total Mass Enthalpy(GJ) 20.2
Pressure(bar) 4.6
Temperature (C) 247.5
Mass Enthalpy (kJ/kg) 227.5
Total Mass Enthalpy(GJ) 26
Mixer Outlet
Pressure(bar) 4.6
Catalytic Reactor
Catalytic Reactor
Heat Duty 45789.7 MJ/hr
Temperature (C) 600
Catalytic Reactor Inlet Catalytic Reactor Outlet

Pressure(bar) 4.6 Pressure(bar) 4.6
Temperature (C) 220.1 Temperature (C) 600
Mass Enthalpy (kJ/kg) 47.97 Mass Enthalpy (kJ/kg) 328.16
Total Mass Enthalpy(GJ) 5.8 Total Mass Enthalpy(GJ) 39.9
42

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Heat Exchanger
Gas Cooler
43

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Cooler Condenser
Cooler Condenser Liquid Outlet

Pressure(bar) 4.6
Temperature (C) 50
Cooler Condenser Inlet
Pressure(bar) 4.6
Temperature (C) 150
Total Mass Enthalpy(GJ) 104.3 Cooler Condenser Gas Outlet
Pressure(bar) 4.6
Temperature (C) 50
Cooler Condenser
Heat Duty 1971 MJ/hr
Gas Compressor
Gas Compresser
Net work required 3.887 MW
Gas Compresor Outlet

Pressure(bar) 12
Gas Compresor Inlet
Pressure(bar) 4.6
Temperature (C) 50
44

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Adsorption unit
45

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SCR
Ammonia-Tail gas mixer
46

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Air cooler
Bleacher
47

4.3 Process Flow Diagram
lOMoARcPSD|16598989
48
Stream Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 24 25 26 27
Ammonia Ammonia Filtered Ammonia to Ammonia to Reactor Filtered Compressed Air to Secondary Cooled Reactor Heat exchanger Condenser Condenser Gas Compressor Cooler Absorber Secondary air & Tail gas Tail gas to SCR Product
Stream Name Feed Vapour Ammonia Mixer 1 Mixer 2 Inlet Air Feed air Air Mixer 1 air to Cooler secondary air Outlet Outlet gas Liquid Out Out Water In Acid Out striped gases Out Mixer 2 SCR Inlet Outlet Acid
NH3(kg) 7769.5 7769.5 7769.5 7480 289.5 7480 - - - - - - - - - - - - - - - - - 289.5 74.8 -
O2(kg) - - - - - 26611.2 28040.3 28040.3 28040.3 26611.2 1429.1 1429.1 9222.4 9222.4 2464 - 2464 2464 - 0.18 4544.79 3773.4 3773.4 3773.4 3739.6 -
N2(kg) - - - - - 87595.2 105484.6 105484.6 105484.6 87595.2 17889.4 17889.4 87718.4 87718.4 87718.4 - 87718.4 87718.4 - 2.55 14961.86 102674.9 102674.9 102674.9 103095 -

NO(kg) - - - - - - - - - - - - 12672 12672 2072.4 - 2072.4 2072.4 - 0.01 0.01 171.6 171.6 171.6 8.6 -
NO2(kg) - - - - - - - - - - - - - - 9897.4 - 9897.4 9897.4 - 0.34 0.34 174.1 174.1 174.1 8.7 -
N2O(kg) - - - - - - - - - - - - 193.6 193.6 193.6 - 193.6 193.6 - 0.19 0.19 193.6 193.6 193.6 9.7 -
HNO3(kg) - - - - - - - - - - - - - - - 8704.1 - - - 26140 - - - - - 26140
H2O(kg) - - - - - - - - - - - - 11880 11880 910.8 9725.8 910.8 910.8 4387.7 12300 31.68 182.2 182.2 182.1 522.7 12268
Total(kg) 7769.5 7769.5 7769.5 7480 289.5 121686.4 133524.9 133524.9 133524.9 114206.4 19318.5 19318.5 121686.4 121686.4 103256.6 18429.9 103256.6 103256.6 4387.7 38443.27 19538.87 107169.8 107169.8 107459.2 107459.1 38408
Pressure(bar) 4.6 4.6 4.6 4.6 4.6 4.6 1 1 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 12 12 12 12 12 12 12 4.6 4.6 4.6
Temperature (C) 1.8 30 30 30 30 220.1 30 30 247.5 247.5 247.5 25 600 150 50 50 181.26 40 30 40 25 25 580 577 500 25
Mass Enthalpy (kJ/kg) 4070 2700 2700 2700 2700 47.97 4.84 4.84 227.5 227.5 227.5 1.02 328.16 857.06 38.7 1475.9 174.2 10.87 16000 - - 17.1 583.7 574.7 441.8 -
Total Mass Enthalpy(GJ) 31.6 21 21 20.2 0.8 5.8 0.6 0.6 30.4 26 4.4 negligible 39.9 104.3 4 27.2 18 1.1 70.2 - - 1.8 62.6 61.8 47.5 -
lOMoARcPSD|16598989
4.4 Energy Requirements of the Process and Utility Selection
Based on above energy balance calculations, energy requirements of key equipment are iden-
tified in the table and Utility selection for these are proposed as below.
Equipment Energy demand/released Utility

