CHAPTER 1

INTRODUCTION

1.1 Background of Process Design

A comprehensive feasibility study is to be conducted to evaluate the viability of constructing a
nitric acid production plant. The determination of the plant capacity and plant location for the
production of nitric acid is an essential part of the overall project. These decisions will significantly
impact of the effectiveness and efficiency of the production process. The findings of the market
study indicate that nitric acid exhibits significant potential, primarily driven by the growing
demand for various products including fertilizers, explosives, dyes, and pigments. Three different
production pathways were proposed following a thorough online research task. The selection of
the pathway shall be determined by taking into account various operational considerations such as
yield, conversion, selectivity, temperature, pressure, and so on. Additionally, cost considerations,
including gross profit analysis, shall also be take into consideration. A complete health and safety
analysis will be conduct on the chosen pathway.

1.2 Design Project Objectives and Scopes

The primary objective of this process design work is to develop a comprehensive plan for the
development of a nitric acid production facility that display competitiveness in the marketplace,
friendly to the environment, and sustainable development. The safety and durability of the
designed plant are key elements that have given a significant consideration. In order to accomplish
the stated objectives, a comprehensive list of scopes had been finalized. The following is a listing
of the project scopes:

• A literature review is to be carry out on the topic of nitric acid and its current production
methodologies.
• A comprehensive business and market study is to be taken for nitric acid. The objective of
this study is to present a comprehensive analysis of the current state of the nitric acid
industry.
• A complete analysis of the plant production capacity and plant location, along with a
justification for these decisions.
• A complete analysis of all potential production pathways and determine the optimal
pathway based on well-founded justifications.
• A comprehensive health and safety analysis for all chemicals present in the selected
pathway.
• A block flow diagram (BFD) requires to produce so that the process of making nitric acid
can be seen and analyse more easily.
• A manual calculation will be perform to cross check the material and energy balance with
the simulated design process with Aspen HYSYS software.
• A comprehensive process flow diagram (PFD) that encompasses all relevant equipment
and stream information.
 CHAPTER 2

LITERATURE REVIEW

2.1 The Nitric Acid

Inorganic acids, specifically nitric acid with chemical formula of HNO , are widely recognized as
inorganic bulk chemicals that possess a diverse array of applications (Ciesielczyk, 2020). The
concentration of nitric acid in this solution can vary between 30% and 70%. The chemical process
that is used for the production of nitric acid involves the oxidation of ammonia, resulting in a
release of nitric oxide. Nitric acid is produced when nitrogen oxide is reacted with water
(Cheremisinoff, 1995).

The production of nitric acid can be achieved through a different approach involving the
dehydration of concentrated sulphuric acid under near atmospheric pressure conditions, followed
by a subsequent bleaching system. In addition, the concentrated acid vapour is directed out of the
column and enters a countercurrent condenser system, where it undergoes condensation to
transform into liquid acid (Speight, 2017).

Figure 2.1: Chemical structure of Nitric Acid (Admin, 2023)

2.1.1 Chemical and Physical Properties

The compound known as nitric acid has a molecular weight of 63.01 g/mole. It is observed in the
form of white crystals, characterized by a melting point of -41.6 ˚C and a boiling point of 82.6 ˚C.
The density of nitric acid is measured to be 1.859 g/cm . The substance in question possesses an
apparent scent at a concentration level of 1 part per million (ppm) as reported by (Pub, 2023). In
this section, we present Table 2.1, which provides an in-depth overview of the physical properties
related to nitric acid. In addition, it is important to remember that nitric acid displays that vary
solubility features when disintegrated in different solvents, as demonstrated in Table 2.1.
 Table 2.1: Physical and Chemical Properties of Nitric Acid (Stern et al., 1960)

Property Value

Molecular weight (g/mole) 63.01

Melting point (℃) -41.6

Boiling point (℃) 82.6

Density at 21.1 ℃ (g/cm3) 1.5129

Viscosity at 20 ℃ (cP) 0.746

Heat of combustion at 25 ℃ (kJ/mol) -174.10

Heat of fusion at 25 ℃ (kJ/mol) 10.50

Heat of vaporization at 25 ℃ (kJ/mol) 39.1

Specific heat (J/mol.K) 59.38

Enthalpy of formation

Liquid (kcal/mol) 26.50

Gas (kcal/mol) 18.21

2.1.2 Application of Nitric Acid

The application of nitric acid is widely used in various industrial applications, including but not
just the production of ammonium nitrate for fertilisers, the synthesis of plastics, and the
manufacturing of dyes (the, 2022). The production of nitric acid is mainly affected by the fertiliser
industry. The consumption of nitric acid in the production of ammonium nitrate and calcium
ammonium nitrate is of crucial significance due to their broad uses as fertilisers (Bhanu Pratap &
Ishty, 2020).

A portion equivalent to 3% of the total nitric acid is employed as an intermediate compound

during the production process of toluene diisocyanate (TDI). Toluene diisocyanate (TDI) is a
chemical compound extensively employed in the production of polyurethane foams, which find
wide-ranging applications in various industries such as automotive, transportation, carpet and
furniture (Sharma et al., 2017).
 The utilisation of 4% of nitric acid is observe as an intermediate step in the production
processes of various chemicals, including nitrobenzene and nitrochlorobenzenes. The compound
nitrobenzene serves as a base in the process of synthesis of aniline, an essential reagent used for
the production of various dyes (Department of Chemistry, 2016).

The application of nitric acid occurs frequently in the polymer industry, specifically in the
production of intermediate chemicals. Notably, it contributes a significant role in the synthesis of
hexanedioic acid, also known as adipic acid, which serves as an essential ingredient in the
manufacturing process of polyamides. Adipic acid, a chemical compound which is frequently used
in various industrial applications, including the synthesis of nylon, polyurethanes, and other
commercially significant products. The process of industrial adipic acid synthesis involves the
usage of nitric acid for the oxidation of a combination of cyclohexanone and cyclohexanol,
commonly referred to as ketone and alcohol-oil (Isac-García et al., 2016).

Figure 2.2: Major Application of Nitric Acid (Department of Chemistry, 2016)

2.2 Development of Nitric Acid Processing Technologies

2.2.1 Chile Saltpetre Process

In the past centuries, the manufacturing of nitric acid in a commercial scale was started with
neutralizing the Chile Saltpetre with concentrated sulphuric acid to produce the dilute nitric acid.
Chile Saltpetre consist of about 35-60 % of NaNO3, some KNO3 and NaCl therefore it is necessary
to extract the NaNO3 from it before reacting with the strong acid (Gupta, 2020). The reaction
equation is shown below:

NaNO + H SO → NaHSO + HNO

Nitric acid vapors are obtained when the raw materials are reacted at 200 ℃. However, the
process was no longer practiced since the second decade of the nineteenth century due to the
intermittency of the process. The concentration of the yield nitric acid might differ along the
different stages of the operation (Norman and Harry, 1920).

2.2.2 Birkeland-Eyde Process

Birkeland-Eyde process was then developed by combining atmospheric oxygen and nitrogen
within a regenerative furnace operating at a temperature of approximately 2000℃. The formation
of nitric oxide occurs with a yield of approximately 2% (Daniels, 1951).

The present method involves the application of thermal energy to compressed air through
the utilization of an electric arc, resulting in an elevation of its temperature to a range of 3000 -
4000℃. The subsequent step involves the rapid cooling of the substance within a power conversion
unit, resulting in a temperature reduction to approximately 2000℃. This process is carried out
promptly to ensure efficient energy conversion. The electricity produced during this phase is then
efficiently redirect back to the arc heaters, thereby facilitating a sustainable and self-sustaining
energy cycle. The nitric oxide (NO) generated within the arc undergoes rapid cooling through the
application of a water spray, resulting in a reduction of its temperature to approximately 1400℃.
The process commences with the reaction of nitric oxide (NO) with additional oxygen (O ),
resulting in the formation of nitrogen dioxide (NO ). Subsequently, the generated nitrogen dioxide
undergoes conversion into nitric acid (HNO ) through absorption in water. However, due to the
high operating temperature, this process has higher energy consumption with poor yield of nitric
acid (Frank, 1969).
Equation that present in absorption tower
2NO + O → 2NO

1
2NO + O + H O → 2HNO
2

The process begins with the reaction of nitric oxide (NO) with additional oxygen (O ), resulting in
the formation of nitrogen dioxide (NO ) (Gupta, 2020).

Figure 2.3: Simple Flow Diagram of an Industrial High Temperature Arc Nitrogen Process
(Frank, 1969)
Equation of Oxidation of Nitrogen Monoxide
4NO + 2H O + O → 4HNO
The conversion of nitrogen monoxide (NO) to nitric acid (HNO ) was conducted through a series
of oxidation and hydration reactions, resulting in a product that is analogous to that obtained from
the oxidation of ammonia. The previously described process has now become useless.
Subsequently, the nitrogen dioxide undergoes conversion into nitric acid ( HNO ) through
absorption in water (Gupta, 2020).

2.2.3 Ostwald Process

The first operational establishment applying the Ostwald process was initiate in 1906 at Gerthe,
Germany (Thiemann et al., 2000). This section provides a description of the industrial production
of nitric acid through the Ostwald process. The process comprises three sequential chemical steps.
The first phase of the process entails the catalytic oxidation of ammonia (NH ) by reacting it with
atmospheric oxygen O ). This reaction leads to the formation of nitrogen monoxide (NO), which
occurs as a homogeneous gas-phase conversion. The subsequent stage involves the oxidation of
the nitrogen monoxide byproduct, resulting in the formation of nitrogen dioxide or dinitrogen
tetroxide. The final stage of the process involves the absorption of nitrogen oxides, resulting in the
production of nitric acid (Groves & Sasonow, 2010). Figure 2.4 clearly depicts the simple process
flow of the Ostwald process. The overall equation of the process is shown below:

NH + 2O → HNO +H O

Figure 2.4: Simple Flow Diagram of an Industrial Nitric Acid Production Plant (Thiemann
et al., 2000)
In the present study, it was observed that a conversion rate ranging from 93% to 98% of
the feed ammonia can be achieved when a suitable catalyst was utilized. The primary product of
this conversion process is nitrogen monoxide while the secondary product produced from the side
reaction is dinitrogen monoxide. Ammonia oxidation is limited by the reaction kinetics at low
temperatures (200℃ – 400℃), where nitrogen and dinitrogen monoxide are formed preferentially.
However, with the temperature ranging from 400℃ 600℃, the mass transfer limits the reaction
rate and dominates above 600℃ (Thiemann et al., 2000).
There are two technologies equipped with Ostwald process which are mono-pressure and
dual-pressure. Mono-pressure was first applied in the industry with the three reactions occur at the
same pressure level. It can be classified into mono medium pressure and mono high pressure where
the operating pressure is about 4-6 bar and 8-12 bar respectively. The selection of operating
pressure is based on the needs of the company as low pressure will have better efficiency on
ammonia oxidation while high pressure will enhance the absorption performance (ThyssenKrupp,
2004).
In order to cope with this issue, dual pressure plant was invented to have low pressure at
the process of ammonia oxidation and high-pressure during absorption. An additional NOx
compressor will be added before entering the absorption column (ThyssenKrupp, 2004). The dual
pressure process that aims to combine the best aspects of both mono processes will produce nitric
acid up to 1500 tons/day (Phoenix Equipment Corporation, 2019). However, it has its drawback
too which require higher operating cost to overcome the utility uptake used to maintain the pressure
difference.
Mono pressure plant often requires less initial capital than dual pressure plant due to the
absence of additional compressor. However, the variable cost might be higher in mono pressure
plant as more ammonia feed and catalyst are needed. Therefore, dual pressure nitric acid plant is
normally installed for larger capacity plant as it is more profitable than small scale plant (Phoenix
Equipment Corporation, 2019).
 CHAPTER 3

MARKETING AND BUSINESS STUDIES

3.1 Objective of Market and Business Study

It is important to carry out market and business studies before building a chemical production plant.
With the principle of supply and demand, it is vital to understand consumer and industry demands
to determine the capacity of a nitric acid chemical plant. Additionally, there are several factors that
affect the demand for nitric acid and directly impact the market. Hence, data collection and analysis
are important for market and business studies. It can be a study of the nitric acid market by segment
and region. As a result, it can help to determine the potential direction of the nitric acid plant in
terms of focusing on which region and which industry to target. Therefore, data collection and
analysis must be conducted for analytical purposes. Hence, a few objectives are set before starting
the market study:

1. To identify the current market demands.

2. To predict the future trend of market demands.

3. To identify the key factors affecting the HNO3 market.

4. To target customers based on the business and market study.

To study the market of HNO3 by segment and region.

