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UEMK4324 Process and Plant Design I

Production of Ammonia

Assignment 2
Feasibility Study on Process Plant

Rev. Date
0 13/02/2020

Group No: 1

Student ID Name

1600139 Udayanair Balakrishnan Nair

1606658 Chan Xu Yao

1600582 Tai Jin Jin

1600607 Woh Ye Wei

1600485 Wong Li Xuan


TABLE OF CONTENTS

TABLE OF CONTENTS ii
OBJECTIVES 1

CHAPTER
1 FEASIBILITY STUDY ON PROCESS PLANT 2
1.1 Background of the Process Design 2
1.1.1 History of Ammonia 2
1.1.2 Chemical and Physical Properties of Ammonia 3
1.1.3 Application of Ammonia 5
1.2 Marketing and Business Studies 6
1.2.1 Market Survey 6
1.2.2 Supply and Demand 7
1.2.3 Price Trend 8
1.2.4 Future Prospect of the Product 9
1.3 Plant Capacity 11
1.4 Reaction Pathway 12
1.4.1 Analytic Study of Various Reaction Pathway in Ammonia Production 12
1.4.2 Gross Profit Evaluation of Various Reaction Pathways 40
1.4.3 Selection of The Optimal Pathway 47
1.5 Plant and Process Safety Consideration 52
1.5.1 Chemical and Physical Properties of the Identified Chemicals 52
1.5.2 Flammability and Toxicity Properties of the Identified Chemicals 52
1.5.3 Possible Consequences and Safety Measures of the Identified Hazards 53
1.5.4 List of SDS Sources 55
1.6 Plant Location 63
1.6.1 Oryol Industrial Park, Oryol Region, Russia 63
1.6.2 Kwinana Industrial Park, Perth, Western Australia, Australia 68
1.6.3 PT. Indonesia Morowali Industrial Park (IMIP), Sulawesi Tengah Region,
Indonesia 76
1.6.4 Selection of the Most Optimal Plant Location 82
REFERENCES 84
APPENDICES 89

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OBJECTIVES

i. To study on the background of the process, properties and the various applications of
ammonia.
ii. To conduct an analysis on the market and business studies on ammonia as well as the
current and future trends of ammonia.
iii. To design a plant design scheme with maximized production capable in fulfilling the
consumer demand on a local as well as global scale.
iv. To research and propose a suitable location for the plant and the capacity of the overall
production.
v. To study on the different possible ammonia production pathways and identifying the most
optimum alternative.
vi. To identify all hazards associated with the chemicals used for production and referring to
safety data sheets (SDS).
vii. To propose recommendations on safety measures in handling identified hazards.
viii. To design a plant with quality production while abiding to the environmental safety
regulations and occupational health standards.

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CHAPTER 1

1 FEASIBILITY STUDY ON PROCESS PLANT

1.1 Background of the Process Design

1.1.1 History of Ammonia


The first discovery and collection of gaseous ammonia were done by an English chemist, Joseph
Priestley in 1774. In the year of 1785, a French chemist carried out further investigation in order
to identify the composition in the gaseous ammonia discovered. After that, Adolph Frank and
Nikodem Caro found out that nitrogen can be used to react with calcium carbide to form calcium
cyanamide. The calcium cyanamide formed in the reaction could then undergo hydrolysis to form
ammonia. However, this reaction pathway was not utilized much in the production of ammonia in
the early 20th century because a lot of energy is needed in order to carry out this production process.
(Pattabathula and Richardson, 2016)

People used more than 100 years to study on how to convert nitrogen into ammonia since
all the discovered reaction pathways were hard to apply in the industry until the emerge of a
process invented by Fritz Haber, a German chemist. The technology found led to a huge
breakthrough in the development of the modern ammonia industry. This technology patent was
sold to BASF, a German chemical company. Carl Bosch, the German chemist, scaled the
laboratory-scaled technology into industrial-scaled. Hence, the synthesis process of ammonia is
now known as the Haber-Bosch process, as shown in Figure 1.1. (Varotto, 2015) The raw feed
materials used in this process are nitrogen and hydrogen. This synthesis process is an exothermic
and reversible reaction. Therefore, the temperature of the process must be maintained at around
400 to 450 °C, while the pressure should be kept at 200 atm. The first commercial ammonia
production plant based on Haber-Bosch process was built by BASF in Oppau, Germany with a
production capacity of 30 metric tonne per day. (Pattabathula and Richardson, 2016)

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Figure 1.1: The Haber-Bosch Process Flow for the Synthesis of Ammonia. (Clark, 2013)

1.1.2 Chemical and Physical Properties of Ammonia


Ammonia is a nitrogen-hydrogen compound with the chemical formula of NH3 and the molecular
weight of 17.031 g/mol. As shown in Figure 1.2, the molecular structure of ammonia is in trigonal
pyramidal shape with the nitrogen atom located at the apex of pyramid. The nitrogen atom passes
through the hydrogen triangle plane continuously like an umbrella turning inside out when the
strong wind blows, this motion is the so called inversion. Naturally, ammonia exists in the Earth
mainly attributes to the volcanic activities or decomposition of nitrogen-containing substances.
(Appl, 1999) At room temperature, ammonia exists as a colourless gas with a strong pungent odour,
which can be found easily in the toilets, but it is usually exported and delivered to the customer as
a compressed clear liquid in sealed container or cylinders. Ammonia can be liquefied easily due
to the strong hydrogen bonding formed in between the molecules. Besides, ammonia is a type of
flammable gas which will reacts with oxygen to produce nitrogen and water, or nitrogen (II) oxide
and water.

Figure 1.2: The Molecular Structure of Ammonia. (Kraemer, 2018)

Some general information of ammonia is listed in Table 1.1 that follows.

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Table 1.1: General Information of Ammonia.
Properties Properties Value References
IUPAC Name Azane (National Center for
Biotechnology Information, 2020)
Molecular Formula NH3 or H3N (International Labour
Organization, 2013)
Molecular Weight 17.0 (International Labour Organization,
(g/mol) 2013)
Physical State Gaseous state (Lide, 2005)
(Room Temperature)
Colour Colourless (International Labour Organization,
2013)
Odour Strong pungent smell (International Labour Organization,
2013)
Melting Point (°C) -77.7 (O’Neil, 2013)
Boiling Point (°C) -33.35 (O’Neil, 2013)
(at 760 mmHg)
Flash Point (°C) 132.3 (Lide, 2005)
Auto-ignition Temperature 630 (International Labour Organization,
(°C) 2013)
Relative Density (g/L) 0.70 (International Labour Organization,
2013)
Solubility in Water 0.54 (International Labour Organization,
(g/mL at 20 °C) 2013)
Vapour Pressure 1013 (International Labour Organization,
(kPa at 26 °C) 2013)
Heat of Combustion 382.8 (Lide, 2005)
(kcal/mol)
Heat of Vaporization 5.581 (O’Neil, 2013)
(kcal/mol)
pH (Aqueous Solution) 0.01 N: 10.6 (O’Neil, 2013)
0.10 N: 11.1
1.00 N: 11.6
Specific Heat (J/kg·k) 2097.2 at 0 °C (Eggeman, 1999)
2226.2 at 100 °C
2105.6 at 200 °C

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1.1.3 Application of Ammonia
Ammonia has been widely used in various industries, as shown in Figure 1.3. Normally, it is being
used as the source of nitrogen in the chemical reaction processes. Ammonia can be utilized in the
production process of some products that people need to use daily.

Figure 1.2: The Application of Ammonia in Various Industries. (Grand View Research, 2017)

Based on Figure 1.3, most of the ammonia produced by the industry is used in agricultural
sector as fertilizers. Ammonia contains nitrogen which is one of the essential elements that is
needed by the plants to grow. The presence of nitrogen content in the fertilizers will affect the
ability of a plant to produce protein. Besides, ammonia also can be used to manufacture liquid
fertilizer solutions which contain ammonia, urea and aqua ammonia. Ammonia is one of the
sources of livestock feeds. In most of the agricultural industry, ammonia and urea are used as a
source of protein to feed the animals. Moreover, ammonia can be used to provide a protective layer
for long term storage of some crops such as corn. (Grand View Research, 2017)

Due to its unique thermodynamic properties, ammonia can absorb a significant amount of
heat energy from surroundings, thus ammonia is widely used as a type of refrigerant gas in cold
storage industry or in the air-conditioning devices. Ammonia is the most environmental-friendly
refrigerant in the world because the usage of ammonia will not deplete the ozone layer or lead to
pollution. Hence, the refrigeration system that used ammonia as its refrigerant is considered to be
more sustainable and safer to use as compared to other chemical refrigeration systems. (Grand
View Research, 2017)

Ammonia is used as the starting material in the manufacturing process of drugs. The drugs
that used ammonia to produce have the function to inhibit the growth and multiplication of certain
species of bacteria. Besides, ammonia is one of the strong antiseptics. Gaseous ammonia is widely

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used in medical field as a respiratory stimulant in order to prevent people from fainting. (DrugBank,
2015)

Ammonia is one of the materials used in order to manufacture synthetic fibres such as
rayon and nylon. Ammonia is used in the manufacturing process of caprolactam as a neutralizing
agent in order to make sure the pH value of the reaction is always around 7. Caprolactam is the
raw material used to produce nylon fibres. Apart from that, the catalytic oxidation of propylene
and ammonia will produce acrylonitrile which can be used to manufacture acrylic fibres and resins.
Moreover, ammonia is used in the cotton dyeing process. (Zumdahl, 2018)

As a type of chemical compound, it is not only being used in the manufacturing process,
ammonia can be used in daily household cleaning process. For example, ammonia itself or the
cleaning products that contain ammonia can be used to clean the bathtubs, sinks, tiles and so on.
The dirty stains can be removed easily if household cleaning agents that contain ammonia is used.
(ChemicalSafetyFacts.org, 2020)

Apart from that, ammonia is also being utilized in petroleum industry. Ammonia is used to
neutralize the acid constituents of crude oil. It also helps to prevent the corrosion to occur on the
drilling equipment. (Hanania, Stenhouse and Donev, 2015)

1.2 Marketing and Business Studies


1.2.1 Market Survey
China, the most populous country in the world, is the largest consumer of ammonia in the Asia
Pacific region and in the global market. With just 11.3% arable land, there is a need to produce the
crops with a higher yield to meet the high agricultural products demand. The demand for food
grains is then driving the fertilizers market. (Mordor Intelligence, 2018)
In Asia Pacific, India is the second largest ammonia consumer with 99% of urea in the
country is used for direct application for growing food crops, which are mainly paddy rice and
wheat. Indonesia is the third largest ammonia consuming country in the region, which is mainly
driven by urea demand as a direct application fertilizer. Meanwhile, biofuel industry contributes
significantly to urea demand in Thailand. (Wainwright, 2018)
In Europe, fertilizer companies have been involved in long-term agreements in recent years
with other market players, who are dealing with ammonia and its products. For instance, in 2016,
Yara International made an agreement with MicroAccount to acquire one of their business segment,