(MW)
Air Compressor 8.3 Electricity
Ammonia Evaporator 3.1 Low Pressure Steam
Catalytic Reactor 12.7 Steam Generation (High Pressure)
Cooler Condenser 20.4 Cooling Water
Gas Compressor 3.9 Electricity
Gas Cooler 4.7 Cooling Water
Absorber 7.2 Cooling Water
Bleacher 0.5 Cooling Water
SCR 4 Steam Generation (Low Pressure)
Air Cooler 1.2 Cooling Water
Utility calculations are available as Appendix 3
Net heat duty of the catalytic reactor is used to generate high pressure steam of 10 bar by ex-
changing heat. Then this high-pressure steam is sent through a steam turbine which generates
1.1MW of electricity.
Further, tail gas leaving the SCR unit at 500C will be expanded through a gas turbine to gen-
erate 6.4 MW of electricity.
The produced power can be utilized within the plant itself increasing its energy efficiency.
The plant has an electricity deficit of only 4.7MW which should be obtained from the na-
tional grid.
The SCR unit has a heat duty of 4MW. We can generate 3MW of low pressure steam at
0.2bar and it will be used for Ammonia evaporation. This is more than 96% of the heating
49

lOMoARcPSD|16598989
requirement for Ammonia and the balance heat requirement will be provided from the ex-
haust of the steam turbine.
Cooling water is required to cater the energy released from equipment like cooler condenser,
gas cooler, absorber, bleacher and air cooler. We will be using sea water at ambient tempera-
ture which can be sourced easily.
50

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4.5 Site layout
51

lOMoARcPSD|16598989
CHAPTER 5: CONCLUSIONS
With an annual global demand over US$14.114 billion and a compound annual growth rate
of 4.72% it is a timely opportunity to start a nitric production plant in Sri Lanka. Factors such
as Sri Lanka is an agricultural country which import all their fertilizers needs from abroad
though we have a highly pure dolomite deposit, strongly influences starting nitric plant here.
Sri Lanka currently spent over US$ 250,000 per year only on importing nitric acid itself. The
opportunity of reducing the annual fertilizer importing cost given with that, we could save
millions of rupees by starting a nitric acid production plant. Apart from that we can generate
over net profit of Rs. 2702.7 million per annum with a payback period of 8 years are also
strongly influences starting nitric acid production plant in Sri Lanka.
There are three main processes available for production of nitric acid in industrial scale
namely, Nitrate process, Birke lend-eyed process and Ostwald process. From those three Ost-
wald process was chosen because it is the most economically viable process among those.
Ostwald process is a three-step process involving ammonia and air as raw materials. Three
main steps involve oxidation of ammonia using atmospheric oxygen, further oxidation of ni-
tric oxide to nitrogen dioxide and absorption of produced nitrogen dioxide to form nitric acid.
There are few different Ostwald processes as well. From those dual pressure Ostwald process
was chosen as it produces concentrated nitric acid than other processes. Considering ease of
land acquisition, transportation of raw materials and products, availability of water and suita-
bility of climate Hambantota was chosen as plant location.
As mentioned above main raw materials for the process are ammonia and ambient air. Liquid
ammonia is imported from abroad while air is taken from atmosphere and filtered before us-
ing. With production rate of 200,000 MT nitric acid per year it was calculated that a
7769.5kg/h ammonia feed is required while air feed required for the optimum operation was
calculated as 133524.9 kg/h. Feed water required for the operation of absorption unit is
4387.7 kg/h and it is taken from the national water supply. Water required for cooling and
steam generation is decided to fulfil from sea water and it is estimated to be 2914 ton/h. Tail
gas produced from the process is treated in a SCR unit to reduce the NOx percentage before
releasing it to the atmosphere. Tail gas rate produced is 107459.1 kg/h with respective ammo-
nia, oxygen, nitrogen, nitric oxide, nitrogen dioxide, nitrous oxide and water vapor composi-
tions of 0.07, 3.48, 95.94, 0.01, 0.01 & 0.49.
Energy balance was performed to find the total energy required for the operation of the plant.
Total energy requirement is estimated to be 66 MW of which 12.2 MW is electrical energy
requirement and rest is thermal energy requirement. Using steam generation and suitable tur-
bines 7.5 MW of electricity is produced inside the plant itself thus recovering high amount of
thermal energy. So, the net energy requirement for the plant is 58.5 MW of which 4.7 MW is
electrical energy requirement and rest is thermal energy requirement. Required additional
electrical energy requirement of 4.7 MW is decided to take from the national grid.
52