3.2 Market by Segment

The market can be segmented by concentration, which is dilute nitric acid and concentrated nitric
acid. The process of diluting nitric acid requires mixing a solution of concentrated nitric acid with
water. It is used in heavy industrial processes, such as steel pickling, which aids in the oxidation
removal of stainless-steel sheets. The manufacturing of explosives, dyes, and pharmaceuticals also
requires diluted nitric acid. On the other hand, concentrated nitric acid has a greater amount of
nitrogen oxides compared to dilute nitric acid (Dataintelo, 2023). Based on Figure 3.1,
concentrated nitric acid is dominated the market share in 2022 and is anticipated to continue to
dominate during the forecast period due to its oxidizing and acidic characteristics (Research, 2023).
 Figure 3.1: Nitric Acid Market Share by Concentration (Research, 2023)

In the aspect of application, the market is divided into fertilizers, adipic acid, toluene
diisocyanate, nitrobenzene, and others. The fertilizers sector had the largest market share in 2023
and is projected to dominate the market in 2030 as shown in Figure 3.1. This is because the raw
material of fertilizers is nitric acid and the fertilizers such as ammonium nitrate and nitro
phosphates are produced on a large scale to cope with the increased demand for food and
agricultural activities. Therefore, the market would grow dramatically as a result of the increased
usage of fertilizers to boost agricultural productivity and satisfy the growing demand for high-
quality foods. As a result, the market has benefited from the increased demand for nitric acid from
the agriculture industry. Next, adipic acid holds the second-largest market share in 2023 and is
anticipated to continue growing over the forecasted period. This is due to adipic acid being
generate from nitric acid as one of the raw materials and is extensively used in the production of
nylon to manufacture automotive trunk lids and body panels (Research, 2023). Nylon is the
substitution of metal components during the production of automobiles due to its lightweight
nature which contributes to a reduction in vehicle weight and leads to less fuel consumption and
carbon emissions (Research, 2023). In addition, toluene di-isocyanate is a common ingredient in
the manufacturing of soft foam for mattresses and car seats while nitrobenzene is used to produce
lubricating oil for car engines (IndustryARC, 2023).

Figure 3.2: Global Nitric Acid Market by Application in USD Billion (Research, 2023)
 The segmentation of the nitric acid market can be based on its usage in various end-use
industries, which includes but is not limited to agrochemicals, explosives, automotive, electronics,
and other sectors. Based on the data presented in Figure 3.2, it is obvious that the agrochemicals
industry presently requires the highest market share compared to other industries. This advantage
is projected to persist all over the forecasted period. The main reason behind this sustained market
share is the increasing production of fertilizer derived from nitric acid. Next, the automotive
industry has the second largest market share and is expected to increase tremendously in the future
due to its rapid development and rising car demand. This increased car demand will increase the
production of cars and consequently drive the usage of nitric acid in the manufacturing of
automotive parts and lubricants in large quantities. Furthermore, the nitric acid market is also
driven by the explosives industry. This is because large quantities of nitric acid are required as a
precursor to produce explosives. Lastly, nitric acid also plays a crucial role in the electronics
industry for cleaning and etching processes (Research, 2023).

Figure 3.3: Global Nitric Acid Market by End-use Industry in USD Billion (Research,
2023)

The United States became known as a popular consumer and producer of nitric acid within
the North American region. The nitric acid market in Europe is defined by an important presence
of countries such as Germany, France, and the United Kingdom. The Asian region, especially
China and India, have experienced a significant rise in the demand for nitric acid due to the rapid
expansion of their industrial and agricultural sectors. Procurementresource (2018) claimed that in
the Asia Pacific region, there is an industrial base for the fabrication of agrochemicals, fertilizers,
explosives, polyurethane foams, and other products. Moreover, a derivative of nitric acid,
Ammonium Nitrate (NH4NO3), is used to fabricate Ammonium Nitrate Fuel Oil (ANFO). ANFO
is widely used in the mining industry for the production of bulk industrial explosives, particularly
in China.
3.3 Market by Region
Historically, the demand for nitric acid has been influenced by several factors, such as industrial
growth, agricultural practices, and the production of fertilizers and explosives. The existence of
known agricultural and industrial activities within particular areas has a positive relationship with
a higher need for nitric acid. Based on the findings reported by Admin (2020), it is obvious that
China holds the reputation of being the biggest global producer of agricultural goods. The position
can be assigned to the the nation's broad land area, which provides ample space for agricultural
activities. According to statistical data, China feeds 22% of the world's population, and 23% of
rice is produced in China. The second country is the United States (U.S.), with around 80% of
wheat production coming from the U.S. Every year after 1990, the agriculture field has expanded
by 5%, with a yearly increase of 0.84% in the production of farm workers. Besides, other countries
like India, Russia, France, and Mexico use nitric acid for agricultural activity. Figure 3.4 shows
the data analysis of agriculture in China and the United States.

Figure 3.4: Data Analysis of Agriculture in China and United states

To summarize, the industry in Europe is leading customer for purchasing fertilizer and
explosives. In particular, Eastern and Western Europe have the highest demand for nitric acid,
contributing to the most significant nitric acid imports worldwide. The Asia Pacific is the second-
largest region importing nitric acid due to the demand for vehicles, rapid urbanization, and growing
interest in lightweight air vehicles. North America ranks third, expanding its automobile
production, followed by Africa and the Middle East (Exportgenius., 2018). Because the different
countries will have their demands for nitric acid according to their primary focus on which field
or sector, it will give a different dominant market. In addition, it is worth noting that several other
nations, namely India, Russia, France, and Mexico, employ nitric acid in their agricultural practice.
In this report, Figure 3.4 presents a comprehensive data analysis comparing the agricultural sectors
of China and the United States.
 Figure 3.5: Nitric Acid Market Share by Region (Precedenceresearch, 2022)

Table 3.1: Import Value of Nitric Acid for Different Regions (Exportgenius.in., 2018)

Region Import Value Region Export Value

Europe USD 157 million Europe USD 156 million

Asia USD 97 million Asia USD 87 million

America USD 31 million America USD 30 million

Latin America and

USD 17 million Middle East USD 7 million
the Caribbean

Latin America and

Africa USD 11 million USD 2 million
the Caribbean

Middle East USD 6 million Africa USD 1 million

3.4 The Market Demand
In 2022, the market for nitric acid was estimated to be worth USD 28.56 billion, and by 2030, it is
anticipated to be worth USD 33.46 billion. Over the forecast period, the global market is expected
to expand at a compound annual growth rate (CAGR) of 2% (Vantage, 2022).

Figure 3.6: Market Size of Nitric Acid from 2022 to 2023 (Vantage, 2022)

The main factor that drives up the need for nitric acid on a global scale is the expanding
population and concerns about food security. Figure 3.6 has shown the continual growth of the
population over the world (Scientific American, 2022).

Figure 3.7: Global Population Growth (Scientific American, 2022)

Ammonium nitrate, an essential component of fertilisers is produced through nitric acid as

a feedstock. Nitric Acid is now in more demand as a result of this factor. The largest consumer of
nitric acid in the industry is the fertiliser sector. For example, nitrogen-based fertilisers like urea
and ammonium nitrate are made using nitric acid. Due to the rising worldwide population and the
need to enhance food production, there has been a surge in the need for fertilisers with nitrogen as
a primary component. This is because one of the nutrients necessary for plant growth and
development is nitrogen. By encouraging quick and strong vegetative development in plants, it
can raise crop output. Additionally, it can enhance crop quality by assisting in the growth of strong
and healthy plant tissues that are less vulnerable to illnesses, pests, and environmental challenges.
As a result of the continued growth of crop, there will be enough food. Nitric acid consumption
from the fertiliser industry has surged as a result. The use of nitric acid in the fertilizer industry is
expected to continue to grow in the future because it is driven by continued population growth and
the need to increase food production.

Besides that, about 30% of the world's demand for nitric acid is met by the electronics
sector. The increasing reliance on nitric acid in the electronics industry can be given to a number
of important aspects that are promoting its use and boosting the nitric acid market. The rising need
for lightweight and compact electronic devices is one of the main driving factors. In order to meet
the demands of portable electronics such as tablets, wearable gadgets and smartphones, there is an
increasing need for smaller and more efficient components. Because the components made of nitric
acid offer the required precision and dependability, it is essential for enabling the miniaturisation
of electronic equipment. In order to achieve the appropriate size and performance of components,
nitric acid is also needed in the fabrication process such as integrated circuits and microchips.

In the years to come, it is anticipated that the electrification trend already present in the
automotive industry would dramatically increase demand for nitric acid. The transition to electric
and hybrid vehicles from fuel vehicles involves the utilization of sophisticated electronic systems
and parts for power management, control and connectivity. The effective operation of these
vehicles depends on the use of sensors, power electronics and more that are based on nitric acid.
Nitric Acid demand in the automotive industry is therefore being driven by the growing use of
EVs around the world.

Additionally, a significant element fuelling the growth of the nitric acid market is the rapid
expansion in the industry of semiconductors. Semiconductors are essential parts of electronic
devices because they provide the basis for integrated circuits and other electronic systems. In many
steps of the manufacture of semiconductors, nitric acid is essential. It is used to clean and etch
silicon wafers, which are necessary for making microchips and other semiconductor devices.
Another component of the metallization procedure, which is essential for establishing electrical
connections inside semiconductor devices, is nitric acid. As a result of improvements in fields like
the Internet of Things (IoT), 5G technology and artificial intelligence (AI), the demand for
semiconductors is predicted to expand in parallel with the demand for nitric acid.
 Based on Figure 3.8, it can be noticed that Germany, Japan, Malaysia, Belgium and France
have a high percentage of imported nitric acid as compared to other countries. This is because
these countries are the leading industrialized nation, which has a strong industrial sector that
includes the mechanical, electronics, chemical, and automotive industries. Therefore, these
countries need a lot of nitric acid to carry out the manufacturing process. However, the supply of
nitric acid to the manufacturing process through its own production is inadequate. Thus, these
countries need to import nitric acid from other countries to fulfill the demand. In the future, the
industrialized nation will continue to grow due to the development of technology.

Figure 3.8: Importers of Nitric Acid in 2021 (OEC, 2021)

Due to the expansion of the agricultural sector and innovative technologies like fuel cells
and solar energy systems, Europe dominated the nitric acid market in 2021 with a 65.5% share.
With a share of 24.3%, the Asia-Pacific area is the second-largest market for nitric acid. The main
reason is the world's expanding population and rapid economic development, particularly in China
and India. The use of fertiliser and industries has grown significantly in these two nations in recent
years (Vantage, 2022).
3.5 The Production and Supply
Figure 3.9 shows that due to the enormous supply of raw materials, Korea is the primary producer
and the largest exporter of nitric acid. In 2021, the percentage will reach 27.6% of all exports with
a value of USD 115 million.

Figure 3.9: Exporters of Nitric Acid in 2021 (OEC, 2021)

With a focus on petrochemicals, industrial chemicals, and speciality chemicals, South

Korea has built up a strong and modern chemical sector. In many industrial operations, including
the creation of fertilisers, explosives, pharmaceuticals and dyes, nitric acid is an essential chemical
to use as a raw material. Due to the local production capabilities, the country is able to export a
sizable amount of nitric acid to satisfy international demand. Besides that, chemical producers in
South Korea have made an impression on themselves internationally and are known for their high-
quality nitric acid production. As a result of their investments in cutting-edge production
techniques and strict adherence to quality control guidelines, their products are competitive in the
international market. Due to its strong international competitiveness, South Korea is able to export
a significant amount of nitric acid to the world (TechSciResearch, 2022).