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the Farm Management System business in Bulgaria and Romania. This segment is associated with
the trading of fertilizers and other agrochemicals. (Persistence Market Research, 2017)
In Latin America, Argentina and Brazil are the prominent crop producer countries. The
consumption of fertilizers in this region was around 11% of the global consumption. Trinidad and
Tabago is the major exporter of ammonia, with the export capacity of 4.4M tonnes. (Persistence
Market Research, 2017)
In Middle East and Africa, the demand for ammonia for the production of modified
fertilizers is raising remarkably. The demand accounted for approximately 46% of the global
estimated demand for ammonia, which as pegged at approximately 62M tonnes in 2016. Fertilizer
manufacturers are focusing on establishing a direct supply chain with the oil and gas refineries to
produce nitrogen directly from refineries and from chemical manufacturers in order the enhance
the production, which will decrease the inventory cost and increase their operational efficiency.
(Persistence Market Research, 2017)
In North America, there has been a considerable decrease in the quality of soil due to the
regular use of chemical fertilizers. In order to apply sustainable methods of agriculture, the demand
for organic fertilizers is increasing. As a consequence, the growth of inorganic fertilizers including
those derived from ammonia might face challenges in the near future, which in turns affecting the
ammonia market growth. (Persistence Market Research, 2017)
In Malaysia, Petronas Chemicals Group Berhad (PChem) is the major ammonia
manufacturer in Malaysia and South East Asia. The plants are located at Kertih (1.13 million
tonnes per annum inclusive of oxogas and carbon dioxide production), Gurun (1.15 mtpa inclusive
of urea and methanol production), and Bintulu (1.20 mtpa inclusive of urea production). Sabah
Ammonia and Urea (SAMUR) Project introduced by PChem in 2016 is a green field urea
production facility located at Sipitang, Sabah with methane as feedstock. The cost is $1.9B with
urea and ammonia capacities of 1.20 mtpa and 0.74 mtpa respectively. The main export
destinations of the products are Thailand, Australia and New Zealand. However, excess supply
and low demand of ammonia and urea from industrial application were observed in the same year.
(Petronas Chemicals Group Berhad, 2016)

1.2.2 Supply and Demand


According to The Observatory of Economic Complexity (2017), the top exporters of ammonia are
Trinidad and Tobago ($965M), Russia ($789M), Canada ($467M), Saudi Arabia ($455M) and
Algeria ($425M). The top importers are the United States ($1.11B), India ($600M), South Korea
($381M), Ukraine ($276M) and Belgium-Luxembourg ($263M).

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China, Russia, United States and India have the highest ammonia production and reserves,
with 43.6M, 14M, 11.6M and 10.8M metric tons of ammonia being produced in 2017 respectively.
(U.S. Department of the Interior and U.S. Geological Survey, 2019)
Being as the largest corn producer and exporter in the world, United States highly relies on
the import of ammonia despite of its large ammonia capacity. Its large corn plantings maintain the
continued demand for nitrogen fertilizers. According to the United States Department of
Agriculture (USDA), the country corn growers planted 36.1M hectares of corn in the 2018 crop-
year. Corn acreage in the 2019 crop-year is expected to remain similar because of anticipated
higher returns for corn compared with other crops. Trinidad and Tobago contributed 66% to the
ammonia import sources of U.S. (U.S. Department of the Interior and Unite States Geological
Survey, 2019)
The global ammonia market concentration is fragmented in nature, in other words, the
market is highly competitive without dominant players. However, the reputable ammonia
manufacturing companies include BASF SE, Qatar Fertiliser Company, SABIC, CF Industries
Holdings Inc., and EuroChem. (Mordor Intelligence, 2018)
CF Industries Holdings, Yara International and Nutrien are the top global producers of
ammonia, with capacities of 10.10 mtpa, 8.20 mtpa and 7.50 mtpa, respectively, in 2017.
(GlobalData, 2018)

1.2.3 Price Trend


Figure 1.4 shows the average prices of anhydrous ammonia in United States as reported by the
USDA. Since 2015, the prices have ranged from a higher of more than $700 per tonne to a low of
$400 per tonne. After anhydrous ammonia spent most of 2018 around $500 per tonne, prices
jumped to more than $600 per tonne in early 2019. The prices have then fallen about 22% from
the spring prices. The increase in intended corn acres for 2019 helped drive the prices up at the
beginning of the year and falling commodity prices could be contributing to the decline. The
intended corn acres for 2020 will determine if prices shift in the new year. (Branch, 2019)

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Figure 1.4: Reported Prices for Anhydrous Ammonia, Urea, and Liquid Nitrogen (28%) in Jan
2015 – Jan 2019. (Widmar, 2019)
Figure 1.5 illustrates the average prices of anhydrous ammonia in China as reported by
China Petroleum and Chemical Industry Federation. The price was reported at 3,160 RMB per
tonne in November 2019. This records a decrease from the previous number of 3,200 RMB per
tonne for October 2019. The data reached an all-time high of 3,550 RMB per tonne in October
2018 and a record low of 1,960 RMB per tonne in July 2016. (CEIC Data, 2019)

Figure 1.5: China’s Average Monthly Market Price for Liquid Ammonia (>99.8%) in Jan 2015 –
July 2019. (CEIC Data, 2019)

1.2.4 Future Prospect of the Product


According to Fior Markets (2019), the global ammonia market is expected to grow from $52.71B
in 2017 to $81.42B by 2025, at a compound annual growth rate (CAGR) of 5.59% during the
forecast period from 2018 to 2025. CAGR is the rate of return that would be required for an
investment to grow from its beginning balance to its ending balance, assuming the profits were
reinvested at the end of each year of the investment’s lifespan. (Murphy, 2019) Asia Pacific region
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emerged as the largest market for ammonia with a 39.26% share of revenue in 2017. Increasing
demand is anticipated to boost Asia pacific region to grow at a CAGR of 7.89% over the forecast
period. It is worth mentioning that the application of ammonia as refrigerant in large cooling
system grows at the highest CAGR of 7.67% because of its high efficiency and better heat transfer
properties. Ammonia is now being favourable as a refrigerant as it exhibits zero ozone depletion
potential. (Fior Markets, 2019)
Global ammonia capacity is expected to experience a considerable growth over the
upcoming years from around 230 mtpa in 2018 to more than 280 mtpa by 2030. Around 103
planned and announced ammonia plants are expected to come online, primarily in Asia and the
Middle East, as shown in Figure 1.6. (GlobalData, 2019)

Figure 1.6: Global Planned and Announced Ammonia Capacity Additions by Top Ten Countries
(mtpa). (GlobalData, Oil and Gas Intelligence Center, 2019)

Within Asia, India is set to have large capacity additions of 9.27 mtpa by 2030 in order to
target the country’s increasing fertilizer demand and import substitution, which will then
contribute around 20% of the global total ammonia capacity additions. (GlobalData, 2019)
Within the region of Middle East and Africa, Iran is identified as the second highest country
in terms of capacity additions. The country is set to add 7.67 mtpa of planned and announced
ammonia capacity from newly built and expanded plants by 2030. (GlobalData, 2019)
Dangote Industries Ltd, Oteko and Nagarjuna Fertilizers and Chemicals Ltd are expected
to lead globally with highest ammonia capacity additions of 2.90 mtpa, 2.50 mtpa and 2.05 mtpa,
respectively in 2030. (GlobalData, 2019)

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1.3 Plant Capacity
The production capacity of a chemical plant is a fundamental measure of its economic potential,
and an integral factor in the assessment of a plant’s value. It can be defined as the maximum
average throughput that satisfies four constraints: i) it takes into account the production restrictions
imposed by the existing equipment, materials, and labour; ii) it is sustainable for an extended and
specified period of time; iii) it assures product quality requirements are met; and iv) it does not
exceed the safe operating limits of the facility. (Ogle and Carpenter, 2014)

Based on the previous studies in Chapter 2, it can be clearly seen that the global ammonia
demand is expected to increase steadily in the coming years mainly due to the need of more
fertilizers in order to produce more agricultural products for global increasing population.
Therefore, it might be ideal for the interested investors to penetrate this sector.

It is stated by GlobalData that there is a 50 mtpa increase in ammonia demand from 2018 to 2030.
Based on Figure 2.3, the total global planned and announced ammonia capacity additions is
roughly 42 mtpa by 2030, indicating that there is around 8 mtpa of ammonia still in demand. Since
the ammonia production plants worldwide have an average capacity of 0.8 to 2 mtpa, therefore,
the new ammonia production plant is proposed to have a capacity of 1 to 1.5 mtpa, provided that
the mode and sustainability of the production are outstanding enough in order to compete with the
other suppliers, and to reduce the risk of oversupply.

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1.4 Reaction Pathway
1.4.1 Analytic Study of Various Reaction Pathway in Ammonia Production
The most fundamental method to synthesize ammonia in the current practice of the industry is via
the Haber- Bosch Process. The Haber – Bosch Process was created by Fritz Haber in 1905 which
was developed in 1910 by Carl Bosch. In this process, ammonia is manufactured from the mixing
of Hydrogen and Nitrogen gas at approximated ratio of 3:1. This mixture of gas is pressurized to
high pressures of up to 300 bar and preheated to 400 to 500°C prior to reacting over a catalyst
where traditionally iron is used. (Pattabathula & Richardson, 2016) . Therefore, the raw materials
required for the synthesis of ammonia is gaseous Nitrogen and Hydrogen.

Haber Process 𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇋ 2 𝑁𝐻3 (𝑔) ∆𝐻°𝑟𝑥𝑛 = −92.44 𝑘𝐽/𝑚𝑜𝑙 (1)

Haber process is the most common method used to manufacture ammonia, however there exist
variations amongst production plant globally. The variation results from the production of
hydrogen gas technology. This is because, nitrogen can be easily obtained from the air but there
are several methods to produce the hydrogen gas. In this age, the most commonly used feedstock
to produce hydrogen would be based on fossil fuels such as light hydrocarbons and coal. However,
the ammonia synthesis process is independent of the type of synthesis gas production process,
although the operating conditions is affected by the quality of the synthesis gas. (Appl, 1999)
Therefore, the production of ammonia in corresponding to different hydrogen production
technology is analysed in various feedstock and will be discussed in next sub-section as is Table
1.2 below; For all the reaction pathway discussed, the list of all chemicals involved is as shown in
Table 1.3.
Table 1.2: Summaries of Reaction Pathway
Reaction Process Section
Pathway
I. Natural Gas-Based Hydrogen Production - Steam Reforming 1.4.2
II. Coal-Based Hydrogen Production – Coal Gasification 1.4.3
III. Water-Based Hydrogen Production – Alkaline Electrolysers 1.4.4
IV. Biomass-Based Hydrogen Production- Biomass Pyrolysis 1.4.5
V. Outsourcing of Hydrogen 1.4.6

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Table 1.3: Chemicals Involved in all Reaction Pathways of Ammonia Production.
Chemical Molecular Chemical Chemical Structure Reaction
Weight Formula Pathway
Methane 16.04 CH4 I,II,

Water 18.02 H2 𝑂 I,II,III,IV

Oxygen 32.00 𝑂2 I,II,III,IV

Nitrogen 28.01 N2 I,II,III,IV

Hydrogen 2.016 H2 I,II,III,IV

Carbon 28.01 CO I,II


Monoxide

Carbon Dioxide 44.01 CO2 I,II

Coal (Carbon) 12.01 C II

Sodium 40.00 NaOH III,IV


Hydroxide

Potassium 56.11 KOH III,IV


Hydroxide

Ammonia 17.03 𝑁𝐻3 I,II,III,IV,V

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1.4.1.1 Reaction Pathway I: Natural Gas-Based Hydrogen Production - Steam Reforming

Figure 1.7: Modern Ammonia Plant with Natural Gas Feed. (Pattabathula & Richardson, 2016)