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“Mechanism of Nitric Oxide Oxidation Reaction,” Journal of Chemical Theory and Compu-
tation, 2011.
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erProducts/Nitric%20Acid.pdf .
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tions.com/media/products_services/fertilizer_plants/nitrate_plants/brochure_ni-
tric_acid_scr.pdf .
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erseurope.com/fileadmin/user_upload/user_upload_prodstew/documents/Booklet_nr_2_Pro-
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Oxford, 1999.
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[42] M. Frank Douglas, “ Nitric acid : manufacture and uses / by F.D.Miles. Prep. under
the auspices of Imperial Chemical Industries, Ltd,” 1961. [Online]. Available:
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http://www.essentialchemicalindustry.org/chemicals/nitric-acid.html. [Accessed 11 07 2018].
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APPENDICES
APPENDIX 1
Preliminary calculations
For preliminary calculation, NH3 feed to reactor of 100kmol/h and 1h operation is considered.
Catalytic reactor
Air to ammonia ratio is 9:1. Thus, inlet ammonia concentration is 10%.
Therefore, air feed to the reactor = 100 x 90/10 = 900 kmol
Composition of air is taken as 79% & 21% v/v of N2 & O2 respectively.
Inlet O2 amount = 900 x 0.21 = 189 kmol
Inlet N2 amount = 900 x 0.79 = 711 kmol
Following reactions occur in the catalytic reactor,
Reaction 1: 4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)

Reaction 2: 4NH3 (g) + 3O2 (g) → 2N2 (g) + 6H2O (g)
Reaction 3: 4NH3 (g) + 4O2 (g) → 2N2O (g) + 6H2O (g)
Conditions inside the reactor and catalysts favor the reaction 1 resulting 96% yield of NO
NO produced = 100 x 0.96 = 96 kmol
Water produced = 96 x 6/4 = 144 kmol
Oxygen required = 96 x 5/4 = 120 kmol
Remaining ammonia will react to form N2 & N2O in similar quantities according to the reac-
tion 2 & 3.
N2 produced = N2O produced = 100 x 0.02 x 2/4 = 1 kmol
Water produced = 100 x 0.04 x 12/8 = 6 kmol
Total water produced = 144 + 6 = 150 kmol
Oxygen required = 100 x 0.04 x 7/8 = 3.5 kmol
Oxygen to the outlet = 189 – (120 + 3.5) = 65.5 kmol
N2 to the outlet = 711 + 1 = 712 kmol
Water to the outlet = 144 + 6 = 150 kmol