Besides South Korea, Belgium and Germany are the next two nations that export nitric acid
in significant quantities. These nations have solidified their positions as major exporters of nitric
acid, which has had a considerable positive impact on their economies. With a 17.9% export share,
Belgium got significant benefits from its exports of nitric acid. Nitric Acid exports contributed to
approximately USD 74.4 million for the nation. The nation can act as a hub for the export of
chemicals like nitric acid due to its advantageous position in Europe and effective logistics
infrastructure.Onthe other hand, Germany has a 13% export share of nitric acid and has made
$54.2 million from exports.
3.6 The Future Prospect on the Nitric Acid Market
Nitric acid has long been indispensable across a range of industries. By gazing into the future, it
is worth exploring the prospects of nitric acid, taking into account its current applications,
emerging trends, and global developments. While predicting the exact trajectory is challenging, a
comprehensive assessment can shed light on the role nitric acid might play in this ever-evolving
world.

According to Figure 3.10, the nitric acid market value was worth US$ 30.58 billion in 2022
and is projected to achieve a value of approximately US$ 31.60 billion in the year 2023.
Furthermore, it is expected to reach around US$ 39.7 billion by 2030, exhibiting a compound
annual growth rate (CAGR) of 3.32% during the forecast period (Market Research Future, 2023).
The nitric acid market is expected to grow tremendously and register a strong growth over the
assessment period.

Figure 3.10: Nitric Acid Market Size by 2030 (Precedence Research, 2021)

Figure 3.11: Global Concentrated Nitric Acid Market Trend (Research Nester, 2023)
 Based on the Figure 3.11, the Asia-Pacific region is forecasted to display significant
opportunities for the growth of nitric acid market by the year 2035. The forecast period (2023 to
2035) anticipates a substantial CAGR of 4% for the demand of nitric acid in the Asia Pacific region.
The growth of the nitric acid market is mostly driven by the increasing demand from manufacturers
of fertilizers and the growing utilization of fertilizers in agricultural economies across the globe
(Future Market Insights Inc, 2023). In the foreseeable future, the demand for fertilizers is projected
to surge rapidly as the growing population leads to an increased need for food production. To meet
the rising global food demand, there is a requirement for additional cultivable land. Consequently,
the demand for fertilizers, and therefore nitric acid, is on the rise, and the global fertilizer industry
is expected to witness a CAGR of approximately 5.2 % during the forecast period (Research Dive,
2022). Other than that, rising construction activity also benefits the nitric acid market as toluene
di-isocyanate (TDI) and nitric acid are intermediates used in the production of wood and floor
coatings, polyurethane foams, and insulating materials. Additionally, changing consumer lifestyles,
expanding remodelling projects, and new government initiatives act as driving factors for the
growth of nitric acid market (Skyquest, 2023).

While it is challenging to predict the future with certainty, examining current trends and
global developments provides valuable insights into the prospects of nitric acid. Its diverse
applications in agriculture, defence, clean energy, electronics, and water treatment place nitric acid
as a chemical compound with valuable prospects. However, the future of nitric acid hinges on
factors such as technological advancements, environmental concerns, regulatory changes, and the
availability of alternative chemicals or processes. By embracing innovation, sustainability, and
responsible resource management, the potential of nitric acid can be harness and leverage its
benefits to shape a brighter future. As short, nitric acid is anticipated to have a significant demand
in the future.

3.7 Plant Capacity

Plant capacity refers to the production of a manufacturing plant that could achieved within a
timeframe. It is very important for a company to determine the plant capacity for a startup project
to meet the demand of the market. Overcapacity in the chemical plant will result in surplus of
inventory which will lead to the additional storage space required and the price rivalry in the
market as the selling price of the product must be lowered in order to sell the excess production.
Therefore, estimation of the plant capacity can be carried out by surveying the existing plant
capacity from the competitor around the world as shown in Table 3.2.
 Table 3.2: Production Capacity of Nitric Acid HNO3

No Company Plant Location Capacity (tpa)

1 TKG Hu Chem Yeosu, South Korea 1080000

2 JSC Navoiyazot Navoiy, Uzbekistan 495000

3 INEOS Köln Cologne, Germany 495000

4 Pakarab Fertilizers Limited Khanewal, Pakistan 455400

5 Akdeniz Gubre Sanayi Mersin, Turkey 405280

6 Enaex S.A Mejillones, Chile 305250

7 CF Industries Donaldsonville, 287100

Louisiana, USA

8 Dorogobuzh PAO Smolensk, Russia 272000

9 DFPCL Dahej, India 240900

10 Haifa Chemicals Ltd Mishor-Rotem, Israel 127710

11 KEMAPCO Aqaba, Jordan 115000

12 Thai Nitrate Co Rayong, Thailand 69300

Average 362328/362300

From the Table 3.2, it clearly depicts that most of the HNO3 plant capacity ranging from
250000 tpa to 500000 tpa while the average plant capacity is about 362300 tpa. It can be noticed
that the HNO3 plant in the South Korea holds the largest capacity and it also proves the finding in
market supply study where South Korea is the primary manufacturer and the largest exporter. As
discussed in the previous section, the demand for nitric acid is expected to elevate due to the
growing global population and improvement in the electronics industry. Therefore, the new HNO3
plant capacity was proposed to be 400000 tpa to satisfy the rising demand.
 CHAPTER 4

REACTION PATHWAY

4.1 Reaction Pathway A: Catalytic Oxidation of Ammonia

The most common approach used in the manufacturing industry for the production of nitric acid
involves the Ostwald process. Three of the chemical process are the oxidation of ammonia,
oxidation of nitric oxide and absorption of dinitrogen tetroxide.

The overall chemical reaction is the outcome of three primary chemical product reactions.
This particular process involves the oxidation of anhydrous ammonia is reacted with air in a
catalytic converter to nitric oxide, by using a platinum or rhodium gauge catalyst under specific
conditions. The most commonly used catalyst is made of 90% platinum and 10% rhodium gauze
constructed from squares of fine wire (Thiemann et al., 2000). Based on the present experimental
conditions, it has been observed that the oxidation of ammonia to nitric oxide (NO) occurs through
an exothermic reaction. Figure 4.1 depicts a catalytic converter employed for the oxidation of
ammonia.

Figure 4.1: Ammonia Oxidation Catalytic Reactor

The second main chemical reaction process involves the oxidation of nitric oxide. The
oxidation of nitric oxide, which is produce during the process of ammonia oxidation, is an essential
process. The process involves the passing of a stream through a condenser in order to achieve
cooling. The non-catalytic reaction between nitric oxide (NO) and residual oxygen (O ) results in
the formation of nitrogen dioxide (NO ) (Diego et al.).
 The ending stage in the manufacturing of weak nitric acid entails the aqueous absorption
process of NO and N O , resulting in the formation of nitric acid. The release of gaseous NO
occurs during the absorption of N O . The reaction rate is determined by a series of three separate
steps. Firstly, the oxidation of nitrogen oxide (NO) to nitrogen dioxide (NO ) occurs in the gas
phase. Secondly, the reacting oxides undergo physical diffusion, transferring from the gas phase
to the liquid phase. Finally, a chemical reaction takes place within the liquid phase. These three
steps collectively determine the overall rate of the reaction. In the field of absorption towers, it is
normal for the implementation of a strayed tower design, although packed towers may often be
used (Diego et al.). Figure 4.2 depicts the absorption column employed for the process of
absorption in water. It is apparent that the tail gas will be discharged from the top part of the
column, while the nitric acid will be emitted from the lower part. (Edward & Marcin, 2002).

Figure 4.2: A Commercial Nitric Acid Absorption Column (Edward & Marcin, 2002)

4.1.1 The Reaction Scheme and Mechanism

Figure 4.3: Reaction Scheme of Oxidation of Ammonia (Katsounaros et al., 2018)

Based on the Figure 4.3 scheme, it is observed that the adsorbed ammonia undergoes a
slow process of dehydrogenation, resulting in the formation of NH and NH. The rapid process
under consideration below is in lead with the comparatively slow recombination reaction involving
NH and OH, resulting in the formation of H and H O. The compound N serves as a catalyst for the
production of NO through the intermediate NOH (Katsounaros et al., 2018).
 Figure 4.4: Mechanism that Ammonia attached on the Catalyst (Borodin et al., 2021)

The chemisorption of oxygen atoms occurs in the hollow sites, while the adsorption of
NH takes place through the nitrogen atom on the surface atoms of Pt. The observed condition
suggests that the adsorption of oxygen is dependent upon the specific characteristics of the surface
structure (Borodin et al., 2021).

The catalytic properties of a Platinum-Rhodium (Pt Rh) catalyst in relation to its ability
to weaken the bonds between gas molecules. Specifically, impact of catalyst on the triple bond in
a nitrogen molecule (N ≡ N) and the strong bond between two hydrogen atoms in a hydrogen
molecule (H . The Pt-Rh catalyst has been widely recognised for its exceptional catalytic activity
in various chemical reactions. In this context, the phenomenon under consideration occurs at the
interface of the catalyst, where gas molecules engage in intermolecular interactions with the
surface atoms. Consequently, these interactions result in weakening intramolecular bonds of the
surface atoms (Hannevold et al., 2005).

Figure 4.5: Reaction Pathway in Absorption Column (Katsounaros et al., 2018)

 Table 4.1: Summation of Main Product Reaction

Enthalpy of
Main and Side Product Reaction Reaction,
°
∆!"#$ (kJ/mol)

Ammonia oxidation reaction 4NH & + 5O & → 4NO + 6H O & Eq 4.1 -905.2

Oxidation of nitric oxide 2 NO & + O ↔ 2NO -114

& & Eq 4.2

Nitrogen dioxide dimerization 2NO →N O Eq 4.3 -58.08

& &

Dinitrogen tetroxide absorption 3N O & + 2H O → 4HNO & + NO & Eq 4.4 -104.76

Absorption of nitric oxide Eq 4.5

3NO & +H O → 2HNO + NO & -117

Overall chemical reaction NH + 2O & → HNO +H O Eq 4.6 -252.3

In order to facilitate the re-oxidation of the nitrogen monoxide ( NO) compound and
eliminate nitrogen dioxide (NO ) from the resulting acid product, an additional air stream is
introduced into the column (Diego et al.).
4.1.2 Comparison Between the Type of Ostwald Process
According to Jacob et al. (2013), it has been declared that both types demonstrate an identical
mechanism and chemical reaction. The differences remain in the operating pressure over the
oxidation and absorption techniques, as well as the addition of an additional compressor unit
placed between the ammonia conversion stage and the heat recovery. Besides, another difference
is the method of using extended adsorption to attain NOx reduction, but reduction method is
interchangeable between single-pressure and dual-pressure. A single-pressure plant applies the
same pressure in the oxidation and absorption process, while a dual-pressure plant applies a high
pressure in absorption process and low pressure in ammonia oxidation. The reason is because
oxidation process is favoured by low pressure, but the absorption process is favoured by high
pressure (Ave, 2000). Figure 4.6 shows the differences in process flow of Single Pressure and Dual
Pressure.

Figure 4.6: Nitric acid production with Single Pressure (left) and Dual Pressure (right) (Ave,
2000)
4.1.3 The Process Description
Single-Pressure Process

Figure 4.7: Process flow diagram for single-stage pressure process (Environmental
Protection Agency, 1991)

In accordance with the results obtained from comprehensive analysis, it has been determined that
the solitary plant exhibits a favourable annual yield of 92% (Ferrer & Marzo, 2008).

Ammonia Oxidation Reaction

The process involves the combination of compressed air and anhydrous ammonia, which
are then introduce into a shell and tube converter. This converter is specifically designed to include
both a preheater and a steam heat recovery boiler-super heater within the same reactor shell. The
converter section includes of a specific number of sheets made of Pt-Rh alloy (Edward & Marcin,
2002). These sheets are in the form of wire gauge with a mesh size ranging from 60 to 80. The
catalyst densely packed in layers within the tube. The contact time and downward passage duration
of the gas within the catalyst zone is measured to be 2.5E-4 seconds, while being heated to a
temperature of 850℃ - 900℃ with a pressure range from 8 – 11 bar. The observed yield for nitric
oxide demonstrates a range spanning from 93% - 98% through the usage of a catalyst (Thiemann
et al., 2000). The catalytic reactor illustrates an important ammonia selectivity to nitric oxide, with
a reported yield of 90% (Chatterjee & Joshi, 2008).