Natural gas is a hydrocarbon composed of Methane (CH4). Therefore, in this reaction, natural gas
would be used as a feedstock in the production of ammonia. Based on Figure 1.7, the natural gas
undergoes catalytic steam reforming (SMR) at high temperature, where the natural gas reacts
with steam over a Nickel based catalyst to produce bulk hydrogen and carbon monoxide in a
reversible process. Along with, the steam reforming method is employed in over 85% of world
ammonia production. (Baboo, 2015). Assuming the feed contains pure methane, 50 % of the
hydrogen produced is from the methane and remaining is produced from water. Since this reaction
is highly endothermic, in accordance to Le Chatelier's principle, a large amount of heat is required
to shift the equilibrium to the right. In addition, the steam to carbon ratio of the feed is customarily
3.0 but varies between 2.5 to 5.0 because a high steam to carbon ratio is required to prevent the
formation of coke. The operating conditions of the primary reformer are typically around 40 bar
with a temperature of up to 1100°C. The exit stream of this process consists of hydrogen, carbon
monoxide, methane, and water. The steam reforming reaction is usually followed by the water gas
shift reaction where carbon monoxide is reacted with steam to produce carbon dioxide. The
reactions that takes place in the primary reformer is shown in the equations 2 to 5. (Appl, 1999)

General Steam
𝐶𝑛 𝐻2𝑛+2 (𝑔) + 𝑛𝐻2 𝑂(𝑔) ⇋ 𝑛𝐶𝑂(𝑔) + (2𝑛 + 1)𝐻2 (𝑔) (2)
Reforming

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Assuming Methane (CH4) is used,

Primary
𝐶𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ⇋ 𝐶𝑂(𝑔) + 3𝐻2 (𝑔) ∆𝐻°𝑟𝑥𝑛 = +206 𝑘𝐽/𝑚𝑜𝑙 (3)
Reformer
Primary
𝐶𝑂(𝑔) + 𝐻2 𝑂(𝑔) ⇋ 𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) ∆𝐻°𝑟𝑥𝑛 = −41.20 𝑘𝐽/𝑚𝑜𝑙 (4)
Reformer
Overall
Equation of
𝐶𝐻4 (𝑔) + 2𝐻2 𝑂(𝑔) ⇋ 𝐶𝑂2 (𝑔) + 4𝐻2 (𝑔) ∆𝐻°𝑟𝑥𝑛 = +164.8 𝑘𝐽/𝑚𝑜𝑙 (5)
Primary
Reformer

Thus, the remaining methane in the exit stream (5-15 %) of the primary reformer is reacted
with oxygen in the secondary reformer to produce hydrogen, carbon monoxide and carbon dioxide
and not to mention, to supply the required amount of nitrogen for the synthesis of ammonia. The
reaction in the secondary reformer is exothermic due to the reaction between hydrogen and oxygen.
The heat generated provides the necessary temperature required for the complete conversion of
remaining methane into hydrogen and oxides of carbon. (Appl, 1999) The reactions that take place
in the secondary reformer is shown below. AL-Dhfeery & Jassem (2012), stated Eq. 6 and 7 depicts
the combustion reaction that provides the necessary energy for the reforming reaction as in Eq. 8.

Secondary 3
𝐶𝐻4 (𝑔) + 𝑂2 (𝑔) ⇋ 2𝐻2 𝑂(𝑔) + 𝐶𝑂(𝑔) ∆𝐻°𝑟𝑥𝑛 = −519.8 𝑘𝐽/𝑚𝑜𝑙 (6)
Reformer 2
Secondary 1
𝐻2 (𝑔) + 𝑂2 (𝑔) ⇋ 𝐻2 𝑂(𝑔) ∆𝐻°𝑟𝑥𝑛 = −242.0 𝑘𝐽/𝑚𝑜𝑙 (7)
Reformer 2
Secondary
𝐶𝐻4 (𝑔) + 2𝐻2 𝑂(𝑔) ⇋ 𝐶𝑂2 (𝑔) + 4𝐻2 (𝑔) ∆𝐻°𝑟𝑥𝑛 = +164.8 𝑘𝐽/𝑚𝑜𝑙 (8)
Reformer
Overall
Equation of 2𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) ⇋ 𝐶𝑂2 (𝑔) + 𝐶𝑂(𝑔) + 𝐻2 𝑂 + 3𝐻2 (𝑔)
(9)
Secondary ∆𝐻°𝑟𝑥𝑛 = −597.0 𝑘𝐽/𝑚𝑜𝑙
Reformer

In addition, natural gas contains significant amount of organic sulphur compounds of up to


10 ppm by volume that are very detrimental to the performance of the iron catalysts used in this
reaction. Hence, prior to the steam reforming reaction, the natural gas feed undergoes a
desulphurization process. Firstly, the feedstock is preheated in the convection area of the primary
reformer to 350-400°C and it is treated in the desulphurization vessel. Next, the organic sulphur
compounds are converted to hydrogen sulphide over a bed of cobalt-molybdenum catalysts that is
supported by a specially treated alumina. Then, the hydrogen sulphide is removed by allowing the
process stream to flow over the pelletised zinc oxide catalyst. Once, the zinc oxide bed is exhausted
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it is usually replaced instead of regenerated. The exit stream usually contains less than 0.1ppm of
sulphur compound. Commonly, the hydrogen utilized in this reaction is recycled from the
synthesis process. (Steinberger-Wilckens & Sampson, 2019)

Desulphurization 𝑅 − 𝑆𝐻(𝑔) + 𝐻2 (𝑔) ⇋ 𝑅 − 𝐻(𝑔) + 𝐻2 𝑆(𝑔) (10)


Catalytic
𝑍𝑛𝑂(𝑠) + 𝐻2 𝑆(𝑔) ⇋ 𝑍𝑛𝑆(𝑠) + 𝐻2 𝑂(𝑔) (11)
Adsorption

Next, the process stream contains both Nitrogen and Hydrogen. However, to prevent the
oxidation of the iron catalyst in the ammonia synthesis, the carbon oxides and water needs to be
removed. The water can easily be removed by condensation. The carbon monoxide however is
converted to carbon dioxide via the water gas shift reaction to reduce the CO concentration from
12-15% to 0.2-0.4% of CO (on a dry basis). This process occurs in the High Temperature Shift
Convertor (HTSC) where at 400°C the process stream is flowed over a bed of iron oxide/chromium
oxide catalyst that reduces the CO concentration from 12-15% to 3% of CO (on a dry basis) only
due to the limitation equilibrium shift at high temperatures. Hence, the process stream is cooled
before entering the Low Temperature Shift Convertor (LTSC) containing copper oxide/zinc oxide
catalysts that operates at 200-220°C that achieves a CO concentration reduction to 0.2-0.4% (on a
dry basis). (Pattabathula & Richardson, 2016)

Following the shift conversion, the process stream contains hydrogen, nitrogen, carbon
dioxide and excess process steam. Hence, the gas is cooled and condensed to remove the excess
steam prior to the removal process of carbon dioxide. CO2 is removed from the process stream via
the absorption column where mainly aqueous amine solution (Methyl diethanolamine) and water
are used as the absorbent. The process stream leaving the columns contains only 0.3% of CO2 at
6°C and 23 bar, with 99% efficiency. Since, minute amount of carbon oxides may poison the
ammonia synthesis catalyst, the remaining carbon oxides are removed in the methanation process.
Prior to the methanation step, the process stream is pre-heated to 314°C. The methanation process
converts remaining carbon oxides to methane and water. In the ammonia synthesis, methane is
regarded as an inert has it would not impede the reaction. However, the water needs to be removed
via cooling at 14°C in a separator downstream of the methanator. Although, hydrogen is consumed
but this step is necessary to prevent the poisoning of the catalyst. (European Fertilizer
Manufacturers’ Association, 2000). The reaction of shift conversion and carbon dioxide removal
are expressed in equation E12- E15.

16
Shift (12)
𝐶𝑂(𝑔) + 𝐻2 𝑂(𝑔) ⇋ 𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) ∆𝐻°𝑟𝑥𝑛 = −41.20 𝑘𝐽/𝑚𝑜𝑙
Convertor
Methanator
𝐶𝑂2 (𝑔) + 4𝐻2 (𝑔) ⇋ 𝐶𝐻4 (𝑔) + 2𝐻2 𝑂(𝑔) ∆𝐻°𝑟𝑥𝑛 = −165.0 𝑘𝐽/𝑚𝑜𝑙 (13)
R1
Methanator
𝐶𝑂(𝑔) + 3𝐻2 (𝑔) ⇋ 𝐶𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ∆𝐻°𝑟𝑥𝑛 = −206.0 𝑘𝐽/𝑚𝑜𝑙 (14)
R2
Overall
Equation of 2𝐶𝑂(𝑔) + 6𝐻2 (𝑔) ⇋ 2𝐶𝐻4 (𝑔) + 2𝐻2 𝑂(𝑔) 𝐻°𝑟𝑥𝑛 = −712.2 𝑘𝐽/𝑚𝑜𝑙
Carbon Simplified as,
Oxides 𝐶𝑂(𝑔) + 3𝐻2 (𝑔) ⇋ 𝐶𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) ∆𝐻°𝑟𝑥𝑛 = −356.1 𝑘𝐽/𝑚𝑜𝑙 (15)
Removal

Figure 1.8: Modern Kellogg Ammonia Convertor. (Hooper, 1991)


Finally, the process stream containing hydrogen and nitrogen in a ratio of 3:1 undergoes
multiple compression stages with cooling and water separation between the stages to remove
remaining water. The process stream is compressed up to 235 bar and is pre-heated to 200°C prior
to entering the ammonia synthesis reactor as shown in Figure 1.8. The outlet of the reactor is fixed
at 300°C where the gas stream is cooled to 5°C prior to entering a separator. The bottom product
from the separator is expanded with a valve to 5 bar. The liquid ammonia at this state is
approximated to be about -8°C. To remove the impurities, the liquid ammonia enters a flash tank.
Due to unfavourable equilibrium condition and exothermic properties of this reaction, low

17
conversion of 20-30% per pass in the converter is achieved. Hence, the resultant flash gas is
recompressed and mixed with the top product of the separator before entering the synthesis gas
loop of which is displayed in Figure 1.9. The final product of liquid ammonia of 99.8% purity
from the flash tank is achieved via the synthesis loop. The pressure in the synthesis loop is
maintained by substituting the reacted gas with the fresh make-up synthesis gas. The concentration
of inert such as methane and argon is controlled within a 10% mole fraction via the purge system.
Furthermore, thorough heat removal rate is required due to immense exothermic property of the
ammonia synthesis, thence it can be observed in Figure 1.10 there are several heat exchangers in
the ammonia synthesis reactor. (Jenssen, et al., 2016)

Figure 1.9: Basic Ammonia Synthesis Loop. Source: (Hooper, 1991)

Figure 1.10: High Pressure Ammonia Synthesis Loop. Source: (Hooper, 1991)

18
Ammonia
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇋ 2 𝑁𝐻3 (𝑔) ∆𝐻°𝑟𝑥𝑛 = −92.44 𝑘𝐽/𝑚𝑜𝑙 (46)
Convertor

Hence, the overall chemical equation for this reaction pathway can be concluded by the
combination of Equations 5, 9, 15 and 16.