lOMoARcPSD|16598989
Cooler - condenser
Inlet stream will have same composition as the reactor outlet stream.
NO2 combines with this water to produce a 45% w/w solution
Reaction 5: 3NO2 + H2O → 2HNO3 +NO
Assume gas and condensed liquid are in equilibrium with each other at outlet temperature.
Cooler-condenser: Outlet temperature = 50 oC
Operating pressure = 4.6 bar (4.5atm).
At 50 0C vapor pressure of water over 45% HNO3 is 49.5 mmHg
Mol fraction of water in outlet gas stream = 49.5 / (760 x 4.5) = 0.0145
As first trial it is assumed that all water is condensed;
Then water condensed = 150 kmol = 2700kg
Taking subsidiary basis as 100kmol of HNO3 (100% basis) in condensate:
Amount of water to form 100 kmol HNO3 = 100 x 0.5 = 50 kmol = 900 kg
Mass of 100 kmol HNO3 = 100 x 63 = 6300 kg
Water required to dilute HNO3 to 45% = 6300 x 55/45 = 7700 kg
Total water required to form diluted acid = 900 + 7700 = 8600kg
So changing back to original basis:
HNO3 formed = 100 x (water condensed per 100kmol of feed)/ (total water to form
45% acid per 100kmol HNO3)
=100 x 2700/8600 = 31.4 kmol
NO2 consumed = 31.4 x 3/2 = 47.1kmol
H2O reacted = NO formed = 31.4 x ½ = 15.7 kmol
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Condensed water not reacted with NO2 = 150 -15.7 = 134.3 kmol
Taking NO in outlet gas is equal to NO formed from above reaction
Balance of oxides:
NO2 in outlet = NO in inlet – HNO3 formed – NO in outlet = 96 - 31.4 - 15.7 = 48.9

kmol
Balance on oxygen:
Oxygen into unit= [NO/2 +O2 + H2O/2]inlet = 96/2 + 65.5 + 150/2 = 188.5 kmol
Oxygen out of unit = [NO/2 +NO2+O2 + 3/2 x HNO3 +H2O/2]outlet
= 15.7/2 + 48.9 + O2 outlet + 1.5 x 31.4 + 134.3/2 = 171 + O2 outlet
So, O2 in outlet = 188.5 - 171 = 17.5 kmol
Total flow of gas = 712 + 15.7 + 48.9 + 17.5 = 794.1 kmol
Water vapor in gas stream = 794.1 x 0.0145 = 11.5 kmol
Water condensed = 134.3 – 11.5 = 122.8 kmol
For the proceeding calculations, it is assumed that outlet product stream from the bleacher unit
does not contain any dissolved gasses. So all the dissolved gasses in the liquid outlet stream
from the absorption unit are extracted in the bleacher and are fed back with the incoming sec-
ondary air back to the absorber.
Absorber
Absorption tower temperature = 25 oC
Gas and liquid inlets linked to the absorber from cooler-condenser will have the same compo-
sitions as the outlets from cooler-condenser. NO in the inlet stream to absorber = 15.7 kmol
O2 in the inlet stream from the condenser = 17.5 kmol
Reaction 6: 2NO + O2 → 2NO2
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O2 required to oxidize NO coming in = 15.7/2 = 7.85 kmol
Free O2 in the inlet stream = 17.5 – 7.85 = 9.65 kmol
Reaction 7: 4NO2 + 2H2O + O2 → 4HNO3
O2 required to oxidize NO formed = (48.9 + 15.7)/4 = 16.15 kmol
Additional O2 required = 16.15 – 9.65 = 6.5 kmol
Let y be the molar flow rate of secondary air (Impact of the NOx in secondary air is ne-
glected).
O2 in from secondary air = 0.21y
N2 in the tail gas = 0.79y + 712
O2 in the tail gas =0 .21y – 6.5
For satisfactory operation the tail gases from absorber should contain about 3% O2
Therefore y = 153.7 kmol
O2 in the tail gas = 25.8kmol
N2 in the tail gas = 833.4 kmol
Taking NO 0.15% v/v in the tail gas;
NO in the tail gas = (25.8+833.4)*0.002 = 1.3 kmol
This NO is not oxidised or absorbed.
Thus unreacted O2 = 25.8 + 1.3(1/4+1/2) = 26.8 kmol
Absorber pressure = 12 bar (11.84atm)
Assuming tail gas is saturated with water at the absorber temperature 25 oC
Partial pressure of water = 0.032 atm
Mole fraction of water = 0.032/11.84 = 0.0027
Therefore water vapour in tail gas = (25.8+833.4)*0.0027 = 2.3 kmol
HNO3 formed = 48.9 + 15.7 - 1.7 = 62.9 kmol = 3962.7 kg
Stoichiometric H2O required = 2*62.9/4 = 31.5kmol
Concentration of the acid leaving the tower = 0.68 w/w
Water required for dilution = (3962.7+1978.2)*0.32/.68 = 2795.7 kg = 155.3 kmol
Water as inlet (19) = Total water required + 1% extra
= (155.3 + 31.5 + 2.3 – 11.5 – 122.8)x1.01 = 55.4 kmol
xiii