The gaseous by products generated by the reactor, which exhibit a NO concentration

ranging from 10-12%, undergo a series of heat recovery processes. These processes involve the
usage of a heat recovery boiler, a super heater, and a quenching unit. The primary objective of
these units is to facilitate the rapid removal of a significant portion of the heat present in the product
gases. Subsequently, the cooled gases are direct into the oxidizer-absorber system (Gupta, 2020).
Oxidation of Nitric Oxide
The nitric oxide generated as an outcome of the ammonia oxidation process undergoes a
cooling process within the cooler/condenser apparatus. In this apparatus, the nitric oxide undergoes
a non-catalytic reaction with oxygen. The reaction under consideration involves the formation of
nitrogen dioxide (NO ) and its liquid dimer, dinitrogen tetroxide (N O ). The production of NO
and reaction time can be achieved by operating at lower temperatures, specifically below 38℃ and
higher pressures, reaching up to 8 bar (Thiemann et al., 2000).

Absorption of Nitric Oxide

The usage of secondary air serves for the purpose of improving the oxidation process
within the absorption tower, as well as providing the extraction of residual nitrogen oxides from
the resulting acid product. The absorption efficiency can be enhanced by using a high operating
pressure during the absorption process. The application of high-pressure absorption techniques has
been observed to enhance system efficiency and improve the overall absorption rate. The
extraction of an aqueous solution containing 55% – 65% nitric acid from the bottom part of the
tower is an essential stage in the process. It is important to note that the concentration of nitric acid
in this solution can range from 30% to 70% nitric acid. The tail gas stream, which made up of 0.2%
of nitric oxide (NO) (Environmental Protection Agency, 1991). The operating temperature for the
absorber is 40 - 43 ℃ (Chatterjee & Joshi, 2008).

Dual Pressure
The equipment employed in the single-pressure process is identical to that employed in the dual-
pressure process. This section will focus on the additional equipment. The process of ammonia
oxidation is conducted under low-pressure conditions, specifically at a pressure of 5 bar. The
heat generated during the reaction is subsequently capture and employed by a heating boiler. After
passing through the cooler or condenser, the gas is compress to around 12 bar for absorption
whereby the absorption column is operated at high pressure of 10 bar. The absorption is then
enhanced by internal water cooling, which gives a concentration of up to 70 % and an absorber
efficiency of around 96%. After that, the nitric acid produced in the absorption process will
transfer to an external bleacher to remove the dissolved NO. The bleach gases are then compress
and pass through the absorber. The resulting tail gas is reheated and sent to energy-recovery turbine,
heat is saved to drive the compressor (EPA, 2010). With the design of the Dual-Pressure process,
the product of 68 wt% of nitric acid can achieve an overall annual yield of 95% (Ferrer and Marzo,
2020). Figure 4.8 illustrates the Dual-Pressure nitric acid manufacturing process with operating
conditions.
Figure 4.8: Dual-Pressure Ostwald Process with Operating Condition (Kapteijn, 2003)

According to Postma, L. and Muñoz, P. (n.d), a few things need to be highlighted in the dual
pressure process: first, the acid solution will form when the temperature of the nitrous gas gets
close to its dew point, because the acid solution will condense. When condensation happens, the
re-evaporate water will concentrate the acid and cause a serious corrosion problem. The cold spots
and dead zone will affect seriously. Besides, the coolers, condensers and heat exchangers will
likely suffer corrosion problems, especially if the vapour temperature is near the dew point.
Moreover, it is highly likely that the coolers, condensers, and heat exchangers will encounter
corrosion issues, particularly when the vapor temperature gets closer the dew point. Therefore,
proper selection of operating temperature and location of equipment can minimise the
condensation effect. Dual pressure processes also enable low emission of harmful gasses: NO2 and
N2O, which contribute to acid rain, greenhouse effect and ozone layer reduction. There are three
ways to reduce it:

1. The N2O formation is eliminated by the presence of modified Pt/Rh gauzes.

2. The N2O is removed between the outlet of the gauze and the absorption tower.
3. The N2O is detached at the hottest location of the absorption tower downstream, which is
the expander upstream.
4.1.4 The List of Process Conditions
In this technical report, we present Table 4.2, which provides an in-depth review of the operational
information related to the Ostwald process for the production of nitric acid. This table consists of
all the relevant data necessary for a thorough understanding of the process.

Table 4.2: The General Information for Ostwald Process for Both Pressure

Reaction Pathway A – Ostwald Process

Single - Pressure Dual - Pressure

Raw Material Ammonia in aqueous solution and oxygen

Overall Chemical Equation +, -. + 2/ 0 → ,+/ -. +, O 1

Operating Temperature

Catalytic Convertor 850℃ - 900 ℃ 881.85 ℃

Cooler/Condenser Below 38℃ 37 ℃

NOx Compressor - 172 ℃

Absorption Column 40℃ 22 ℃

Operating Pressure

Catalytic Convertor 8 bar 5 bar

Cooler/Condenser 8 bar 4 bar

NOx Compressor - 12 bar

Absorption Column 9 bar 10 bar

Reaction Phase Gas and Liquid

Catalyst Platinum-Rhodium

By-product Nitrous Oxide and Nitrogen Dioxide

Yield 92% 95 %

Selectivity 90% -
4.1.5 Advantages and Disadvantages of Ostwald Process
The advantages and disadvantages of both the Ostwald process are presented in Table 4.3 and
Table 4.4.

Table 4.3: Advantages and Disadvantages of Single Pressure Ostwald Process

Advantages Disadvantages

• The cost is reduced due to the usage of • The effectiveness of the overall process
a reduced amount of equipment. decreases due to the influence of the
• The single-pressure process involves fluctuation in pressure.
taking advantage of increased pressure • The experimental findings indicate that
for the conversion of ammonia. The the rate of decomposition of the catalyst,
increased pressure level provides in the absence of a catalyst recovery
several benefits in relation to equipment system, shows a significantly higher
design, such as smaller dimensions of rate of decrease at a temperature of
the converter and a simplified layout of 973 °C compared to 866 °C. The
the heat exchanger train. observed condition indicates a higher
• The increase in temperature and rate of catalyst loss in the single-stage
pressure levels improves the energy pressure process.
recovery from the process. • The efficiency of the absorber
• The fact of limited space availability decreases, requiring the usage of a
may potentially provide a useful larger absorber, resulting in a raised
situation for carrying out the single- cost.
pressure process.

Table 4.4: Advantages and Disadvantages of Dual Pressure Ostwald Process

Advantages Disadvantages

• Less raw material of ammonia is • Require high capital cost for

needed to produce nitric acid construction and installation
• Longer catalyst life
• Replace catalyst after a long period
• Higher ammonia conversion
• Lower NO2 content in final product
4.2 Reaction Pathway B: Birkeland-Eyde Process
In 1903, Norwegian industrialist and scientist Kristian Birkeland and Sam Eyde created Birkeland-
Eyde process. Birkeland-Eyde process was the traditional way to produce nitric acid on an
industrial scale (Ashadul Adalder, 2022). Air was used to generate nitric acid (HNO ), which was
then utilized to produce fertilizer. In Norway, factories that utilized this process were constructed
in Rjukan and Notodden (ChemEurope, 2023). Since this process needed 15 megawatts hour per
ton of nitric acid (MWh/ton), a hydroelectric plant in Norway was used by Birkeland to generate
electricity (Ashadul Adalder, 2022). The power provided to the Birkeland-Eyde plant experienced
a significant increase, starting from 2.24 kW in 1903 and reaching 238.6 MW by 1928 (Kevin H.
R. Rouwenhorst, 2021).

4.2.1 Chemical Reaction

Firstly, nitric oxide (NO) is generated from the reaction between atmospheric nitrogen and oxygen
through an electric arc. Next, nitrogen dioxide (NO ) is generated through the oxidation of NO.
After that, water is added to react with NO and nitric acid ( HNO ) is produced which is
subsequently purified using fractional distillation. The chemical reactions are presented in
Equation 4.7 – 4.9 (Kevin H. R. Rouwenhorst, 2021).

N (g) +O (g) → 2NO(g) (4.7)

2NO(g) + O (g) → 2NO (g) (4.8)

3NO (g) + H O(l) → 2HNO (aq) + NO(g) (4.9)

4.2.2 Process Description

Figure 4.9 shows the Birkeland-Eyde process scheme. Firstly, a centrifugal compressor was used
to compress the air at 8 atm and the air was preheated before delivering it to an electric arc
generated between two co-axial copper electrodes that were water-cooled (Maslan, 1969). These
electrodes were positioned between the poles of a powerful electromagnet, resulting in the
conversion of air into NO in the furnace and a yield of 5 % of nitric oxide could be obtained. The
temperature of the furnace was around 3000 °C. Next, NO from the outlet of the furnace was
rapidly quenched to temperatures ranging from 800 to 1000 °C in the cooling chamber because
NO was not stable. This step was to prevent the reversible reaction occur where NO was converted
back to N and O . After that, NO was oxidized into NO slowly in an oxidation chamber at a
temperature of 275 °C (Kevin H. R. Rouwenhorst, 2021). At this stage, the conversion of NO
was highly dependent on the concentration of NO. The higher the concentration of NO, the faster
the conversion of NO (Ashadul Adalder, 2022). The mixture of NO and NO exited from the
economizer at approximately 200 °C was then underwent cooling in the cooling tower to bring the
temperature down to 50 °C and compressed at 120 psia before being introduced into an absorption
tower. This is because absorption capacity improves at lower temperatures. Finally, the resulting
NO gas was then sent to an absorption column packed with quartz. NO gas entered the bottom
of the column while water was supplied from the top of the column. Water was used to absorb
NO gas to generate HNO . HNO in water could be obtained as the bottom product which
required further purification using fractional distillation. Alkaline absorption columns were used
to further absorb the unabsorbed NO3 , however, around 3 % of NO3 would still be released into
the atmosphere (Kevin H. R. Rouwenhorst, 2021).

Figure 4.9: Birkeland-Eyde Process Scheme (Kevin H. R. Rouwenhorst, 2021)

4.2.3 Operating Conditions and Output
Table 4.5 summarizes the operating conditions and output of the process.

Table 4.5: General information for Birkeland-Eyde Process

Reaction Pathway B - Birkeland-Eyde Process

Raw Material Air and water

Type of Chemical Involved Nitric oxide (NO), nitrogen dioxide (NO ), nitric acid (HNO )

Chemical Reaction Involved N (g) +O (g) → 2NO(g) 2NO(g) + O (g) → 2NO (g) 3NO (g) + H O(l) → 2HNO (aq) + NO(g)

Overall Chemical Equation N (g) + 3O (g) + H O(l) → 2HNO (aq) + NO(g)

Type of Equipment Birkeland-Eyde furnace Oxidation Chamber Absorption column

Operating Temperature 3000 °C 275 °C 50 °C

Operating Pressure 8 atm - 120 psia

Reaction Phase Gas phase Gas phase Aqueous phase

By-product - - Nitric oxide (NO)

Conversion 5 % of nitric oxide - 30 % of nitric acid

Product Yield - - 30 % of nitric acid

Purity - - 68 %

Production - - 60 g/kWh
4.2.4 Advantages and Disadvantages of Birkeland-Eyde Process
The advantages and disadvantages of the Birkeland-Eyde process are presented in Table 4.6.

Table 4.6: Advantages and Disadvantages of Birkeland-Eyde Process

Advantages Disadvantages

• Feasible for large-scale industrial • High energy consumption (Kevin H. R.

production. Rouwenhorst, 2021).
• The process utilizes atmospheric • A large hydroelectric plant is required
nitrogen, oxygen, and water as raw to provide sufficient electricity to the
materials which are abundant and easily electric arc for operation (Ashadul
accessible. Therefore, additional Adalder, 2022).
nitrogen sources are not required which • High operating costs due to its energy-
can reduce the production costs. intensive nature.
• Workers' safety is impacted by the
extremely high temperature in the
furnace.
• NOx emissions which contribute to air
pollution and smog formation. These
pollutants may negatively impact the
environment and human health.
(Queensland, 2023).
• Electric arc operations are extremely
complex and skilled technicians are
required.
• Low conversion and product yield.