E-5 𝐶𝐻4 (𝑔) + 2𝐻2 𝑂(𝑔) ⇋ 𝐶𝑂2 (𝑔) + 4𝐻2 (𝑔)


E-9 2𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) ⇋ 𝐶𝑂2 (𝑔) + 𝐶𝑂(𝑔) + 𝐻2 𝑂 + 3𝐻2 (𝑔)
E-15 𝐶𝑂(𝑔) + 3𝐻2 (𝑔) ⇋ 𝐶𝐻4 (𝑔) + 𝐻2 𝑂(𝑔)
E-16 𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇋ 2 𝑁𝐻3 (𝑔)
𝟐𝑪𝑯𝟒 (𝒈) + 𝟐𝑶𝟐 (𝒈) + 𝑵𝟐 (𝒈) ⇋ 𝟐 𝑵𝑯𝟑 (𝒈) + 𝟐𝑪𝑶𝟐 (𝒈) + 𝑯𝟐 (𝒈)
Overall (17)
Equation ∆𝑯°𝒓𝒙𝒏 = −𝟖𝟖𝟎. 𝟕 𝒌𝑱/𝒎𝒐𝒍

94%

Figure 1.11: Conversion of Methane Against Temperature in Steam Reforming Process. (Chiesa,
2010)

19
Figure 1.12: Conversion of methane with respect to selectivity of carbon monoxide. Source:
(Zhang, et al., 2017)
According to the experimental data in Figure 1.11, the methane conversion in the SMR
reaction increases as the temperature increases. (Chiesa, 2010) This is in accordance to the Le
Chatelier’s principle since it is an endothermic reaction. Based on Figure 1.11, at a temperature of
1000°C, pressure of 40 bar and a steam to carbon ratio of 3.0 the methane conversion is about
94%. From this figure, it can also be observed the conversion increases with an increase in steam
to carbon ratio. However, a large steam to carbon ratio strongly burdens the energy balance of the
process, hence a large ratio is not desired. On the other hand, the selectivity of carbon monoxide
increases linearly to the conversion of methane as depicted in Figure 1.12. To explain from a
thermodynamics aspect, it is caused by the competitive reaction between the SMR as the main
reaction and the WGS as the side reaction to produce hydrogen. Since, the SMR reaction occurs
at high temperature, it would inhibit the WGS reaction that converts carbon monoxide to carbon
dioxide and hydrogen due to the exothermic property of the WGS reaction. (Zhang, et al., 2017).
Another study described, steam reforming conducted at low temperatures produced a hydrogen
yield of 2.5 mol per mol of methane consumed at a steam to carbon ratio of 3.0. (Khzouz &
Gkanas, 2017)

In a nutshell, the steam reforming of natural gas is widely used commercially across the
globe in the manufacturing of ammonia and the overall equation for this reaction pathway is
expressed in Eq. 17. However, the downside of utilizing steam reforming method would be the
volatility and the seasonal demands of natural gas that causes the unstable price hike of natural
gas. (Steinberger-Wilckens & Sampson, 2019) Nevertheless, this technology is well established at
an advanced stage of optimization in plants. In addition, as compared to other fossil fuels natural
20
gas has advantage of the highest hydrogen to carbon ratio. Therefore, natural gas has lower energy
demanding reaction as well as one of the lowest carbon dioxide emissions as compared to other
fossil fuels. According to Jenssen, et al., (2016), on the basis of one ton of ammonia produced,
steam reforming emits 1.6 tons of carbon dioxide, while heavier hydrocarbon such as heavy fuel
oil and coal emits 2.5 tons and 3.8 tons respectively. Nonetheless, the synthesis of ammonia is
based on natural gas, hence it is independent towards the variations of the feedstock composition.,
steam reforming of natural gas. Likewise, a study conducted by Welaya, et al., (2012), concluded
that steam reforming of natural gas obtained the highest fuel processing efficiency of up to 96.05%
in the production of hydrogen gas.

Table 1.4: Summary of Reaction Pathway I: Steam Reforming of Methane


Method Reaction Pathway I via Catalytic Steam Reforming (SMR)

Ammonia Haber-Bosch Process via Modern Kellogg Ammonia Convertor


Synthesis
Reagents Nitrogen Hydrogen Ammonia

Reagent Obtained Desulphurised methane Heated and pressurized


Fabrication from air. undergoes steam reforming and hydrogen and nitrogen gas
Process purification process to obtain enters the main reactor for
Description pure hydrogen gas. ammonia synthesis.
Operating Air enters 1st Reformer Main Reactor
Parameters secondary Pressure: 40 bar Pressure: 235 Bar
reformer at Temperature: < 1,100 °C Temperature: 200 °C
atmostpheric Steam to methane ratio: 3.0 Nitrogen to hydrogen feed
conditions. Catalyst: Nickel ratio: 1:3
Oxide/Aluminium Oxide Separator/ Flash Tank
Pressure: 5 Bar
2nd Reformer Temperature: -8 °C
Pressure: 40 bar
Temperature: 700 – 1000°C
Catalyst: Nickel
Oxide/Aluminium Oxide
Overall 2𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) + 𝑁2 (𝑔)
Chemical ⇋ 2 𝑁𝐻3 (𝑔) + 2𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) ∆𝐻°𝑟𝑥𝑛
Reaction = −880.7 𝑘𝐽/𝑚𝑜𝑙
Yield/ 94 ~ 96.05% (Hydrogen Production)
Selectivity

21
1.4.1.2 Reaction Pathway II: Coal- Based Hydrogen Production – Coal Gasification

Figure 1.13: Production Pathway of Ammonia from Coal. (Pattabathula & Richardson, 2016)

The gasification of coal to obtain hydrogen in the synthesis of ammonia has long been utilized in
China. Being the largest ammonia producer in the global market, over 70 % of the ammonia
produced by China are from coal. This is due to the abundance of natural resources such as coal
in China as well as the high prices of natural gases and oil that allows coal to be preferred. (Aziz,
et al., 2017).
Coal gasification is a partial oxidation process where fuel-rich gas consisting large amounts
of carbon monoxide and hydrogen that is produced when coal is subjected to steam and oxygen at
temperatures up to 1400°C and pressure more than 50 bar. (Wagner, et al., 2008). Whereby,
hydrogen being the desired end-product to manufacture ammonia. The carbon monoxide would
be removed as carbon dioxide via the water gas shift reaction. The two raw materials required for
this process would be the coal water slurry and oxygen. Due, to the exothermic reaction between
coal and oxygen, the gasification temperature of about 1350°C is sustained through the internal
combustion of oxygen without the requirement of external heat. (Wagner, et al., 2008). The main
reactions of coal gasification are as below. (Zhang, et al., 2017)

22
1
Gasification with 𝐶 + 𝑂2 ⇋ 𝐶𝑂 ∆𝐻°𝑟𝑥𝑛 = −110.4 𝑘𝐽/𝑚𝑜𝑙 (18)
2
Oxygen
Combustion with
𝐶 + 𝑂2 ⇋ 𝐶𝑂2 ∆𝐻°𝑟𝑥𝑛 = −394.1 𝑘𝐽/𝑚𝑜𝑙 (19)
Oxygen
Boudouard
𝐶 + 𝐶𝑂2 ⇋ 2𝐶𝑂 ∆𝐻°𝑟𝑥𝑛 = 172.5 𝑘𝐽/𝑚𝑜𝑙 (20)
Reaction
Primary Water
𝐶 + 𝐻2 𝑂 ⇋ 𝐶𝑂 + 𝐻2 ∆𝐻°𝑟𝑥𝑛 = 131.3 𝑘𝐽/𝑚𝑜𝑙 (21)
Gas Reaction
Secondary Water
𝐶 + 2𝐻2 𝑂 ⇋ 𝐶𝑂2 + 2𝐻2 ∆𝐻°𝑟𝑥𝑛 = 90.2 𝑘𝐽/𝑚𝑜𝑙 (22)
Gas Reaction
Methanation 𝐶 + 2𝐻2 ⇋ 𝐶𝐻4 ∆𝐻°𝑟𝑥𝑛 = −74.9 𝑘𝐽/𝑚𝑜𝑙 (23)
Water Gas
𝐶𝑂 + 𝐻2 𝑂 ⇋ 𝐶𝑂2 + 𝐻2 ∆𝐻°𝑟𝑥𝑛 = −41.2 𝑘𝐽/𝑚𝑜𝑙 (24)
Shift Reaction
Overall Coal 3
6𝐶 + 𝑂2 + 6𝐻2 𝑂 ⇋ 3𝐶𝑂 + 4𝐻2 + 2𝐶𝑂2 + 𝐶𝐻4
Gasification 2 (25)
Reaction ∆𝐻°𝑟𝑥𝑛 = −226.6 𝑘𝐽/𝑚𝑜𝑙

From Equations 20, 21, and 22 it can be observed that an increase in temperature would
intensify the Boudard reaction as well the primary and secondary gas reaction that would favour
the production of hydrogen and carbon monoxide. Simultaneously, carbon dioxide concentration
reduces at high temperatures. This is because, although reactions 19, 22, and 24 produces CO2, but
at high temperatures the Boudouard reaction (Equation predominates.
Based on Figure 1.13, it can be observed the production pathway of ammonia from natural
gas and coal has only minute differences. By which, the coal gasification pathway has additional
process to remove impurities found in coal prior to the ammonia synthesis.
The main components of a coal based ammonia production plant includes the air
separation unit (ASU) that serves to separate oxygen and nitrogen from the air. In the unit,
Pressure swing Adsorption (PSA) is utilised for the cheaper nitrogen gas production, which is
suitable to the ammonia plant capacity. PSA apply the carbon molecular seive to separate out the
oxygen from the air through adsorption of oxygen onto the carbon molecular sieve; while the
nitrogen molecules with smaller size can by-pass the molecular sieve and hence producing the
pure nitrogen gas with purity up to 99.9999% (based on the inlet pressure (4-13 bar) and
temperature (10- 25 °C)) for the ammonia synthesis. (Copco, 2020).
The sour gas shift unit (SGS) that is analogous to water gas shift reaction, acid gas removal
unit and the ammonia synthesis unit. The ASU supplies the required oxygen to the gasifier where
the coal is converted to synthesis gas containing CO, CO2, H2 and CH4. Followed by the gasifier,
the particulate matter are removed and steam is added in the SGS unit. The SGS facilitates to

23
remove the sulphur components in the process stream with the aid of the molybdenum (CoMo)
catalyst as well as to reduce the remaining CO % to less than 1% via the conversion of CO to CO2.
(Pattabathula & Richardson, 2016)

Sour Gas Shift 𝐶𝑂 + 𝐻2 𝑂 ⇋ 𝐶𝑂2 + 𝐻2 ∆𝐻°𝑟𝑥𝑛 = −41.20 𝑘𝐽/𝑚𝑜𝑙 (13)


Ammonia
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇋ 2 𝑁𝐻3 (𝑔) ∆𝐻°𝑟𝑥𝑛 = −92.44 𝑘𝐽/𝑚𝑜𝑙 (14)
Synthesis

The CO2 and sulphur composed from the SGS unit is removed from the process stream via
the AGRU unit that exploits a chilled methanol scrubbing solution such as Rectisol. The overhead
CO2 product from the AGRU is usually vented or used for the manufacturing of urea and the
sulphur is usually further recovered in a sulphur recovery unit.
To ensure complete removal of residual CO and CH4, the syngas from the AGRU enters a
nitrogen wash unit that is fed with nitrogen gas from the ASU. This is because it is crucial to
ensure the highest possible removal of CO, as minimal traces of CO would poison the catalyst of
ammonia synthesis process. Hence, the nitrogen washes out all the impurities as well as to give
the stoichiometric hydrogen to nitrogen ratio. The ammonia synthesis is identical to that of steam
reforming plants. However, due to the liquid nitrogen wash unit, a higher purity of synthesis gas
allows a more simpler and efficient ammonia synthesis loop that does not require the purging of
impurities. (European Fertilizer Manufacturers’ Association, 2000). The overall equation of this
reaction pathway of ammonia from coal is expressed below.