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Total unreacted NO2 = 0.1% of the tail gas = (25.8+833.4)*0.001 = 0.86 kmol
(Impact of the unreacted NO2 on previous calculations are negligible)
Therefore, Liquid stream (21) composition;
HNO3 = 62.9 + 31.4 = 94.3 kmol
H2O = 155.3 kmol
By considering solubility of gases in the acid solution:

o
Element Partial pressure (atm) Solubility @ 25 C mol
(mol/kg*atm) [5]
NO 0.023 0.0019 0.12
NO2 0.018 0.034 1.71
O2 0.37 0.0013 1.34
N2 11.41 0.00065 20.7
N2O 0.014 0.025 1
Gas stream (22) will consist of the secondary air supply, the stripped gases from the acid so-
lution and water vapor;
Bleacher pressure = 12 bar (11.84atm) and the gas stream is saturated with water;
H2O vapor in the stream = (0.032/11.84)*153.7 = 0.4 kmol
Bleacher
Liquid inlet composition to the bleacher is same as the liquid outlet from absorber.
Gas inlet to the bleacher is the secondary air mix calculated as y in earlier section.
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Gas outlet composition from the bleacher is same as the gas inlet to the absorber (all the gase-
ous components which were in the acid liquid inlet will be bleached off)
Liquid outlet composition from the bleacher;
H2O = 155.3 – 0.4= 154.9 kmol
HNO3 = 94.3 kmol (68% concentration of acid is maintained)
SCR
From the SCR 95% NOx conversion is achieved
Reaction 8: 4NO + 4NH3 + O2 → 4N2 + 6H2O
Reaction 9: 2NO2 + 4NH3 + O2 → 3N2 + 6H2O
Reaction 10: 2N2O → 2N2 + O2
Hence;
Required NH3 for the reaction = 1.3 * 0.95 + 0.86* 0.95 * 2 = 2.87 kmol
Required O2 = 1.3*0.95/4 + 0.86*0.95/2 – 1*0.95*0.5= 0.24 kmol
N2 produced = 1.3*0.95*1+0.86*0.95*3/2+1*0.95 = 3.41 kmol
H2O produced = 1.3*0.95*6/4 + 0.86*0.95*3 = 4.3 kmol
Considering above and inlet air flow rates, Outlet gas stream compositions would be;
N2 = 833.4 + 3.41 = 836.81 kmol O2 = 26.8 – 0.24 = 26.56 kmol
NO2 = 0.86 * 0.05 = 0.043 kmol NO = 1.3*0.05 = 0.065 kmol
H2O = 2.3+4.3 = 6.6 kmol N2O = 1 * 0.05 = 0.05 kmol
NH3 concentration in the tail gas should be maintained below 5ppm;
Thus 1kmol/h NH3 in the gas leaving SCR is acceptable
Total NH3 required = 2.87 + 1 = 3.87 kmol
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Therefore, Input raw material flow rates to the total process:
Air (1) = 900 + 153.7 = 1053.7 kmol/h
Ammonia (23) = 100 + 3.87 = 103.87 kmol/h
Scale up for actual production rate
200,000 mt/year HNO3 is the actual production rate
In kg/h = 200,000 x 1000/8000 =25,000 kg/h
103.87 kmol of ammonia produces 5940.9kg of HNO3
100kmol of ammonia will produce 5719.55kg of HNO3
Thus, Scale up factor = 25000/5719.55 = 4.371
To allow for unaccounted physical losses let’s round up to 4.4
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APPENDIX 2
Compressor
Input Conditions of the air flow stream,
Inlet air flow rate = 4636 kmol/hr (79% - N2 , 21%- O2 v/v Compositions)
Inlet Temperature = 30 C Inlet pressure = 1 bar
Operating Parameters for the Compressor,
Discharge Pressure = 4.6 bar Isentropic Efficiency = 75%
By simulating the above by using ASPEN Plus,
Output Stream Temperature = 247.5 C
Output Stream Enthalpy = 227.5 kJ/kg
Inlet Stream Enthalpy = 4.84 kJ/kg