• Low purity.
4.3 Reaction Pathway C: Chile Saltpetre
Editors of Encyclopaedia Britannica (2023) stated that in 1648, nitric acid (HNO3) was first
produced by a German chemist – Johann Rudolf Glauber, in a laboratory by heating potassium
nitrate, (KNO3), with concentrated sulphuric acid (H2SO4). This method is named the Chile
Saltpetre method, and Chile Saltpetre is referred to as sodium nitrate NaNO3 and is also the raw
material used to produce HNO3. This production combines alkaline nitrate salt and H2SO4, through
heating (Sciencemadness.org., 2018). There is a concern about the choice of nitrate salt, which can
either be potassium or sodium nitrate. However, it is strictly advised to avoid using ammonium
nitrate, as it can lead to the production of a lower grade of HNO3 due to the occurrence of side
reactions. Calcium nitrate can also be use in this method, but this salt has peculiarities that make
the reaction slightly different from Glauber's classic synthesis. In addition, the H2SO4 must have
a concentration of more than 60% if you want to produce an azeotropic HNO3 or around 95% if
you want to produce a red-fuming HNO3 (RFNA). Concentrated phosphoric acid (H3PO4) can also
use to produce azeotropic HNO3, but the H3PO4 will slowly attack the glassware because this
synthesis involves a heating process.

4.3.1 The Reaction Scheme and Mechanism

The formation of nitric acid through sodium nitrate and sulphuric acid is a decomposition reaction.
Decomposition reaction is a process where the bond between the compound break to form a new
product. In the Chile Saltpetre process, when temperature is applied to the reactant, the NaNO3
will decompose into Na+ and NO3- while the H2SO4 will decompose into H+ and HSO4-. HSO4- is
known as the bisulphate ion which is a weak acid that will form NaHSO4 when it receives one
proton from the Na atom (Vedantu, 2022). Therefore, at the operating temperature of 200 ℃ the
products formed from the exothermic decomposition reaction are NaHSO4 and HNO3. The
chemical equation of the process is shown in Equation 4.10.

NaNO 4 + H SO → NaHSO + HNO (4.10)

4.3.2 The Process Description
In this subsequent section, a comprehensive examination of the Chile Saltpetre or Nitrate process
will be carried out. The process under discussion is a traditional technique employed during the
1920s. While modern advances have likely replaced its usage, an in-depth analysis of the chemical
process along with technology can still provide helpful insights into the production of nitric acid.
A conventional production process using the Chile Saltpetre method is shown in Figure 4.10.

Figure 4.10: Chile Saltpetre manufacturing process (Norman & Harry)

Several primary reactions occur during the manufacturing process of Chile Saltpetre. For
instance, the usage of heating in a cast iron retort, the installation of a separator in a distillation
process, as well as the addition of condensation and a scrubber (Gupta, 2020). The overall plant
yield of nitric acid has been estimated to be 95%. The major equipment depicted in the above
figure is clearly label (Norman & Harry).

Heat reaction – Rotating Retort or Drum

The retort is set up at a slight angle to facilitate the continuous flow of materials through it. It
consists of a large rotating drum made of acid-resistant iron or another comparable material. A
solution of sulphuric acid containing 93% concentration is combine with refined Chile Saltpetre
in accordance with the stoichiometric ratio. The resulting mixture is then introduced into a retort
constructed from cast iron, and subsequently subjected to a temperature of 200°C with the help of
fire chamber which label as 13 shown in the figure above. In order to speed up the extraction of
the 56!789 solution, a pipe shall be affix to the discharge point of the retort. Furthermore,
another product that can be obtain is 5!: in the form of vapors. This pipe will serve as an outlet
for the transportation of the product resulting from the heating process (Norman & Harry).
Scrubber
Subsequently, the effluent is conveyed through a vapor pipe into the bleacher. The bleacher has
the ability to distribute acid solutions with a wide range of desired strengths, ranging from 60% -
98% or even higher. The uncondensed nitric acid generated by the bleaching process, along with
the nitrous vapors, flows through a pipe to the acid vapor. Subsequently, it is direct towards one
or more condensers, which may adopt various suitable or commonly used designs. The nitrous
vapors move up in a countercurrent manner to the hot sulfuric acid in the system and proceed to
the scrubbing tower. The scrubbing tower is equipped with standard internal components for
encouraging contact between vapors and liquids. Within the scrubbing tower, the nitric acid vapors
undergo a drying process and receive a partial release of nitrous vapors through the downward
movement of sulfuric acid or mixtures that included sulfuric acid (Norman & Harry).

Cooling and Condense Reaction – cooling water and condenser

The vapors are observed to follow a somewhat direct path, crossing vertical conduits that are linked
by cross tubes. These cross tubes are cooled by the continuous flow of water originating from
cooling water supply. The cooled vapors then proceed to the vapor outlet, which is connected to
the primary conduit leading to the absorption towers which not shown in the figure. These towers
are specifically designed to facilitate the reoxidation and retrieval of nitrous oxides, such as nitric
acid. The recovery of phitrous vapors is a customary practice in the absorption towers, resulting
in the production of nitric acid with a concentration ranging from 68 % - 75 %.

4.3.3 The List of Process Conditions

In this technical report, we present Table 4.7, which provides an in-depth review of the operational
information related to the Chile Saltpetre process for the production of nitric acid. This table
consists of all the relevant data necessary for a thorough understanding of the process.

Table 4.7: The General Information for Chile Saltpetre Process

Reaction Pathway C - Chile Saltpetre Process

Raw Material sodium nitrate in solid and sulphuric acid in liquid

Overall Chemical Equation NaNO 4 + H SO → NaHSO + HNO

Operating Temperature

Retort Reactor 200°C

Cooler/Condenser -
 Scrubber -

Reaction Phase Gas, Liquid and Solid

Catalyst No needed of catalyst

By-product Nitrous Oxide

Yield 95%

Selectivity -

4.3.4 Advantages and Disadvantages of Chile Saltpetre Process

The advantages and disadvantages of the Chile Saltpetre process are presented in Table 4.8.

Table 4.8: Advantages and Disadvantages of Chile Saltpetre Process

Advantages Disadvantages

• Does not have any side reaction. • In practically, it left many unreacted
• The by-product of Sodium bisulfate is sulphuric acid.
profitable. • This method does not have much
resource for the selectivity and
conversion.
• This method is only applicable in lab
scale.
• The equipment used in experiment
could not withstand for long life for
this extreme variation in temperature
during the operation.
 CHAPTER 5

GROSS PROFIT ANALYSIS

5.1 Chemical Pricing

The pricing of the chemicals involved in all the reaction pathway are summarized in Table 5.1
below.
Table 5.1: Prices of Chemicals in USD/lb

Chemicals Price (USD/lb) Purity Sources

Ammonia 0.205 99.9% (Alibaba, 2020)

Nitric Oxide 40.82 99.9 % (Alibaba, 2023)

Nitric Acid 0.406 98.0% (Chemanalyst, 2023)

Sodium Nitrate 0.273 99.0% (Chemi, 2023)

Sulphuric acid 0.021 98.0% (Chemi, 2023)

Sodium Bisulphate 0.440 99.0% (Alibaba, 2023)

Nitrogen 0 - -

Oxygen 0 - -

Water 0 - -
5.2 Gross Profit for Every Reaction Pathway
The gross profit of each reaction pathways is calculated using the information tabulated in Table
5.2, Table 5.3 and Table 5.4 using the equation:

Gross profit = profit of products + by-product – price of feedstock

Table 5.2: Calculation of Gross Profit for Ostwald Process

Reaction NH3 + 2O2 → HNO3 + H2 O

Chemical name Ammonia Oxygen Nitric acid Water

lb-mole 1 2 1 1

Molecular weight 17.031 15.999 63.010 18.015

lb 17.031 31.998 63.010 18.015

lb/lb nitric acid 0.270 0.508 1.000 0.286

$/lb 0.205 0 0.406 0

Gross profit = 1(0.460) + 0.286 (0) – 0.270 (0.250) – 0.508 (0)

= 0.350 $/lb HNO3 produced

Table 5.3: Calculation of Gross Profit for Birkeland -Eyde Process

Reaction :
;
5; + 38; + !; 8 → 2!58: + NO

Chemical Name Nitrogen Oxygen Water Nitric Nitric

Acid Oxide

lb-mole 3/2 3 1 2 1

Molecular Weight 28.01 32.00 18.02 63.01 30.01

lb 42.02 96.00 18.02 126.02 30.01

lb/lb of !58: 0.333 0.762 0.143 1 0.238

$/lb 0 0 0 0.406 40.82

Gross profit = 1(0.406) + 0.238(40.82) – 0

= 10.12 $/lb of HNO produced
 Table 5.4: Calculation of Gross Profit for Chile Saltpetre
Reaction NaNO3 + H2SO4 → HNO3 + NaHSO4

Chemical name Sodium Sulphuric Nitric Acid Sodium

Nitrate Acid Bisulphate

lb-mole 1 1 1 1

Molecular weight 84.995 98.078 63.01 120.06

lb 84.995 98.078 63.01 120.06

lb/lb Nitric Acid 1.349 1.557 1.000 1.905

$/lb 0.273 0.091 0.160 0.350

Gross profit = 1(0.160) + 1.905(0.350) – 1.349(0.273) – 1.557(0.091)

= 0.317 $/lb HNO3 produced
 CHAPTER 6

DETERMINATION OF THE MOST PROMISING REACTION PATHWAY

6.1 Summary of Selection Consideration

The following chapter is dedicated to the process selection for the manufacturing of nitric acid.
Based on an extensive literature survey, the following processes have been identified and tabulated
in table below. A comparative analysis of various nitric acid manufacturing processes is presented
in the following table.

Table 6.1: Summary and Comparison of All Reaction Pathways

Reaction A B C
Pathway

Reaction Process Catalytic Oxidation Catalytic Oxidation Birkeland-Eyde Chile Saltpetre

of Ammonia - of Ammonia - dual Process
single pressure pressure process
process

Operating 850℃ 900℃ 881℃ 3000℃ 200℃

Temperature

Operating Pressure 8 bar 5 bar 8 bar -

Catalyst Pt - Rh alloy - -

Reactor Type Catalytic Reactor Fusion Reactor Retort Reactor

Reaction Phase Gas and Aqueous Gas and Solid, Liquid

Aqueous and Gas

Yield 92 % of nitric acid 95 % of nitric acid 30 % of nitric 95 % of nitric

acid acid

Conversion 95 % of nitric oxide 96% of nitric oxide 5 % of nitric -

oxide

Selectivity 90 % to nitric oxide - - -

Gross Profit 0.1100 $/lb 9.88 $/lb 0.0889 $/lb

Downstream Implementation of Additional Separation and Separation and
Process an absorption and equipment is purification cooling
subsequent required as process is equipment are
purification process compared to single required. required.
is required. pressure process.

Environmental Greenhouse gas emissions, including those Greenhouse gas Greenhouse gas
impact of nitrous oxide, nitric oxide, and minor release to release to
amounts of ammonia gas. environment environment
mainly NO3 mainly nitrous
content gas. gas.

6.2 Selection and Justification for Reaction Pathway

Alternative Pathway A: Catalytic Oxidation of Ammonia (single-pressure)
Based on the analysis conducted, it has been determined that pathway A with single pressure
exhibits the most beneficial reaction pathway. The primary reason for selecting the pathway lies
in the important selectivity and conversion efficiency towards nitric oxide, which results in an
excellent overall yield of nitric acid. The annual yield of nitric acid is observed to be 92%,
indicating a high level of productivity. The nitric oxide conversion rate has been determined to be
95%. The observed yield of the investigated process exhibits a notable increase when compared
to the conventional Birkeland-Eyde Process, which is limited to a maximum yield of 30%. The
observed pathways exhibit more effective levels of selectivity and conversion rates, exceeding
alternative reaction pathways. The nitric acid concentration within the water absorption system
ranges from 57% to 60%. This particular concentration is suitable for both commercial sales and
usage in fertilizer manufacturing procedures. The next aspect relates to the reactor arrangement,
specifically a catalytic reactor. It considers that the cost associated with the catalytic reactor is
significantly lower in comparison to the fusion reactor used for Pathway B. All reaction pathways
require subsequent downstream processes, such as distillation, to improve the level of purity of
the nitric acid. This will result in additional investment and maintenance costs being required. The
gross profit for Ostwald which is 9.88 $/@A, while not the highest, is still non-negative. The
procedure mentioned earlier has the potential to generate revenue within a predetermined payback
period.
Alternative Pathway A: Catalytic Oxidation of Ammonia (dual-pressure)
It is undeniable that a dual-pressure plant will yield more capacity and a shorter payback period
and requires a lower quantity of catalyst compared to a single-pressure plant. The decision to not
select for a dual process can be explained by the limited production capacity of nitric acid at the
plant, as well as the insufficient size of the plant. In addition, it is important to note that the
operational cost associated with dual-pressure systems is significant higher compared to single-
process systems. This is mainly due to the additional equipment required by dual-
pressure systems to achieve optimal conditions. Additionally, an absence of information related
to the selectivity of nitric oxide was observed. The current practice within the industry mainly
involves the application of single-pressure processes, while the application of dual-
pressure processes remains relatively underdeveloped.