Overall 3
6𝐶(𝑔) + 𝑂2 (𝑔) + 𝑁2 (𝑔) + 7𝐻2 𝑂(𝑔) ⇋
Equation of 2
2 𝑁𝐻3 (𝑔) + 2𝐻2 (𝑔) + 2𝐶𝑂(𝑔) + 3𝐶𝑂2 (𝑔) + 𝐶𝐻4 (15)
Reaction
Pathway II ∆𝐻°𝑟𝑥𝑛 = −360.2 𝑘𝐽/𝑚𝑜𝑙

In addition, the gasification methods are defined by the types of gasifier used. However,
most of the gasifier designs are based on fluidized bed that operates above atmospheric pressure.
This facilitates the gasifier to exploit various coal feeds. The CO % by volume is dependant on the
type of gasifiers used. The most commonly used gasifiers designs are the Winkler process, Lurgi
process and Koppers – Totzek process.

Firstly, the Winkler gasifier consists of an isothermal fluidized bed commonly used in
small ammonia production plants. It operates at atmospheric condition with a temperature of
1000°C. The steam and oxygen is injected at the bottom of the fluidized bed. Hence, a composition

24
of less than 1% of methane is achieved in the exit gas that comprises mainly of carbon monoxide
and hydrogen.

On the other hand, the Lurgi gasifiers operates at 25-30 bar where crushed coal as small
as 4mm particle size descends from the top of the gasifier counter-current to the upward gas flow.
High temperature of up to 1000°C is maintained at the bottom of the reactor. However, the colder
temperatures of 600°C at the top of the reactor leads to the formation of impurities such as tars and
phenols in the exit gas. Hence, this requires a higher cost to purify and condition the exit gas to.

Thirdly, Koppers’ – Totzek process is the most commonly employed gasifier in ammonia
plants in countries such as South Africa, China and India due to being the most successful
entrained-flow gasifier. It operates at atmospheric pressure conditions and temperature range from
1500-1600°C. Dry coal dust is fed together with steam and oxygen to the burners of the gasifier at
a high velocity. A water scrubber is utilized to remove the remaining ashes and carbon from the
exit gas. The drawbacks of this gasifier is the need of finely graded coal dust at low operating
pressure conditions. (Appl, 1999)

Figure 1.14: Koppers-Totzek Gasifier System. (Perry, 1978)

25
Figure 1.15: Conversion of Coal Gasification Process Against Temperature. (Zhang, et. al., 2017)

Coal gasification is considered to be one of the cheapest hydrogen production technology


from fossil fuels. However, it has a huge environmental impact as it contains high levels of carbon
monoxide and carbon dioxide in the exit gas of the coal gasification method. Therefore, as
compared to other hydrogen production method, coal gasification has the highest carbon dioxide
emmisions. (Aziz, et al., 2017). Apart from that, the need for fine graded coal as well as
compression costs are further drawbacks of utilizing this method for the production of ammonia
via the Kopper-Totzek gasifier. In addition, the coal gasification process is an energy demanding
process. It can be observed from Eq. 15, there are various byproducts produced from this reaction
pathway. Namely, carbon monoxide, carbon dioxide, methane as well as unreacted hydrogen. To
boot, according to a study conducted by Welaya, et al. (2012), coal gasification is less efficient
than steam reforming of methane since this process produces less hydrogen per mole of carbon
feed. A fuel efficiency of coal to hydrogen of up to 70% only is achieved via the coal gasification
method. (Gray & Tomlinson, 2001). Based on the experimental data in Figure 1.15, it can be
observed the conversion increases as the temperature increases. Whereby, a carbon conversion
rate of up to 75% is achieved at 1050°C, with a gas yield of more than 2.750 Nm3/ kg of coal is
produced (Zhang, et al., 2017)

26
Table 1.5: Summary Of Reaction Pathway II - Coal Gasification.

Method Reaction Pathway II via Coal Gasification


Ammonia Synthesis Haber-Bosch Process via Modern Kellogg Ammonia Convertor
Reagents Nitrogen Hydrogen Ammonia

Reagent Fabrication Pure Nitrogen Feed, From Coal Gasification, followed by purification of the Heated and pressurized hydrogen and
Process Description Air Separation Unit (ASU) exit gas nitrogen gas enters the main reactor for
ammonia synthesis.
Operating Pressure Swing Adsorption 1. Winkler process Main Reactor
Parameters (PSA) • The steam and oxygen is injected at the Pressure: 235 Bar
- Carbon Molecular bottom of the fluidized bed. Temperature: 200 °C
Sieve (CMS) • Pressure: 1 atm Nitrogen to hydrogen feed ratio: 1:3
• Temperature: 1, 000°C.
- Feed: Air • Exit gas consists <1% of methane. Separator/ Flash Tank
- Inlet Pressure: 4- 13bar Pressure: 5 Bar
- Inlet Temp.: 10-25 °C 2. Lurgi process Temperature: -8 °C
• Crushed coal particle size: 4mm
that descends from the top of the gasifier
counter-current to the upward gas flow.
• Pressure: 25-30 bar
• Temp: 600 ~1000°C is maintained at the
bottom of the reactor.

3. *Koppers – Totzek process


• Dry coal dust is fed together with steam
and oxygen to the burners of the gasifier
at a high velocity.
• Pressure: 1 atm
• Temperature: 1, 500 ~ 1, 600 °C.

27
Exit Gas Purification AGRU unit / SGS Unit (Desulphurisation Unit)
Method - Remove sulphur and syngas, by using chilled methanol scrubbing solution.
- Molybdenum (CoMo) catalyst is used.
Nitrogen Washing
• Reduce the concentration of impurities (CO and CH4) while injecting the Nitrogen gas as feedstock.

Overall Chemical 3
6𝐶(𝑔) + 𝑂2 (𝑔) + 𝑁2 (𝑔) + 7𝐻2 𝑂(𝑔) ⇋ 2 𝑁𝐻3 (𝑔) + 2𝐻2 (𝑔) + 2𝐶𝑂(𝑔) + 3𝐶𝑂2 (𝑔) + 𝐶𝐻4
Reaction 2
∆𝐻°𝑟𝑥𝑛 = −360.2 𝑘𝐽/𝑚𝑜𝑙

Yield/ Selectivity 70 ~ 75 % H2 Conversion

Remarks Commersialised and large scale however large amount CO2 emissions.

Note: Winkler Process, Lurgi Process, and Koppers Process are the process available for Gasification process.
*Koppers Process is selected as the most suitable gasification process for coal gasification, because it is the most commersialised technology, with
highest feasibility.

28
1.4.1.3 Reaction Pathway III: Water-Based Hydrogen Production – Alkaline Electrolysers
Aside from fossil fuel-based hydrogen production technologies (e.g. Reaction Pathway I & II),
water-based hydrogen production technologies were also reviewed for a wider range of
consideration. As the name suggested, these technologies utilise water as its main or the only
materials in the process for the generation of hydrogen gas, which is more sustainable and more
environmental friendly process, with lesser green house gases emission to the environment.

Globally, there are about 5% of the hydrogen being generated using the water (Posdziech
et al., 2019), and the number is expecting to be increased in the future, due to the cleaner and more
sustainable process as compared to fossil fuel-based hydrogen source. In summary, the water-
based technologies can be categorised into 3 main sub-parts: Electrolysis, Thermolysis, and
Photolysis. However, due to the sustainability and feasibility for these technologies, water
electrolysis method will be reviewed in details, while slight introductions for the other sub-parts
(Thermolysis and Photolysis). The technologies details and the derivations of overall will be
discussed at the section below.
Currently among these technologies, we selected Alkaline electrolysers as the most suitable
technology for the water-based hydrogen production, as this technologies shows lowest operating
cost with acceptable conversion efficiency (50~60%). The achieved overall chemical equation is
as followed:
Overall Equation for
Reaction Pathway III 𝟑𝑯𝟐 𝑶 + 𝑵𝟐 → 𝑵𝑯𝟑 ∆𝐻°𝑟𝑥𝑛 = −956.44 𝑘𝐽/𝑚𝑜𝑙 (26)

Water Electrolysis
Water Electrolysis is the application of electricity, along with components like cathod, anode and
electrolyte to undergo the electro spliting of the water molecules into hydrogen gas and oxygen
gas through redox reaction as in Figure 1.16 (Nikolaidis & Poullikkas, 2017).The electrolysis of
water is one of the greener alternative methods to obtain hydrogen gas. In general, there were
three common types of water electrolysis for the hydrogen production: Alkaline Electrolyser,
Solid Oxide Electrolyser (SOE), and Proton Exchanger Membrane (PEM) Electrolyser (El-shafie
et al., 2019). As summaries, the data for those three water electrolysis technology is as shown in
Table 1.6.

29
Table 1.6 Summary of The Available Water Electrolysis Technology.
Technology Alkaline Electrolyser Solid Oxide Proton Exchenger
(Nikolaidis & Electrolyser (SOE) Membrane (PEM)
Poullikkas, 2017) (Dincer & Acar, (Nikolaidis &
2014) Poullikkas, 2017)
Operating - 2 types of - 900 ~ 1200 °C - Membrane as
Condition alkaline - Solid oxides Electrolyser
electrolytes (e.g. electrolytes
KOH, NaOH)
Overall Chemical 1
𝐻2 𝑂 → 𝐻2 + 𝑂2 ∆𝐻 = −288 𝑘𝐽 𝑚𝑜𝑙−1
Equation 2
Advantage - Lower Cost - Higher - Lower Operating
Conversion Temperature
- Lesser Corrosion
Disadvantage - Lower Efficiency - Higher - High operating
at lower Voltage Operating cost, as it requires
supply Temperature high purity of
(50 – 80%) - Lesser deionised water
(Bleeker et al., Corrosion
2010)
- Corrosion Issues

From Table 1.6, alkaline electrolysers seems to be the most suitable method as it shows
lowest cost with acceptable efficiency. SOE and PEM shows promising potential which lesser
issues from the process, but the technology is currently under Research and Development phase
where it is not commersialised in current phase. Alkaline Electrolysers used two types alkaline
electrolytes such as potassium hydroxide (KOH), and sodium hydroxide (NaOH) in its process(El-
shafie et al., 2019), resulting in oxygen formation at the anode side, and hydrogen gas formation
at the cathode side. Alkaline Electrolysers are relatively lower cost, but shows low efficiency (50-
60%) and corrosion problems with the application of alkaline electrolytes (El-shafie et al., 2019).
The process flow diagram (Figure 1.16) and overall chemical equations were as shown below:
(27)
Anode Reaction 4 𝑂𝐻 − → 𝑂2 + 2𝐻2 𝑂

(28)
Cathode Reaction 2𝐻2 𝑂 + 2𝑒 − → 𝐻2 + 2 𝑂𝐻 −

1 (29)
Overall Equation 𝐻2 𝑂 → 𝐻2 + 𝑂2 ∆𝐻 = −288 𝑘𝐽 𝑚𝑜𝑙 −1
2

30
Figure 1.16: Flow Diagram of The Water Electrolysis Process (Nikolaidis & Poullikkas, 2017)

Photolysis/ Photo-electrolysis
Similar to Electrolysis, Photo-electrolysis is the harvesting of solar energy using photoelectrical
chemical energy (PEC), to generate the necessary amount of voltage to break down the water
molecules into hydrogen gas and oxygen gas (Kalamaras & Efstathiou, 2013), as shown in Figure
1.17 below.