Net work required for Compressor = 8.273 MW
Ammonia vaporizer
The ammonia will be stored under pressure as a saturated liquid. The saturation temperature
at
4.6 bar is 1.837°C. Assume the feed to the vaporizer is at ambient temperature, 30°C.
Specific heat at 4.6 bar = 2.2 kJ/kgK
Latent heat at 4.6 bar = 1255.37 kJ/kg
Flow to vaporizer = 457 kmol/hr=7769.5kg/hr
Heat input to vaporize=7769.5 [2.2(30 - 1.837) + 1255.37] = 10235 MJ/h
Add 10% for heat losses = 1.1 x 10235 = 11258.4 MJ/h
Ammonia air mixer
Air 247.5 C
114206.4 Kg/hr T3
NH3 Vapour
7480kg/hr
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Cp air = 1 kJ/kgK,
Cp ammonia vapour 2.2 kJ/kgK.
Note: as the temperature of the air is only an estimate there is no point in using other
than average values for the specific heats at the inlet temperatures.
Energy balance around mixing tee, taking as the datum temperature the inlet tempera-
ture to the oxidizer as T3
114206.4*1*(247.5-T3)+7480*2.2*(30-T3)=0
T3=220.1 C
Oxidizer
By simulating the reactor inlet conditions in ASPEN Plus,
Heat duty= 45789.7 MJ/hr
Outlet stream temperature= 600 C
Pressure= 4.6 bar
Outlet stream Mass Enthalpy= 328.16 kJ/kg
Inlet stream mass enthalpy= 47.97 kJ/kg
Heat Exchanger
Reactor outlet gases will be cooled down to 150 C by heat exchanging with the tail
gas (no change in stream composition is assumed). By simulating this on ASPEN Plus Fol-
lowing results were generated.
Outlet Stream Enthalpy = 857.06 KJ/kg
Net Heat Duty = 64389.2 MJ/hr
Cooler Condenser
There are 5 sources of heat to be considered for the energy balance of this unit.
1) Gas sensible heat
Sensible heats of inlet and outlet gases were determined by using ASPEN Plus Prop-
erty data
Sensible Heat of Inlet Stream (14) = 17154.7 MJ/hr
Sensible heat of Outlet Stream (16) = 2684.6 MJ/hr
2) Condensation of cooling of water
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Amount of water condensed = inlet water – outlet water
= 11880 - 910.8
= 10969.2 kg
The steam is considered to condensed at inlet temperature and then cooled to the datum tem-
perature.
Latent heat of water at the inlet temperature and pressure = 2120 kJ/kg
Total heat for condensation and cooling = 2120*10969.2 + 10969.2* 4.18*(150-30)
= 28756.7 MJ/hr
3) Oxidation of Nitric Oxide
The greatest heat load will occur if all the oxidation is occurred in the cooler conden-
ser.
This is the worst condition for the condenser design.
NO + ½ O2 → NO2 (-57.12 kJ)
Moles NO Oxidised = 422.4 - 69.08
= 353.32 kmols/hr
Heat generation = 353.32 * 57120
= 20181.6 MJ/hr
4) Formation of Nitric acid
Amount of HNO3 Formed = 138.16 kmol
Formation of the nitric acid happens as below.
2NO2 → N2O4 ( -57.32 kJ)
N2O4 + H2O + ½ O2 → 2HNO3 (9 kJ)
HNO3(g) → HNO3(L) (-39.48kJ)
Combining the above reactions we can obtain,
2NO2 + H2O + 1/2O2 → 2HNO3
Heat generated per 1 kmol of nitric formed = (-57.32+9+ 2(-39.48))/2
= 63.64 kJ
Total heat generated = 63.64 * 1000 * 138.16
= 8792.5 MJ/hr
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5) Heat of dilution of nitric acid
Assume HNO3 is diluted to 45% by weight.
Specific heat of 45% nitric acid = 0.67
Heat of dilution from enthalpy concentration diagram = -80 Btu/lb = - 186