Alternative Pathway B: Birkeland-Eyde Process

The analysis reveals that the gross profit displays the highest numerical value which is 0.1100 $/@A.
However, it is essential to understand that the operating temperature is very high. Hence, it is
posing a significant risk of unforeseen accidents if appropriate safety measures are not carefully
carried out. The primary factor impacts the decision not to select pathway B relates to the operating
temperature of the Birkeland-Eyde Process, which has the potential to achieve a maximum
temperature of 3000℃. Since it is indeed reliable that higher temperatures can improve efficiency,
it is important to take into account all related costs and challenges. A major drawback is the
increased energy consumption resulting from elevated temperatures. Additionally, the control
process for reactions operating at temperatures as high as 3000℃ presents significant obstacles.
These factors must be carefully evaluated when considering the feasibility and practicality of
employing high temperatures to improve efficiency. Additionally, it is important to note that the
yield of pathway B demonstrated a significantly low efficiency, reaching a simple 30% of nitric
acid. Furthermore, the conversion rate of nitric acid for this pathway was observed to be a simple
5%.

Alternative Pathway C : Chile SaltPetre

Pathway C is not select mainly because it is an old approach and does not have full details with
regard to the reaction pathway. Furthermore, another additional primary factor that prevents the
selection of pathway C has the lowest gross profit which is 0.0889 $/@A when compared to the
other two pathways. The heating temperature of Pathway C, which is set at 200℃, is both low and
easily manageable. The corrosion of the reactor can take place as a result of the heating of sulphuric
acid. This phenomenon will require the replacement of a new reactor as a result of corrosion,
which may result in substantial expenses. The exhaustion of raw materials, such as sodium nitrate
and sulfuric acid, can occur as time passes.
 CHAPTER 7

PLANT AND PROCESS SAFETY CONSIDERATION

The chemicals that include in the selected Ostwald Process are the reactant: ammonia and oxygen;
side product: nitric oxide, water, nitrogen dioxide and dinitrogen tetroxide; product: nitric acid and
catalyst: Platinum-Rhodium.

7.1 Safety Data Sheet

Table 7.1: Sources of Safety Data Sheet of Chemicals
Chemical Safety Data Sheets Date of Link
Revision
Ammonia Sigma-Aldrich, Ammonia 14 May 2020 https://www.sigmaaldrich.com/MY
Safety Data Sheet /en/sds/aldrich/294993
Oxygen Airgas, Oxygen Safety 22 Sept 2020 https://www.airgas.com/msds/0010
Data Sheet 43.pdf
Nitric Airgas, Nitric Oxide 2 Feb 2021 https://www.airgas.com/msds/0010
Oxide Safety Data Sheet 39.pdf
Water LabChem, Water Safety 26 June 2020 https://www.labchem.com/tools/ms
Data Sheet ds/msds/LC26750.pdf
Nitrogen AirLiquide, Nitrogen 17 July 2020 https://sg.airliquide.com/sites/al_sg/
Dioxide Dioxide Safety Data Sheet files/2020/08/03/sds-090-
clp_nitrogen_dioxide.pdf
Nitric Acid ThermoFisher Scientific, 24 Dec 2021 https://www.fishersci.com/msds?pr
Nitric Acid Safety Data oductName=A467250%26product
Sheet Description=NITRIC
Dinitrogen CF, Dinitrogen Tetroxide 1 July 2021 https://www.cfindustries.com/globa
Tetroxide Safety Data Sheet lassets/cf-
industries/media/documents/safety-
data-sheets/dinitrogen-
tetroxide/dinitrogen_tetroxide_mix
ed_oxides_of_nitrogen_na.pdf
Platinum- ThermoFisher Scientific, 27 Dec 2020 https://www.alfa.com/en/msds/?lan
Rhodium Platinum Rhodium foil guage=EN&subformat=CLP1&sku
=41808
 7.2 Physical and Chemical Properties

Table 7.2: Physical Properties of Chemicals and Catalyst Involved

Chemical Chemical Density Molecular Melting Boiling Color Odor Physical Water Solubility
Formula (kg/B: ) Weight (g/mol) Point (°C) Point (°C) State

Ammonia NH 0.73 17.03 -77.7 -33 Colorless Pungent Gas 531 g/L at 20 °C

Oxygen O 1.33 32 -218.4 -183 Colorless Odorless Gas NA

Nitric Oxide NO 1.34 30.01 -163.6 -151.8 Colorless Unpleasant Gas NA

Water H O 997 18.02 0 100 Colorless Odorless Liquid Miscible in any

proportion

Nitrogen NO 3.66 46.01 -11.2 21.2 Yellowish-brown / Pungent Gas Completely

Dioxide brownish red / soluble
yellow / brown / red

Nitric Acid HNO 1404.8 at 63.01 -41.6 83 Colorless Acrid Liquid Miscible in any
20 °C proportion

Dinitrogen N O 1450 92.01 -11.2 21.2 Reddish-brown / Pungent Gas NA

Tetroxide green
Platinum- PtRh NA 297.98 NA NA Gray Odorless Solid Insoluble
Rhodium

*NA: Not available

Table 7.3: Chemical Properties of Chemicals and Catalyst Involved

Chemical pH Stability Reactivity

Ammonia 10 – 12 at 50 Remains stable when • React explosively with halogens, hypochlorites, and acid (Agriculture, 2023).
g/L at 20 °C stored as recommended • May undergo reactions with certain heavy metal compounds such as mercury
and gold (III) chloride that could be prone to explosive behavior when in a dry
state (Chemicals, 2023).

Oxygen NA Stable under normal • Highly reactive with combustible materials, reducing materials, oil, and grease
conditions (Airgas, 2020).

Nitric Oxide NA Stable under normal • Produce toxic and corrosive nitrogen dioxide and nitric acid when reacting with
conditions air, oxygen, water, and moisture (Supply, 2020).
• Can potentially explode during distillation or evaporation (Supply, 2020).
• React vigorously with halogens, nitrogen trichloride, ozone, and chlorine
monoxide (NJHealth, 2009).
• Incompatible with oxidizing agents, reducing agents, combustibles, chlorinated
hydrocarbons, metals, and metal salts (NJHealth, 2009).
 Water 6.0 - 8.0 at Stable under room • Incompatible with metallic sodium (LabChem, 2020).
25 °C temperature • Hazardous products such as hydrogen and oxygen may produce (LabChem,
2020).
Nitrogen Dioxide NA Stable under normal • Incompatible with reducing agents, combustibles, alkalis, oil, and grease
conditions of usage and (AirLiquide, 2020).
storage • Corrosive acids may generate when react with water (AirLiquide, 2020).

Nitric Acid < 1 at 20 °C Remains stable when • Fire may occur when reacts with combustibles and organic material (Scientific,
stored as recommended 2021).
and under room • Incompatible with strong bases, reducing agents, metals, aldehydes, alcohol,
temperature ammonia, and cyanides (Scientific, 2021).

Dinitrogen Acidic when Stable under normal • Contact with ammonia, boron trichloride, carbon disulfide, cyclohexane,
Tetroxide dissolved in conditions fluorine, formaldehyde, nitrobenzene, toluene, incompletely halogenated
water hydrocarbons, propylene, alcohols, and ozone can lead to explosions (CF,
2021).
• Incompatible with water, bases, flammable and combustible materials, copper,
and aluminum (CF, 2021).
• Corrosive to metals when in a moist state (CF, 2021).
Platinum-Rhodium NA Remains stable when NA
stored as recommended

*NA: Not available

7.3 Hazard Identification
The NFPA rating explanation guides are shown in below Table 7.4 while the relevant information
for the environment and safety data analysis are shown in Table 7.5.
Table 7.4: NFPA Rating Explanation Guide
Hazard Number Indication

0 Normal material

1 Slightly hazardous

Health 2 Hazardous

3 Extreme danger

4 Deadly

0 Will not burn

1 Above 200 °F

Fire 2 Between 100 °F and 200 °F

3 Below 100 °F

4 Below 73 °F

0 Stable

1 Unstable if heated

Instability 2 Violent chemical change

3 Shock and heat may detonate

4 May detonate
 Table 7.5: Environmental and Safety Data Analysis for Chemicals Involved

Chemical Hazard NFPA Safety Data Environmental Data

Compound Identification Rating

Ammonia Flammable, Health: 3 LFL: 15 Accidental gas releases

corrosive and will cause contamination
Flammability: 1 UFL: 28
toxic gas of environment.
Instability: 0 Flash Point: 11 °C

Autoignition
temperature: 651 °C

TWA: 25 ppm

STEL: 35 ppm

Oxygen Compressed Health: 0 No data available. Should not be released

gas into the environment, can
Flammability: 0
cause environmental
Instability: 0 pollution.

Nitric Hazardous Health: 4 LFL: - Should not be released

Oxide compressed into the environment, can
Flammability: 0 UFL: -
gas. cause environmental
Instability: 1 Flash Point: - pollution.

Autoignition
temperature: -

TWA: 25 ppm

STEL: 30 ppm

Water Not a Health: 0 No data available. Prevent entry to sewers

hazardous and public waters.
Flammability: 0
substance or
mixture. Instability: 0

Nitrogen Hazardous Health: 0 No data available. Should not be released

Dioxide compressed into the environment, can
Flammability: 0
gas.
 Instability: 0 cause environmental
pollution.

Nitric Acid Reactive & Health: 4 LFL: 15 Should not be released

toxic liquid into the environment. Do
Flammability: 0 UFL: 28
not let product enter
Instability: 0 Flash Point: 11 °C drains.
Autoignition
Temperature: 651 °C

TWA: 2 ppm

STEL: 4 ppm

Dinitrogen Hazardous Health: 4 LFL: - Should not be released

Tetroxide compressed into the environment, can
Flammability: 0 UFL: -
gas. cause environmental
Instability: 0 Flash Point: - pollution.
Autoignition
temperature: -

TWA: 25 ppm

STEL: 38 ppm

Platinum Hazardous Based on No data available. Should not be released

Rhonium Combustion available data, into the environment,
Product the classification will contaminate ground
criteria are not water system
met.

*Abbreviations: LFL – Lower Flammability Limit

UFL – Upper Flammability Limit
TWA – Time-Weighted Average
STEL – Short-Term Exposure Limits
 7.4 Toxicity Properties
Table 7.6: Toxicity Properties of the Chemical Involved

Chemicals Toxicology LC50 Health Hazards Environmental Hazards

inhalation limit

Ammonia 5.1 mg/L • Eye disorders. • Soil acidification

• Respiratory disorders. • Cause water pollution
• Skin disorders. due to its highly soluble
• Allergies. properties in water.
• Cause air pollution by
contributing to haze and
smog formation.
• Cause eutrophication

Oxygen - • Cell damage and death • Promote rapid

combustion that increase
• Collapse of the alveoli in the
carbon dioxide level.
lungs
• Pleuritic chest pain
• Substernal heaviness
• Coughing
• Dyspnea
Nitric 174 ppm • Headache • Will form harmful and
Oxide • Fatigue toxic nitrogen dioxide
• Dizziness gas, which lead to the
• Vomiting formation of smog.