Figure 1.17: Photolysis Process with slight modification (Nikolaidis & Poullikkas, 2017)
The main differences between Photoelectrolysis and Electrolysis is that, Photolysis utilises
semiconductor type of electrodes instead of alkalines or oxides for the generation of the required
voltages. The main advantages of the photoelectrolysis are the free renewable energy were used
for the generation of hydrogen gas, with zero green house gas emission. Although this method
seems to be the most promising method among the other water-based technologies, it is
misfortuned that this technology is still in research and development phase, with very low
conversion efficiency at 0.06% (Akikusa & Khan, 2002) and high capital cost. The chemical
equation for photolysis is as follow:

31
1
Overall Equation 𝐻2 𝑂 → 𝐻2 + 𝑂2 (30)
ℎ𝑣 2

Thermolysis
Thermolysis is the process where water is undergoing decomposition process at higher temperature
to hydrogen and oxygen. The operating temperature is required to be over 2500 °C for the
decomposition of the water to begin, when the gibbs function become zero (Nikolaidis &
Poullikkas, 2017). Due to its high operating temperature, chemical reactions can be combined with
thermolysis to reduce the water decomposition temperature to 900 °C (El-shafie et al., 2019). For
this system, the heat source can be obtained from nuclear reactor or solar heat (refer Figure 1.18)
as a sustainable source of energy (Nikolaidis & Poullikkas, 2017).

Figure 1.18: Thermolysis of Water – Solar, With Slight Modification (Nikolaidis & Poullikkas,
2017)
However, for current phase of this technology the operating temperature is still considered
as not economically feasible as the higher cost is required to maintain the high temperature for
this system, with relatively low efficiency (maximum at 45 % with nuclear reactor (Nikolaidis &
Poullikkas, 2017)). In short for both thermolysis, and chemical assisted thermolysis, the overall
chemical equation is as follow (Kalamaras & Efstathiou, 2013):

1
Overall Equation 𝐻2 𝑂 + 𝐻𝑒𝑎𝑡 → 𝐻2 + 𝑂2 (31)
2

32
Conclusion for Water-based Technologies

In short, the water-based technologies can be categorised into 3 main sub-parts: Electrolysis,
Thermolysis, and Photolysis. Although these technologies can reduce the environmental stress by
the minisation of Green House Gas emission, these technologies still not matured with high cost
and low conversion (maximum of 60 % for alkaline electrolyser). The hydrogen production
process which will use for the reaction pathway III will be the alkaline electrolysers as it is more
most effective, and more profitable for the plant.
For the gross profit calculation, the overall chemical equation is derived as followed, by
selecting alkaline electrolyser as the main reaction pathway.
In the Reaction Pathway III, hydrogen gas with high purity of ~99% is produced and can
will be used as the feedstock for the ammonia synthesis (El-shafie et al., 2019). As the pure
hydrogen gas is supplier into the system, the feed stream of Nitrogen is required to be as pure as
possible to prevent hydrogen explosion. Therefore, similar to coal gasification part: An Air
Seperation Unit is required for the purification of the air into pure nitrogen gas stream. The pure
nitrogen will be fed into the ammonia reactor, along with the pure hydrogen gas under high
temperature and pressure for the synthesis of ammonia. Although the method for each technologies
is different, the final overall equation is similar as shown below, with different energy requiment
based on the method used (e.g. heat energy for thermolysis & electrical energy for electrolysis),
then followed by the conventional Haber-Bosch process.

1 (29)
Overall Equation 𝐻2 𝑂 + 𝐸𝑛𝑒𝑟𝑔𝑦 → 𝐻2 + 𝑂2 ∆𝐻 = −288 𝑘𝐽 𝑚𝑜𝑙−1
2

(13)
Ammonia Synthesis 𝑁2 + 3𝐻2 → 𝑁𝐻3 ∆𝐻°𝑟𝑥𝑛 = −92.44 𝑘𝐽/𝑚𝑜𝑙

Overall Equation for (26)


𝟑𝑯𝟐 𝑶 + 𝑵𝟐 → 𝑵𝑯𝟑 ∆𝑯°𝒓𝒙𝒏 = −𝟗𝟓𝟔. 𝟒𝟒 𝒌𝑱/𝒎𝒐𝒍
Reaction Pathway III

33
Table 1.7: Summary Of Reaction Pathway III - Water-Based Hydrogen Production.
Method Reaction Pathway III
*Water Electrolysis Photolysis/ Photo-electrolysis Thermolysis
Ammonia Synthesis Haber-Bosch Process via Modern Kellogg Ammonia Convertor
Operating Parameters Same as Reaction Pathway II Same as Reaction Pathway II Same as Reaction Pathway II
H2 Feedstock Water Deionised Water Water
Operating Parameters *Alkaline Electolyser is selected Semiconductor type electrodes Temperature: 900~ 2500 °C
Reagent: KOH, NaOH, NaCl
Temperature: 25 ~ 120 °C
Pressure: 1 ~ 25 bar
Catalyst: Nickel-based
N2 Feedstock Pure Nitrogen, Pure Nitrogen, Pure Nitrogen,
from ASU using Air as feedstock from ASU using Air as feedstock from ASU using Air as feedstock
Operating Parameters Same as Reaction Pathway II Same as Reaction Pathway II Same as Reaction Pathway II
Overall Chemical
Reaction 3𝐻2 𝑂 + 𝑁2 → 𝑁𝐻3 ∆𝐻°𝑟𝑥𝑛 = −956.44 𝑘𝐽/𝑚𝑜𝑙 (E26)

Yield/ Selectivity 50 – 80 % for H2 Production, 0.06 % for H2 Production, 45 % for H2 Production,


Remarks Commersialised in low capacity Not Feasible, low efficiency Not Feasible, Low efficiency
Zero Carbon Dioxide Emission, Sustainable Feedstock
*Water Electrolysis is selected as the most feasibible reaction among all the water-based hydrogen production technologies, due to its high
conversion, and technologically more mature with lower operating cost.

34
1.4.1.4 Reaction Pathway IV : Biomass-Based Hydrogen Production- Biomass Pyrolysis
Other than water, biomass is one of the other high potential sustainable feed stocks, especially for
our country with various types of agricultural biomass waste, to generate the required hydrogen
for the ammonia synthesis. In this section, only the gasification and pyrolysis of the biomass
technologies are considered, as it is more reliable and shows higher potential to be implemented.

Biomass Gasification
As similar for the coal partial oxidation process (Reaction Pathway II), biomass gasification is the
process where the biomass is heated until temperature above 1, 000K for the components to be
gasified into hydrogen, carbon oxides, methane, and higher hydrocarbons.(Valenzuela & Zapata,
2019) This process shows high potential to be implemented, due to the ability to breakdown the
complex biomass into simpler form of components (e.g. Hydrogen gas) for the synthesis of other
chemicals (e.g. Ammonia), using the abundant waste generated by the agricultural industry.

However, this process is considered as energy intensive process as it shows lower thermal
efficiency due to the moisture content in the biomass (Kalamaras & Efstathiou, 2013), and it also
requires high energy for the transportation of the bulk biomass to the processing plant. Other than
that, biomass gasification process also shows higher operating cost, due to the high operating
temperature for the gasification to be occurred. In other word, for the generation of ammonia, this
method is not suitable, as the process shows higher cost, resulting in lower profit margin for the
plant.

For additional information, the process shows efficiency of 35~50 %, with increasing
efficiency with higher quality of biomass of lower heating value (lower moisture
content)(Kalamaras & Efstathiou, 2013), and the overall chemical reaction is as followed
(Valenzuela & Zapata, 2019):

Overall Equation: 𝐵𝑖𝑜𝑚𝑎𝑠𝑠 + 𝐻𝑒𝑎𝑡 + 𝑆𝑡𝑒𝑎𝑚


→ 𝐻2 + 𝐶𝑂 + 𝐶𝑂2 + 𝐶𝐻4 + 𝐻𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠 + 𝐶ℎ𝑎𝑟𝑐𝑜𝑎𝑙 (36)
Ammonia Synthesis: 𝑁2 + 3𝐻2 → 𝑁𝐻3 (13)

Overall Chemical Reaction for Reaction Pathway: (37)

3𝐵𝑖𝑜𝑚𝑎𝑠𝑠 + 3𝑆𝑡𝑒𝑎𝑚 + 𝑁2 + 𝐻𝑒𝑎𝑡


→ 𝑁𝐻3 + 3𝐶𝑂 + 3𝐶𝑂2 + 3𝐶𝐻4 + 𝐻𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠 + 𝐶ℎ𝑎𝑟𝑐𝑜𝑎𝑙

35
Biomass Pyrolysis
Biomass pyrolysis is a process where the biomass is decomposed using heat energy to form carbon
and hydrogens (with impurities like H2S due to the sulphur content in the biomass, or carbon oxides,
due to the oxygen content in the biomass). (Valenzuela & Zapata, 2019) This process can be
carried out in the absence of oxygen and air, at 500~900 °C, and 0.1~0.5MPa to prevent/reduce
the formation of byproducts like dioxins, carbon oxides, and etc. This method is more preferrable
as Production Reaction Pathway IV, as this process offers similar/ lower heat energy requirement,
lower green house gas emision, and flexibility of the biomass feedstock (independent to the
moisture content)(Kalamaras & Efstathiou, 2013). The overall chemical reaction is as shown
below:

General Equation: 𝐶𝑛 𝐻𝑚 + 𝐻𝑒𝑎𝑡 → 𝑛 𝐶 + 0.5 𝑚 𝐻2 (38)

By assuming Butane as the feedstock, the general equation can be rewriten into:
General Equation: 𝐶4 𝐻10 + 𝐻𝑒𝑎𝑡 → 4 𝐶 + 5 𝐻2 (39)
Ammonia Synthesis: 𝑁2 + 3𝐻2 → 𝑁𝐻3 (13)

Overall Chemical Reaction for Reaction Pathway: (40)

3𝐶4 𝐻10 + 5𝑁2 + 𝐻𝑒𝑎𝑡 → 5𝑁𝐻3 + 12 𝐶 + 15 𝐻2

Conclusion for Biomass-based Hydrogen Production Technologies


In short, the biomass-based hydrogen production technologies can be categorised bioamss
gasification and biomass pyrolysis. Although these technologies can reduce the environmental
stress by the minisation of Green House Gas emission, and using the waste as renewable feed stock,
these technologies still shows lower profitability as compared to fossil-fuel-based technologies.
The hydrogen production process which will use for the overall comparison will be the pyrolysis
of biomass, as it is more most cost effective, hence more profitable for the plant. The list of
chemicals involved in the process is tabulated in Table 1.8 as shown in next page.
In the Reaction Pathway IV, hydrogen gas, along with the mixture of unreacted
hydrocarbons is produced. With some separation technologies application, the clean hydrogen is
produced and can be used as the feedstock for the ammonia synthesis. As the pure hydrogen gas
is supplier into the system, the feed stream of Nitrogen is required to be as pure as possible to
prevent hydrogen explosion. Therefore, similar to coal gasification part: An Air Seperation Unit

36
is required for the purification of the air into pure nitrogen gas stream. The pure nitrogen will be
fed into the ammonia reactor, along with the pure hydrogen gas under high temperature and
pressure for the synthesis of ammonia. Although the method for each technologies is different, the
final overall equation is similar as shown below, with different energy requiment based on the
method used (e.g. heat energy for thermolysis & electrical energy for electrolysis), then followed
by the conventional Haber-Bosch process.