kJ/kg
Heat to raise the solution to datum temperature 30 C = 0.67*(30-0)*4.186
= 84.1 kJ/kg
Heat generated on dilution at 50 C = 186-84.1
= 101.9 kJ/kg
Quantity of solution produced by dilution of 1kmol of 100% HNO3 = (63/45)*100
= 140kg
Heat generated on dilution of 1 kmol = 140*101.9 = 14266 kJ
Total heat generated = 14266 * 138.16 = 1971 MJ/hr
6) Sensible Heat of Acid
Acid outlet temperature is taken as 50°C, which is above the datum temperature.
Sensible heat of acid = 0.67 x 4.186(50 - 30) x 18429.84= 1033.7 MJ/hr
Therefore Heat balance yields,
Cooling Required= 17154.7 - 2684.6 - 1033.7 + ( 28756.7 +20181.6 +8792.5 +1971)
= 73138.2 MJ/hr
Gas Compressor
Input Conditions of the gas stream,
Inlet gas = 3549.04 kmol/hr (Compositions as cooler condenser gas outlet)
Inlet Temperature = 50 C
Inlet pressure = 4.6 bar
Operating Parameters for the Compressor,
Discharge Pressure = 12 bar
Isentropic Efficiency = 75%
By simulating the above by using ASPEN Plus,
Output Stream Temperature = 181.26 C
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Output Stream Enthalpy = 174.2 kJ/kg
Inlet Stream Enthalpy = 38.7 kJ/kg
Net work required for Compressor = 3.887 MW
Gas Cooler
Compressor Gas gas will be cooled down to 40 C by heat exchanging (no change in
stream composition is assumed). By simulating this on ASPEN Plus Following results were
generated.
Outlet Stream Enthalpy = 10.87 KJ/kg
Net Heat Duty = 16872.7 MJ/hr
Absorber
As similarly calculated for the cooler condenser (taking Datum as 25 C),
Sensible heat from gases of cooler condenser = 1632.9 MJ/hr
Sensible heat from liquids of cooler condenser = 0.67 x 4.186(50 - 25) x 18429.84
= 1292.2 MJ/hr
Sensible heat from secondary Air and strip gases (at Datum temperature) = 0 MJ/hr
Sensible heat from tail gas (at Datum temperature) = 0 MJ/hr
Sensible Heat from water inlet = 4387.68 * 4.186 *(30-25) = 91.8 MJ/hr
Sensible Heat in Acid Outlet (taking temperature out as same as gas inlet 40 C)
= (4.83*12300+2.33*26140)(40-25)
= 1804.7 MJ/hr
Heat due to oxidation = (69.08 – 5.72)*57120 = 3619.1 MJ/hr
Heat due to acid formation = (414.92 -138.16)*63640 = 17613 MJ/hr
Heat due to acid dilution = 276.76*13130 =3633.9 MJ/hr
Hence,
Cooling required = 1632.9 + 0 + 1292.2 + 91.8 – 0 - 1804.7 + (3619.1 + 17613 + 3633.9)
= 26078.2 MJ/hr
Bleacher
Datum temperature = 25 C
Sensible heat from Stream 12,27 and 21 will be zero since they are at datum temperatures.
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Sensible heat stream 20 = 1804.7 MJ/hr (Calculated Earlier)
Therefore, Cooling required = 1804.7 MJ/hr
Air Cooler
Secondary air flow at 247.5 C to 25 C at 4.6 bar at a rate of 19503.92 kg/hr occurs
Using ASPEN Plus and simulating,
Heat duty = 4485.3 MJ/hr
Mass enthalpy of outlet stream = 1.02 kJ/kg
SCR
To find energy requirement of SCR temperature of stream 25 is calculated as below,
ASPEN Plus was used for below calculations,
Stream 22 exchanges heat with the reactor outlet gases to increase its temperature to 580 C
(mass enthalpy =583.7 kJ/kg) in stream 24
Then stream 24 will be mixed with ammonia to produce SCR Inlet (stream 25) which is at
577 C & 4.6 bar (mass enthalpy = 574.7 kJ/kg)
SCR will Operate at 500 C Simulating by using ASPEN Plus,
Net Heat Duty of SCR = 14280.6 MJ/hr
Mass enthalpy of stream 26 = 441.8 kJ/kg
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APPENDIX 3
Catalytic reactor
The catalytic reactor has a heat duty of 12.7MW. Hence, we can generate high pressure steam
from this heat duty and use it for power generation.
Assuming steam pressure to be maintained at 10 bar to be used in the turbine, we can calcu-
late how much steam can be generated from the heat released by the catalytic reactor.
High pressure steam generated=12.7*3600*1000/((2778-762.8)+(5.22*150)) = 16339kg/hr
Accounting for 20% of heat losses,
Realistic Steam generation=13071.2kg/hr
By simulating the process conditions in ASPEN, the possible power generation can be esti-
mated to 1 MW.
Isentropic efficiency of the turbine=0.75
Outlet Temperature =102.8 C
Vapor fraction= 0.9255
SCR
The SCR unit has a heat duty of 4MW. We can generate low pressure steam @0.2bar and it
will be used for Ammonia evaporation.
Quantity of steam generated=4*3600*1000/((2610-251.4)+(4.83*(60-30)))=5751.9kg/hr
Accounting for 20% heat losses,
Steam generation=4601.6 kg/hr
This steam can provide 3MW of heat to vaporize Ammonia and that’s more than 96% total
heating requirement of NH3.
The balance heat requirement will be provided from electricity.
Heat recovery from tail gas
Tail gas coming out of the SCR unit is at 500C. This gas will be expanded through a gas tur-
bine to generate more electricity.
By simulating the process conditions in ASPEN, the potential power generation is estimated
to be 6.4MW.
Isentropic efficiency of the gas turbine=0.75
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Outlet temperature=305C
Outlet pressure=1atm
Cooling requirements
Cooling water is required to cater the energy released from equipment like cooler condenser,
gas cooler, absorber, bleacher and air cooler. We will be using sea water @ambient tempera-
ture which can be sourced easily.
Cooling water requirements of the process = 34MW
Assuming cooling water streams variate from 30-40C,
Amount of cooling water required=2914 t/hr
xxiv