• Acute respiratory distress • Cause air pollution when

syndrome (ARDS) dissolve in water body
• Cause acid rain
• Cause climate change
and global warming
• Cause ozone depletion

Water - • Hyponatremia if consume large -

amount of water.
 Nitrogen 174 ppm • Contact can irritate and burn the • Can damage plant
Dioxide skin and eyes. tissues, decreasing
• Breathing can irritate the lungs growth or reducing crop
causing coughing and shortness yields.
of breath. • Cause acid rains.
• Interfere with the ability to • Cause ozone depletion.
carry oxygen causing headache, • Contributes to global
fatigue, dizziness, and a blue warming and climate
colour to the skin and lips change.
(methemoglobinemia).
• Repeated exposure to high
levels may lead to permanent
lung damage.

Nitric Acid 2.65 mg/L • Inhalation can lead to ocular • Form nitrogen dioxide in
and nasal irritation, sore throat, the presence of the light,
cough, chest tightness, causing depletion in the
headache, ataxia, and ozone layer.
confusion. • Can affect the pH and kill
• Cause delayed pulmonary aquatic organisms.
edema, pneumonitis, bronchitis,
and dental erosion.

Dinitrogen 50 - 138 ppm • A single acute exposure may • Cause acid rains.
Tetroxide cause death. Repeat exposure
to small amounts of nitrogen
oxides may cause lung damage.
• Cause severe skin burns and eye
damage after skin contact.
• Contains gas under pressure,
may explode if heated.

Platinum- - • Skin irritations upon contact. • Can contaminate ground

Rhodium water system.
7.5 Hazard Consequences and Safety Measures
The possible consequences and safety measures on handling the chemicals involved is shown in Table 7.7.
Table 7.7: Associated Hazard, Potential Consequences and Safety Measures of Chemical Involved
Chemical Associated Hazard Potential Consequences Safety Measures

Ammonia - Flammable gas - Decompose at high temperature, - No smoking in the industry area.
- Toxic gas produce flammable hydrogen gas. - Keep away from hot surface, spark and
- Corrosive - High concentration of ammonia will any possible ignition source.
- Hazardous to aquatic environment have irreversible effect on skin and - Store in a well-ventilated place.
respiratory system. - Strictly follow the specific container
- Easily cause fire and explosion at code and close tightly to prevent any
confined spaces. leakage.
- If accidentally inhaled, remove the
victim to ventilated area for fresh air
and immediately call the poison center.
- If get in contact with eyes, rinse with
water immediately and call the poison
center.
- Avoid discharging the chemical into
environment. Dispose it to the licensed
company.
Oxygen - Risk of ignition and fire explosion - Explode if heated; strong oxidizer. - Keep away from combustible
materials.
 - Burns or frostbite may be resulted from - Strictly follow the specific container
in contact with rapidly expanding gas. code and close tightly to prevent any
leakage.
- Stay away from direct sunlight.
- Store in a well-ventilated place.
- No smoking in the industry area.
Nitric Oxide - Corrosive gas - An effective oxidizer that exhibits the - Store in containers that provide a tight
- Hygroscopic gas ability that significantly boost the seal, ensuring limited exposure to
combustion process of many different moisture and sunlight, in a cool and
substances. well-ventilated location.
- Exhibits a notable sensitivity to various - Keep away from exposure to heat,
conditions, particularly during the sources of ignition, as well as moist air
process of distillation. This sensitivity or water.
has been identify as a significant - Wear personal protective equipment
contributing factor to a number of (PPE) such as a face mask, chemical
incidents. safety goggles, gloves, and appropriate
clothing.
- Keep in an area that is separate from
areas that contain grease and oil.
Water - - Health effect if ingestion due to unsafe - Seek medical advice if applicable.
levels contaminants. - Soak up spills with inert solids such as
clay or diatomaceous earth.
 - Worker might fall down due to slippery
surface.
Nitrogen Dioxide - Sensitive to moisture - Combustible and forms a corrosive - Store containers in a location from any
- Corrosive gas solution when reacted with water. possible risk of fire and at a safe
- Hygroscopic gas - A potential for a rapid reaction when distance from sources of heat and
exposed to elevated temperatures. ignition.
- Separate flammable gases and other
materials that are at risk of combustion
within a storage place.
- Keep within a safe distance from
materials that are prone to combustion.
- Store the container in a well-ventilated
area, ensuring that the temperature does
not exceed 50°C.
Nitric Acid - Corrosive metal - Thermal decomposition has the - Ensure that items are stored in
- Oxidizing liquid potential to result in a release of toxic appropriately labeled containers.
gases and vapors. - Use with spark-proof tools and
- - Ignition of fire may occur upon explosion-proof equipment.
contact with combustible or organic - Use only under a chemical fume hood
substances. or in a well-ventilated confined area.
- Avoid contamination to ground water
system.
 Dinitrogen - Flammable gas - Fatal if inhaled. - Evacuate to ventilated area if leak.
Tetroxide - Toxic gas - Explode if heated; strong oxidizer. - No smoking in the industry area.
- Corrosive - Explosion happens if contact with - Strictly follow the specific container
ammonia. code and close tightly to prevent any
- Caused permanent damage to cornea leakage.
and iris. - Prevent in contact with ammonia. Treat
- Overpressure might happen if water the side product immediately and
was added directly. prevent storage.
- Store in a well-ventilated place.
Platinum-Rhodium Flammable solid - Platinum's catalytic properties may - No smoking in the industry area.
encourage the oxidation and ignite of - Equip with explosion-proof instrument.
organic substances. - Extinguish fire with dry sand, alcohol-
- Cause irritation. resistant foam or dry chemical.
- Cause lung damage to workers - Stay away from sparks.
- If accidentally inhaled, remove the
victim to ventilated area for fresh air
and immediately call the poison center.
- If get in contact with eyes, rinse with
water immediately and call the poison
center.
 CHAPTER 8

PLANT LOCATION STUDIES

8.1 Selection of Plant Location for The Nitric Acid Plant

There were three plant locations proposed. Each was evaluated and the final location was decided
based on the maximum net advantages.

8.1.1 Location One: Gebeng Bypass Road, Gebeng Industrial Estate, Pahang, Malaysia.
The fertilizer sector in Malaysia has experienced remarkable growth. In 2020, the country's
fertilizer consumption reached 1,952.1 kilograms per hectare. This represents a substantial
increase from 177 kilograms per hectare in 1971, indicating an impressive annual growth rate of
6.24% over the years (Knoema, 2020). In 2020, Malaysia achieved the highest fertilizer
consumption rate among all countries globally, surpassing New Zealand, which followed with a
fertilizer consumption rate of 1,730 kilograms per hectare (Statista, 2023).

Figure 8.1: Trend of Production of Fertilizer in Malaysia (Statista, 2022)

Figure 8.1 shows the increasing trend of production of fertilizer in Malaysia from 2013 to
2022. Nitric acid is one of the main components in the production of ammonium nitrate and
calcium ammonium nitrate which finds applications as urea and ammonium-based fertilizers. In
short, the high demand of fertilizer in Malaysia indicates that there is a high demand for nitric acid.
Therefore, the suggest location is shown in Figure 8.2.
 Figure 8.2: Satellite Image of Gebeng Bypass Road, Pahang

Coordinates 4°00'45.3"N 103°21'34.4"E (Google Map)

8.1.2 Location Two: Port of Le Harve, France

France is reported as one of the countries that has high demand on nitric acid for the application
of fertilizer, construction and automotive sector. Research has shown that the consumption of the
France fertilizer market is anticipated to increase steadily over the projected period proving the
high demand for nitric acid (Research and Markets, 2022). Besides, France is also dominate in the
construction industry where nitrobenzene is one of the chemicals that plays a vital role in it. Nitric
acid is a crucial raw material in the manufacturing of nitrobenzene, therefore, with the expansion
of construction sector, the demand for nitric acid increase too (Future Market Insights, 2023).

The Port of Le Havre is a deep-sea port located in France which is one of the busiest ports
in France and the fifth largest port in Northern Europe. It consists of different chemical plant such
as fertilizers, plastic and rubber. With direct access to the multimodal connection, for example, the
sea, rail and road, this port is strategic for the supply chain. Also, with an attractive industrial zone
of about total 10000 hectares (free 100 hectares), it provides an enormous logistics space of about
120 hectares (Chemical Parks in Europe, 2023). Figure 8.3 depicts the suggested plant location in
Port of Le Havre.
 Figure 8.3: Plant Location at Port of Le Harve

Coordinates: 49°29'24.7"N 0°12'03.3"E (Google Map)

Location Three: Nanjing Chemical Industrial Park (NCIP) in Nanjing, Jiangsu Province,
China
The Nanjing Chemical Industrial Park (NCIP) is situated in the lively city of Nanjing,
Jiangsu Province, China, and serves as a shining example of China's impressive progress in the
chemical industry. With a strong legacy of innovation, technological expertise, and commitment
to sustainable growth, NCIP has become a leading choice for chemical companies, drawing
interest from both local and global investors who aim to benefit from its strategic benefits
(Schmidkonz, 2005).

In the early 1990s, the NCIP was established with a strategic vision to consolidate and
strengthen China's chemical manufacturing capabilities (Liu, et al., 2022). Over the years, it has
developed into a dynamic and vibrant center of chemical activity. Positioned strategically on the
banks of the Yangtze River, NCIP enjoys a geographical advantage that allows for seamless
connectivity to major transportation networks, facilitating the efficient transportation of raw
materials and finished products within the nation and internationally.

Among China's rapid economic expansion and rising demands for crucial chemical
products, NCIP has emerged as a key player in meeting the nation's growing needs. In an
increasingly interconnected global economy, the decision to construct a nitric acid plant within
this dynamic industrial park holds the potential not only to strengthen China's chemical production
but also to enhance the country's self-reliance and international recognition.

NCIP, being one of China's largest chemical industrial parks, has cultivated a supportive
environment for advanced research, development, and manufacturing. With its state-of-the-art
infrastructure, cutting-edge technologies, and highly skilled workforce, the park offers an ideal
ecosystem for the successful operation of the nitric acid plant. By integrating this new facility into
the well-established network of NCIP, China can substantially strengthen its industrial capabilities
and elevate its standing in the global chemical market (Zeng & Bathelt, 2011).

The demand for nitric acid has been consistently increasing due to its wide-ranging
applications in various industries especially in China. Agriculture, in particular, relies on nitric
acid for fertilizer production, leading to improved crop yield and quality. The population growth
in China increases the demand for food. Thus, the fertilizer used will be increased significantly.
Moreover, the chemical industry significantly uses nitric acid to manufacture diverse products like
explosives, dyes, pharmaceuticals, and plastics (Anastasopoulou, et al., 2016). Additionally, the
growing global emphasis on environmental sustainability has encouraged the use of nitric acid in
producing renewable energy sources like solar cells and biofuels, contributing to the stimulate in
demand for this versatile chemical.

Maintaining a consistent and dependable supply of nitric acid is vital to sustain economic
growth and meet market demands, given its strong and continuous demand. The production of
nitric acid is a complex and energy-intensive process, involving the catalytic oxidation of ammonia.
Therefore, setting up a nitric acid plant necessitates careful consideration of several factors. These
factors include securing access to abundant and cost-effective raw materials, ensuring a stable and
skilled workforce and establishing an efficient transportation network to facilitate the distribution
of the final product. Proper attention to these aspects is crucial for the successful operation and
contribution of the plant to the market.

The specific location of the plant is illustrated in Figure 8.4.

 Figure 8.4: Location of Nanjing Chemical Industrial Park (NCIP)

Coordinates: 32°14'57.8"N 118°49'54.8"E (Google Map)

8.2 Comparison of Potential Location on Different Aspect

Different aspects are discussed in Table 8.1 for better insight of the potential location selected.