1
Overall Equation: 𝐻2 𝑂 + 𝐸𝑛𝑒𝑟𝑔𝑦 → 𝐻2 + 𝑂2 ∆𝐻 = −288 𝑘𝐽 𝑚𝑜𝑙 −1 (41)
2

Ammonia Synthesis: 𝑁2 + 3𝐻2 → 𝑁𝐻3 ∆𝐻°𝑟𝑥𝑛 = −92.44 𝑘𝐽/𝑚𝑜𝑙 (13)

Overall Equation for


Reaction Pathway 𝟑𝑯𝟐 𝑶 + 𝑵𝟐 → 𝑵𝑯𝟑 (42)
∆𝐻°𝑟𝑥𝑛 = −956.44 𝑘𝐽/𝑚𝑜𝑙
III:

37
Table 1.8 Summary of Reaction Pathway IV - Biomass-based Hydrogen Production.
Method Reaction Pathway IV
Biomass Gasification *Biomass Pyrolysis
Ammonia Synthesis Haber-Bosch Reaction
Operating Parameters Same as Reaction Pathway II
H2 Feedstock Biomass Biomass
Operating Parameters Drying Oxidation (Refer Coal Gasification) Temperature: 500~900 °C
Temperature: 100-250 °C Temperature: 900 - 1400 °C Pressure: 0.1~0.5MPa
Pyrolysis Drying * Carried out in the absence of oxygen
Temperature: 200-240 °C, up Temperature: 750- 950 °C and air to prevent coke formation
to 400 °C
N2 Feedstock Pure Nitrogen,
from ASU using Air as feedstock
Operating Parameters Same as Reaction Pathway II
Overall Chemical Reaction 3𝐵𝑖𝑜𝑚𝑎𝑠𝑠 + 3𝑆𝑡𝑒𝑎𝑚 + 𝑁2 + 𝐻𝑒𝑎𝑡 3𝐶4 𝐻10 + 5𝑁2 + 𝐻𝑒𝑎𝑡
→ 𝑁𝐻3 + 3𝐶𝑂 + 3𝐶𝑂2 + 3𝐶𝐻4 + 𝐻𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠 → 5𝑁𝐻3 + 12 𝐶
+ 𝐶ℎ𝑎𝑟𝑐𝑜𝑎𝑙 + 15 𝐻2

Yield/ Selectivity ~ 68.9 % ~ 53 %

Remarks High Energy Usage Commercialised, Low Profit


*Biomass Pyrolysis is selected as the most suitable hydrogen production pathway among the biomass-based hydrogen production, as it is more
commercialised with lower operating cost.

38
1.4.1.5 Reaction Pathway V : Outsourcing of Hydrogen
In current practices, it is clear that fossil-fuel-based hydrogen is more cost efficient for the
hydrogen generation with higher conversion at lower cost. However, by researching for the green
perspective, the utilisation of the fossil-fuel based hydrogen will shows negative impact to the
environment, such as Global Warming, caused by large amount of Green House Gas emission
from the process (CO2, CO, SOx, NOx, organic solvents for carbon oxides separation, and etc.).

On the other hand, the sustainable technology (water, biomass, etc.) is not yet matured in
current phase, and expecting to show improvements overtime and to show potential to be
commercialise in near 5 ~ 10 years, due to the society pressure for the greener and sustainable
industry and technology. Therefore, to fully stay opened for the sustainable technologies,
purchasing hydrogen directly from supplier would be one of the available methods for shorter term
(5~10 years), to allow the buffer duration for the technological advancement of the green
technology, while still generating profit in the meantime.

In this reaction pathway, the Pure Nitrogen gas will be obtained using the ASU as in Reaction
Pathway II. The pure Hydrogen gas and Nitrogen gas will then send to the reactor in excess
ammonia, as in Reaction II to produce ammonia. Since the reaction involved is only ammonia
synthesis, the operating parameters will be following the ammonia synthesis process from reaction
pathway I, and the overall chemical equation is as followed:

Ammonia Synthesis: 𝑁2 + 3𝐻2 → 𝑁𝐻3 ∆𝐻°𝑟𝑥𝑛 = −92.44 𝑘𝐽/𝑚𝑜𝑙 (13)

39
1.4.2 Gross Profit Evaluation of Various Reaction Pathways
Table 1.9: Bulk Chemical Prices.
Chemical Price (USD/kg)
Ammonia 7.000 b
Carbon Dioxide 2.500b
Carbon Monoxide 8.000a
Coal 0.4000b
Hydrogen 2.899a
Methane 0.09386a
Water 0.0023a
a
Value obtained via calculation of which complete steps can be found in Appendix A.
b
Value obtained from online resources whereby comprehensive list is tabulated in
Appendix A.

1.4.2.1 Reaction Pathway I: Steam Reforming of Methane


Overall 𝟐𝑪𝑯𝟒 (𝒈) + 𝟐𝑶𝟐 (𝒈) + 𝑵𝟐 (𝒈) ⇋ 𝟐 𝑵𝑯𝟑 (𝒈) + 𝟐𝑪𝑶𝟐 (𝒈) + 𝑯𝟐 (𝒈)
Equation ∆𝑯°𝒓𝒙𝒏 = −𝟖𝟖𝟎. 𝟕 𝒌𝑱/𝒎𝒐𝒍

Assuming all of the reaction proceeds with 100% conversion efficiency. Therefore, there are
only three raw materials required in this pathway (Nitrogen gas, Natural Gas and Air) since
steam is generated from the process pathway. Withal, Nitrogen is obtained from the atmospheric
air hence no cost for Nitrogen (N2). The natural gas feed is assumed to contain 100% methane
without any impurities.

40
Table 1.10: Gross Profit of Reaction Pathway I.
Reaction path 𝟐𝑪𝑯𝟒 + 𝟐𝑶𝟐 + 𝑵𝟐 ⇋ 𝟐 𝑵𝑯𝟑 + 𝟐𝑪𝑶𝟐 + 𝑯𝟐
Stoichiometric 2 2 1 2 2 1
coefficient
Molecular weight 16.04 32.00 28.01 17.03 44.01 2.016
(kg/kmol)
Mass reacted/produced 32.08 64.00 28.01 34.06 88.02 2.016
(kg)

Mass per kg of NH3 0.9419 1.879 0.8224 1.000 2.584 0.05919


produced (kg/ kg of
NH3)
Market Price (USD/kg) 0.09386a - - 7.000 b 2.500b 2.899a

a
Value obtained via calculation of which complete steps can be found in Appendix A.
b
Value obtained from online resources whereby comprehensive list is tabulated in Appendix A.

𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 ( )
𝒌𝒈 𝑵𝑯𝟑
7𝑈𝑆𝐷 (1𝑘𝑔 𝑁𝐻3 ) 2.500 𝑈𝑆𝐷 (2.584 𝑘𝑔 𝐶𝑂2 ) 2.899 𝑈𝑆𝐷 (0.05919 𝑘𝑔 𝐻2 ) 0.09386 𝑈𝑆𝐷 (0.9419 𝑘𝑔 𝐶𝐻4 )
=[ + + ]− [ ]
𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐶𝑂2 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐻2 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐶𝐻4 𝑘𝑔 𝑁𝐻3
𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 = +𝟏𝟑. 𝟓𝟒
𝒌𝒈 𝑵𝑯𝟑

41
1.4.2.2 Reaction Pathway II: Coal Gasification

𝟑
𝟔𝑪(𝒈) + 𝑶𝟐 (𝒈) + 𝑵𝟐 (𝒈) + 𝟕𝑯𝟐 𝑶(𝒈) ⇋
Overall 𝟐
Equation 𝟐 𝑵𝑯𝟑 (𝒈) + 𝟐𝑯𝟐 (𝒈) + 𝟐𝑪𝑶(𝒈) + 𝟑𝑪𝑶𝟐 (𝒈) + 𝑪𝑯𝟒
∆𝑯°𝒓𝒙𝒏 = −𝟑𝟔𝟎. 𝟐 𝒌𝑱/𝒎𝒐𝒍

Assuming all of the reaction proceeds with 100% conversion efficiency. Therefore, there are
only three raw materials required in this pathway (Nitrogen, Coal and Air). Since steam is
generated from the process pathway, the price of steam was assumed to be zero. Withal,
Nitrogen is obtained from the atmospheric air hence no cost for Nitrogen (N2). The coal feed is
assumed to contain 100% carbon without any impurities.

42
Table 1.11: Gross Profit of Reaction Pathway II.
Reaction path 𝟔𝑪 + 𝟑 + 𝑵𝟐 + 𝟕 𝑯𝟐 𝑶 ⇋ 𝟐𝑵𝑯𝟑 + 𝟐𝑯𝟐 + 𝟐𝑪𝑶 + 𝟑𝑪𝑶𝟐 + 𝑪𝑯𝟒
𝑶
𝟐 𝟐
Stoichiometric coefficient 6 1.5 1 7 2 2 2 3 1

Molecular weight 12.01 32.00 28.01 18.02 17.03 2.016 28.01 44.01 16.04
(kg/kmol)
Mass reacted/produced 72.06 48.00 28.01 126.1 34.06 4.032 56.02 132.0 16.04
(kg) 3
Mass per kg of NH3 2.116 1.410 0.8224 3.702 1.000 0.1184 1.645 3.876 0.4709
produced (kg/ kg of NH3)
Market Price (USD/kg) 0.4000b - - 0.0023 7.000 b 2.899a 8.000b 2.500b 0.09386a

a
Value obtained via calculation of which complete steps can be found in Appendix A.
b
Value obtained from online resources whereby comprehensive list is tabulated in Appendix A.

𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 ( )
𝒌𝒈 𝑵𝑯𝟑
7𝑈𝑆𝐷 (1𝑘𝑔 𝑁𝐻3 ) 2.899 𝑈𝑆𝐷 (0.1184 𝑘𝑔 𝐻2 ) 8.000 𝑈𝑆𝐷 (1.645 𝑘𝑔 𝐶𝑂) 2.500 𝑈𝑆𝐷 (3.876 𝑘𝑔 𝐶𝑂)
=[ + + +
𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐻2 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐶𝑂 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐶𝑂2 𝑘𝑔 𝑁𝐻3
0.09386 𝑈𝑆𝐷 (0.4709 𝑘𝑔 𝐶𝑂2 ) 0.4000 𝑈𝑆𝐷 (2.116 𝑘𝑔 𝐶) 0.0023 𝑈𝑆𝐷 (3.702 𝑘𝑔 𝐻2 𝑂)
+ ]− [ + ]
𝑘𝑔 𝐶𝐻4 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐶 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝐻2 𝑂
𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 = +𝟐𝟗. 𝟑𝟖
𝒌𝒈 𝑵𝑯𝟑

43
1.4.2.3 Reaction Pathway III: Water-Based Hydrogen Production – Alkaline Electrolysers

Overall 𝟑𝑯𝟐 𝑶 + 𝑵𝟐 → 𝑵𝑯𝟑


∆𝑯°𝒓𝒙𝒏 = −𝟖𝟖𝟎. 𝟕 𝒌𝑱/𝒎𝒐𝒍
Equation
Assuming all of the reaction proceeds with 100% conversion efficiency. Therefore, there are only
two raw materials required in this pathway (Pure Nitrogen and Water) with no intermediate
products. Withal, Nitrogen is obtained from the atmospheric air hence no cost for Nitrogen (N2).
However, for the water as raw material, we cannot neglect the cost as in Reaction I & Reaction
Pathway II, the price will be obtained through the industrial water supply company with
assumption that supplied by USA Bryan Municipal Utilities (BMU, 2020).