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chemical engineering principle (University of the Punjab)

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140573U NACJD SENARATHNA

140619T PDT THATHSARA

140622V TMIP THENNAKOON

140627P HGTA THUDUWAGE

Date of submission: 13/07/2018

Department of Chemical and Process Engineering

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LIST OF TABLES ............................................................................................................................................... V

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Table 1- Identity of Nitric Acid [4] ............................................................................................. 8

Figure 1-Applications of Nitric Acid ....................................................................................... 11

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- To design a plant with a production rate of 200,000 MT of Nitric acid plant.

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CHAPTER 2: LITERATURE REVIEW AND PROCESS SELECTION

2.1 Nitric Acid

IUPAC Name Nitric Acid

Chemical Formula HNO3

CAS No. 7697-37-2

Molecular Weight 63.12

Table 1- Identity of Nitric Acid [4]

2.1.2 Physical Properties

Appearance Pale yellow to reddish brown liquid

Melting point -42 0C

Density 1.5129 g/cm3(at 20 0C)

Solubility in water Completely miscible

Vapor pressure 48 mmHg (at 20 0C)

Dissociation Constants (pKa) -1.38

Table 2– Physical Properties of Nitric Acid [4]

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2.1.3 Environmental Parameters & Toxicology

Acute Eco toxicity 24 – hour 40mmol/l (Human) (Inhibitor Con-

2– hour 300mg/m3 (cat) (low toxicity)

500 mg/ m3 (cat) (Lowest published lethal con-

Chronic Eco toxicity 48 hr, saltwater: 100-330 mg/L Agonus cata-

48 hr ,renewal, /aerated water/ :100-300 mg/L

Mobility Nitric acid reduced the amount of carbon min-

Abiotic Degradation Nitric acid will be neutralized by hardness min-

Biotic Degradation Aerobic / Anaerobic: Not applicable (inorganic

Potential for Bioaccumulation Not applicable (ionizable inorganic compound)

Table 3– Environmental Parameters of Nitric Acid [4]

Eye Redness. Pain. Burns.

Skin Serious skin burns. Pain. Yellow discoloura-

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Ingestion Sore throat. Abdominal pain. Burning sensa-

Inhalation Burning sensation. Cough. Laboured breath-

Carcinogenicity In IARC classified strong inorganic acid

Table 4-Toxicology Data of Nitric Acid [4]

2.1.4 Applications of Nitric Acid

Nitric Acid is available in different grades.

Industrial Uses of ammonia include: [4]

• Production of ammonium nitrate –Nitric acid is used in the production of ammonium

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Figure 1-Applications of Nitric Acid

2.2 Market Analysis