Table 8.1: Potential Location and Evaluation on Each Aspect

Site Location Potential Location 1: Gebeng Bypass Potential Location 2: Port of Le Harve, Potential location 3: Nanjing Chemical
Road, Pahang, Malaysia France Industrial Park (NCIP) in Nanjing,
Jiangsu Province, China
Availability of - PETRONAS Chemicals Group - Yara France Ammonia Plant - Sinopec Nanjing Chemical Industrial
Raw Material Berhad. Corporation (Sinopec, n.d.)
(Ammonia) - PETRONAS CHEMICALS
AMMONIA SDN. BHD.
Utilities Electricity Electricity Electricity
- Tenaga Nasional Berhad (TNB) - Électricité de France (EDF) - State Grid Jiangsu Electric Power Co
Water Supply
Water Supply Ltd
- Industrial port supply (52 km of pipe,
- Semambu Water Treatment Plant - Jiangsu Nanjing Power Supply
13.5Mm3/day)
Telecommunication Company
Natural gas
- Telekom Malaysia Water Supply
- Up to 40 bars, all the industrial area are
- Yuangu Water Industry
connected.
Telecommunication
Steam
- China Telecom Nanjing Branch
- Supply over 200,000 tons/yr, 5
industrials connected, additional 10km
steam network in project.
(Chemical Parks in Europe, 2023)
Notable Nitric - PETRONAS Chemicals Group - Matières Plastiques Industrielles, a - Nanjing Quantai I/e Trade Co.,Ltd
Acid Purchaser Berhad plastic fabrication company in Le - Jiangsu Yongli Chemicals
- Polyplastics Asia Pacific Sdn. Bhd Havre, France - Nanjing Chongren Chemical Industry
Eastman Chemicals (M) Sdn Bhd Co., Ltd
Transportation Roads Roads Roads
System and - East Coast Highway which links - Situated at the intersection of the - The Nanjing Yangtze Bridge is known
Infrastructure Kuantan and Kuala Lumpur within 2 major road networks of Europe which as the most famous bridge crossing the
hours. are the the A131 and the A29 Yangtze River. This double-decked
- A railway link connects the integrated highways. truss bridge efficiently accommodates
petrochemical complex in Kerteh - More than ten thousand trucks operate automobiles, trains, and pedestrian
(Terengganu) to Gebeng and Kuantan in the Port of LeHavre every day, traffic, serving as a vital transportation
Port. including some 3500 container-laden link in the region (Yangtze River
- By 2026, the East Coast Rail Link trucks. Cruise, 2009).
(ECRL) which connects the west and - The A28 highway provides direct Air
east coast of Peninsular Malaysia will connection to southwest France, - Nanjing Lukou International Airport
begin operations and further minimize Spain, and Portugal. holds the distinction of being the third
travel time. Air largest airport in eastern China and
Air - There are international flights from serves as a major air hub in the
- 40 km away from Sultan Ahmad Shah Beauvais Paris airport to Brazil, South country. At present, it operates an
Airport. Has multiple domestic routes Korea and China. The airport is about extensive network of over 130 air
and international routes to Singapore. 180 km away from the port. routes connecting 54 domestic
Ports and Waterways destinations and more than 20
- Kuantan International Airport in - The Port of Le Havre is on the Seine international destinations (Nanjing
Gebeng set for 2026 opening. River System and is connected by Airport, 2023).
Ports and Waterways inland river to one of Europe's main - Nanjing Ma'an International Airport
- Kuantan Port, a strategic and consumer areas, the Ile-de-France has been constructed primarily to cater
convenient location that is distanced region. to the transportation needs of the
around 1104 nautical miles from Railways northern part of Jiangsu Province and
Qinzhou Port (An industrial zone in - The main high-performance rail the northeast part of Anhui Province
China). It takes only around 3 – 4 days networks in Europe are linked to the (Travel China Guide, 2023).
to reach. port Port and Waterways
- Takes around 4 – 8 days to reach other - Since late 2005, Naviland Cargo - The Port of Nanjing holds the
ports in China. (Franch) has been the primary distinction of being the world's largest
- Facing South China Sea, a gateway provider of container train services in inland port. Situated on the lower
access to tremendous growth potential the port. reaches of the Yangtze River, it serves
of ASEAN and Asia Pacific market. - Two weekly journeys to Strasbourg as a crucial transportation hub for the
City Infrastructure and five weekly trips to Lyon and region (Waters, 2023).
- The metro system and highway are Bordeaux City Infrastructure
constantly expanding. (World Port Source, n.d.) - Nanjing Jiangbei New Area
Railways
- Nanjing North Railway Station,
Nanjing West Railway Station and
Nanjing South Railway Station (China
Airline Travel, 2023).
Availability to Firefighting facilities - Care in Le Havre: Specialised Firefighting facilities
Support - Equipped with HAZMAT (hazardous platforms to handle hazardous - HAZMAT (hazardous material)
Services material) facilities. For example, product. facilities are available.
Pahang Fire and Rescue Department, - Equipped with SEREP to treat
Petronas Centralised Emergency polluted industrial water.
Facilities and Gebeng Emergency (Chemical Parks in Europe, 2023)
Mutual Aid (GEMA).
Government - Pioneer Status with income tax - NACAG provides new incentives for - The Chinese government frequently
Incentives exemption of 100 % of statutory the installation of effective N2O provides diverse investment
income for a period of 5 years. abatement technology (NACAG, n.d.) incentives to attract both local and
Unabsorbed capital allowances as well - Tax break amounting to 30% of annual international investors to designated
as accumulated losses incurred during R&D expenses up to €100 million industrial parks such as NCIP. These
the pioneer period can be carried (OECD, 2021) incentives can include subsidies of up
forward and deducted from the post - The French government put initiatives to RMB 5 million which equivalent to
pioneer income of the company. in bring down the energy prices to the US$692,319 (Interesse, 2022).
- Investment Tax Allowance of 100 % level of their international - The Nanjing Chemical Industrial Park
on the qualifying capital expenditure counterparts for most energy-intensive will receive a tax benefit with a
incurred within a period of 5 years. industry. lowered enterprise income tax rate of
The allowance can be utilised to offset - To support industrial modernization 15%. Additionally, during the third to
against 100 % of the statutory income and new production lines, €3.5 billion fifth years of operation, the park will
for each year of assessment. Any have been provided by the be entitled to a reward where 50% of
unutilised allowances can be carried government.
 forward to subsequent years until fully the enterprise income tax paid will be
utilised. returned to the park.
- Manufacturing companies in - The maximum amount that
Malaysia are qualified for a tax multinational corporations can receive
exemption on statutory income when establishing R&D facilities in
equivalent to 15% of the value of Nanjing is RMB 5 million
increased exports, provided that the (US$692,252).
goods exported attain at least 50% - Foreign-funded investment companies
value-added. or foreign-funded regional
headquarters that meet the standards
recognized by the Ministry of
Commerce will be given a start-up
subsidy of no more than 5 million
yuan, and the rewards will be cashed
in proportions of 40%, 30%, and 30%
in three years.
Environmental - Integrated industrial area, - Emission of N2O causes greenhouse - Environmental protections are
and Social environmental precautions are effect, hence abatement technology is enforced throughout the integrated
Impact enforced. enforced. industrial sector.
- Unemployment rate was 11.8%, new
establish plant provides employment
opportunities (CEIC, n.d.)
Investment - A world-class chemical and - Has competitive advantages such as - The development in NCIP is
Climate petrochemical industrial zone. superior infrastructure, tax incentives concentrated in the following six
- MCKIP, known as the first Malaysia programmes, highly skilled labour fields: fine chemicals, polymers, life
National Industrial Park joint, with degrees from prestigious sciences and pharmaceuticals,
developed by both Malaysia and engineering institutions. petrochemicals and natural gas
China is located inside the Gebeng - France’s chemical industry serves a derivatives, as well as basic organic
industrial area. wide range of downstream clients and chemical feedstock. NCIP will be the
- Goal: major base of advanced string foundation in the fields of focal point for significant international
manufacturing, modern logistics, agricultural, automotive, energy and chemical investments during the
energy, and raw materials, centre for plastic. coming several years. NCIP was the
shipping finance. - France has geographic advantages as it second chemical industrial park in
- Industrial and production base of is located in the central of Europe and China.
plastics, chemical and petrochemicals, its strategic location between Northern - The largest inland-river port in China
metal industry equipment, auto parts, Europe and the Mediterranean Sea. for the transfer of petrochemical and
stainless steels, food processing, liquid chemical goods is Nanjing Port.
carbon fibre, electronics and electrical - By 2035, it is anticipated that the city
appliances, information will grow to the size of a megacity,
communications, consumer goods and with a permanent population of over
renewable energy. 10 million and a total GDP of RMB 2
trillion ($277 billion).
Other Notable - Created more than 24,000 job - Over 2,600 corporate researchers and - The actual amount of foreign capital
Insights opportunities in 2016. 800 academic researchers in Rouen, used in 2021 was US$5.01 billion, an
- Has more than 50 international Caen and Le Havre universities. increase of 11.1 percent over the
companies - Four high engineering schools with previous year. Since China's reform
- Malaysia – China trade hits US $100 R&D laboratories and training and opening up, around 10,000
billion in 2018. programmes in Chemical Engineering, foreign-invested companies have
- Tremendous growth in the last decade, Materials and Plastic Processing flocked to Nanjing.
attracting a total investment of more (Chemical Parks in Europe, 2023) - By 2020, the city has spent more than
than RM30 billion. RMB 40 billion ($5.69 billion) on
research and development.
Labour Supply - The working age population has - The working age population was - Working age population is 4.7 million
increased from 16.8 million in 2006 27.27 million in 2021 in 2022.
to around 22.31 million in 2017
(Statista, 2022).
Economic In 2022 In 2022 In 2022
Facts Population: 1.54 million people Population: 67.9 million people Population: 9.144 million (metro area)
GDP: RM61,395 million GDP: €2351 billion GDP: RMB 1.635 trillion
GDP Per Capita: RM47,177 GDP Per Capita: €39214 GDP per capita: RMB 170,450
Minimum Hourly Wage: RM7.21 Minimum hourly wage: €11.52 Minimum Hourly Wage: RMB 20
Minimum Monthly Wage: RM1,500 Minimum monthly wage: €1,747.20 Minimum Monthly Wage: RMB 2280
(The Sun Daily, 2023). (35 hours/week) (China Briefing, 2022)
(Choose France, 2023)
8.3 Selection and Justification for Plant Location

The choice of plant location depends significantly on the company’s values and size. Table 8.1
listed all the relevant factors, making it easier to compare and select the most suitable location
efficiently. Out of the suggested potential locations, China stands out with its highly developed
chemical industrial park. Both China and France have a significant economic advantage due to
ample raw material supply and strong demand in various industries. On the other hand,
Malaysia’s market demand is notably lower than that of China and France, which is expected
given its smaller size as a country.

Other than considering the economic prosperity, the plant locations’ geographical
accessibilities and transportations should be focused. In China, NCIP is approximately 75 km
away from the Nanjing Lukou Airport, the third largest international airport in eastern China.
With its extensive network of over 130 air routes connecting 54 domestic and more than 20
international destinations. It is beneficial for exports and logistics supports in terms of service
and transport. In addition to that, selecting China as the location offers cost and time savings
in product transportation compared to France, as the airport is approximately 180 km away
from the port. On the other hand, Malaysia’s airport is closer, but it lacks the extensive network
of both domestic and international flights available in China, providing only multiple domestic
routes and international flights limited to Singapore.

Furthermore, the seaport of Nanjing, situated in China, holds the distinction of being
the world’s largest inland-river port, playing a pivotal role as a crucial transportation hub for
the region. Positioned on the lower reaches of the Yangtze River, it enjoys seamless
accessibility to China’s extensive hinterland and maintains excellent connectivity with major
industrial and commercial centres. Additionally, serving as a significant component of the
maritime Silk Road, the port facilitates trade between China and various countries in Asia,
Europe, and Africa. The journey from NCIP to the port via Jiangbei Boulevard Expressway
typically takes around 32 minutes.

Nanjing has an ample labour supply, and statistics indicate a rise in the working-age
population across China. When comparing labour costs, the minimum hourly wage in China is
nearly five times lower than that in France. Additionally, frequent labour strikes in France over
the past few years suggest that it may not be an ideal location for establishing a new plant. On
the other hand, despite Malaysia’s lower labour cost, its working population is not as abundant
as that of China, potentially impacting the availability of skilled labour. Lastly, it is worth
noting that the Chinese government regularly offers a variety of investment incentives to attract
both local and international investors to NCIP.

In conclusion, the most favourable location for nitric acid production is deemed to be
NCIP, China. It offers a host of advantages, ranging from its strategic location and robust
infrastructure to a skilled labour force and government incentives. These factors collectively
make it a prime choice for businesses looking to build a new plant, capitalize on China’s
economic growth, and access both domestic and global markets.