Table 1.12: Gross Profit of Reaction Pathway III.


Reaction path 𝟑𝑯𝟐 𝑶 + 𝑵𝟐 ⇋ 𝟐 𝑵𝑯𝟑
Stoichiometric coefficient 3 1 2

Molecular weight 18.02 28.01 17.03


(kg/kmol)
Mass reacted/produced 54.06 28.01 34.06
(kg)
Mass per kg of NH3 1.5872 0.8223 1.000
produced (kg/ kg of NH3)
Market Price (USD/kg) 0.0023a - 7.000 b

a
Value obtained via calculation of which complete steps can be found in Appendix A.
b
Value obtained from online resources whereby comprehensive list is tabulated in Appendix A.

𝑼𝑺𝑫 7.000 𝑈𝑆𝐷 (1 𝑁𝐻3 ) 0.0023 𝑈𝑆𝐷 (1.5872 𝑘𝑔 𝐻2 𝑂)


𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 ( ) =[ ]− [ ]
𝒌𝒈 𝑵𝑯𝟑 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐻2 𝑂 𝑘𝑔 𝑁𝐻3
𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 = +𝟔. 𝟗𝟔𝟑
𝒌𝒈 𝑵𝑯𝟑

44
1.4.2.4 Reaction Pathway IV: Biomass-Based Hydrogen Production
Overall
𝟑𝑪𝟒 𝑯𝟏𝟎 + 𝟓𝑵𝟐 + 𝑯𝒆𝒂𝒕 → 𝟓𝑵𝑯𝟑 + 𝟏𝟐 𝑪 + 𝟏𝟓 𝑯𝟐
Equation
Assuming all of the reaction proceeds with 100% conversion efficiency. Therefore, there are only
two raw materials required in this pathway (Pure Nitrogen and Butane (Biomass)). Similar to the
previous section, Nitrogen can be obtained from the atmospheric air hence no cost for Nitrogen
(N2), and by assuming the biomass is obtained as the waste treatment process, no cost for butane
(biomass) as well. For the products, as the char is collected as waste, no value for the char as well.

Table 1.13: Gross Profit of Reaction Pathway IV.


Reaction Path 𝟑𝑪𝟒 𝑯𝟏𝟎 + 5𝑵𝟐 ⇋ 𝟐 𝑵𝑯𝟑 + 𝟏𝟐 𝑪 + 𝟏𝟓 𝑯𝟐
Stoichiometric 3 5 2 12 15
Coefficient
Molecular Weight 58 28.01 17.03 12.01 2
(kg/kmol)
Mass 58.04 120.05 34.06 144.12 30
Reacted/Produced
(kg)
Mass per kg of NH3 1.704 3.525 1.000 4.231 0.8808
Produced (kg/ kg of
NH3)
Market Price - - 7.000 b 0.4000b 2.899a
(USD/kg)
a
Value obtained via calculation of which complete steps can be found in Appendix A.
b
Value obtained from online resources whereby comprehensive list is tabulated in Appendix A.

𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 ( )
𝒌𝒈 𝑵𝑯𝟑
7.000 𝑈𝑆𝐷 (1 𝑁𝐻3 ) 0.4000 𝑈𝑆𝐷 (4.231 𝑘𝑔 𝐶)
= [ +
𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐶 𝑘𝑔 𝐶
2.899 𝑈𝑆𝐷 (0.8808 𝑘𝑔 𝐻2 )
+ ]
𝑘𝑔 𝐻2 𝑘𝑔 𝐻2
𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 = +𝟏𝟏. 𝟑𝟐𝟑
𝒌𝒈 𝑵𝑯𝟑

45
1.4.2.5 Reaction Pathway V: Purchasing Hydrogen gas from other supplier

Overall 𝑵𝟐 (𝒈) + 𝟑𝑯𝟐 (𝒈) ⇋ 𝟐 𝑵𝑯𝟑 (𝒈) ∆𝑯°𝒓𝒙𝒏 = −𝟗𝟐. 𝟒𝟒 𝒌𝑱/𝒎𝒐𝒍


Equation
Assuming all of the reaction proceeds with 100% conversion efficiency. Therefore, there are only
two raw materials required in this pathway (Pure Nitrogen and Hydrogen gas). Similar to previous
section, Nitrogen is obtained from the atmospheric air hence no cost for Nitrogen (N2).

Table 1.14: Gross Profit of Reaction Pathway V.


Reaction Path 𝟑𝑯𝟐 + 𝑵𝟐 ⇋ 𝟐𝑵𝑯𝟑
Stoichiometric Coefficient 3 1 2
Molecular Weight (kg/kmol) 2.016 28.01 17.03
Mass Reacted/Produced (kg) 6.048 28.01 34.06

Mass Per Kg of NH3 Produced 0.1776 0.8223 1.000


(Kg/ Kg Of NH3)
Market Price (USD/kg) 2.899a - 7.000 b

a
Value obtained via calculation of which complete steps can be found in Appendix A.
b
Value obtained from online resources whereby comprehensive list is tabulated in Appendix A.

𝑼𝑺𝑫 7.000 𝑈𝑆𝐷 (1 𝑁𝐻3 ) 2.899 𝑈𝑆𝐷 (0.1776 𝑘𝑔 𝐻2 )


𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 ( ) =[ ]− [ ]
𝒌𝒈 𝑵𝑯𝟑 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝐻2 𝑘𝑔 𝑁𝐻3
𝑼𝑺𝑫
𝑮𝒓𝒐𝒔𝒔 𝑷𝒓𝒐𝒇𝒊𝒕 = +𝟔. 𝟒𝟖𝟓
𝒌𝒈 𝑵𝑯𝟑

46
1.4.3 Selection of The Optimal Pathway
As conclusion, there are five options for the selection of the best reaction pathways, based on five
different hydrogen sources (natural gas, coal, water, biomass, and suppliers). In the selection
process, the aspects like profitability, environmental impacts, selectivity/ yield, and raw material
availability for each reaction pathway which requires more consideration for the pathway selection
process. Hence, to simplify and categorise those factor, two categories, namely profitability and
environmental impacts are generated.

The aspects like operating condition of the ammonia synthesis process (e.g. temperature,
pressure, raw material requirements), raw material availability (price and cost of raw materials),
overall selectivity and yield, and the gross profit for the reaction pathway is categorised as
profitability. On the other hand, the environmental impacts take in considerations of greenhouse
gas (GHG) emission, usage of organic solvents (for example: usage of MDEA in removal of
carbon oxide), sustainable feedstock, and etc.

Consequently, based on each aspect, the reaction pathways are compared and rated in the
scale 1 to 5, where 1 indicates the lowest, while 5 indicates the best for each aspect. From the
scale/ orders for each reaction, the overall score can be evaluated as shown in the rubric below
(Table 1.15). In the balancing of the environmental perspective and profitability, 70 % is allocated
for the profitability and the remaining 30 % is allocated for the environmental perspective
respectively. This percentage is considered as optimal, to ensure minimal pollutants can be
generated throughout the process, and at the same time, generating profit and allow the expansion
for the plant as well.

Table 1.15: Rubric of Pathway Scoring System.


Aspects/ Indicators Scores
Profitability Total Score: 70%
a) Ammonia Synthesis Process 15% (from the scale 1 to 5)
b) Raw material availability & the 15% (from the scale 1 to 5)
respective Production Process

c) Overall Selectivity/ yield, 15% (from the scale 1 to 5)


d) Gross Profit 25% (from the scale 1 to 5)

Environmental impacts Total Score: 30%

Feasibility Total Score: 100%


= Profitability + Environmental Impacts
47
From the previous section, the summaries for the five available reaction pathway are
tabulated in Table 1.16 below. Based on the results, the reaction pathways are compared and rated
in the scale of 1 to 5, with respect to each aspect in terms of profitability and environmental
impacts as mentioned before. Correspondingly, the scoresheet for each of the reaction pathway is
tabulated in Table 1.17.

From the Table 1.17, reaction pathway IV and V recorded the lowest feasibility scores as
compared to the rest. This is because, reaction pathway V achieved the lowest gross profit since it
also requires pure Nitrogen feedstock. In addition, reaction pathway IV is deemed to be unfeasible
due to the low gross profit values as well as the fact that this pathway produces the lowest yield
and selectivity of hydrogen gas that further reduces its feasibility in the production of ammonia.

From an environmental perspective, electrolysis of water (Reaction pathway III) recorded


the highest score as the most environmentally friendly pathway, since it achieved the lowest
greenhouse gas emission as compared to the rest. On the contrary, on the virtue of highest
production cost of hydrogen gas that resulted from tremendous amount of electrical consumption,
this pathway scored the lowest profitability. Therefore, water electrolysis (Reaction Pathway III)
is not suitable for the synthesis of ammonia

Based on the ultimate scoresheet, coal gasification (reaction pathway II) is the most
profitable reaction pathway with high availability of raw materials and high gross profit thence
racking up the highest score in terms of probability. However, coal gasification scored the lowest
score in terms of environmental impact due to highest carbon dioxide emission per mass of
ammonia produced. Thus, coal gasification (reaction pathway II) displays lower feasibility score
as compared to the steam reforming process.

On the other hand, steam reforming (SMR) tallied the highest score of 4 out of 5 in terms
of overall feasibility by virtue of several reasons. Firstly, steam reforming (reaction pathway I)
has the most cost efficient feedstock that is readily available virtually anywhere. Although, the
environmental impact of steam reforming cannot be neglected, but when considering on an eco-
costs/value ratio (EVR), SMR is deemed the best possible option and easily commercialized as
compared to other pathways. In conclusion, steam reforming (Reaction Pathway I) is the most
optimal pathway for the synthesis of ammonia, with high profitability and relatively cleaner
reaction pathway.

48
Table 1.16 Executive Summary of All Reaction Pathways.
Reaction I II III IV V
Pathway
Method Steam Reforming Coal Gasification Alkaline Biomass Pyrolysis Outsourcing
Electrolysers Hydrogen
Ammonia Haber-Bosch Process
Synthesis
Operating Main Reactor Separator/ Flash Tank
Parameters Pressure: 235 Bar Pressure: 5 Bar
(Ammonia Temp: 200 °C Temperature: -8 °C
Systhesis) N2 to H2 feed ratio: 1:3

H2 Methane/ Natural Gas Coal Water Biomass Suppliers


Feedstock
Operating 1st Reformer 2nd Reformer Koppers – Totzek Alkaline Biomass Pyrolysis -
Parameters process Electolyser Temperature:
(Hydrogen Pressure: 40 bar Pressure: 40 bar 500~900 °C
Production) Dry coal dust is fed Reagent: KOH,
Temperature: Temperature: together with steam NaOH, NaCl Pressure:
< 1,100 °C 700- 1000°C and oxygen to the 0.1~0.5MPa
burners of the gasifier Temperature:
Catalyst: Catalyst: at a high velocity. 25 ~ 120 °C * Carried out in the
Nickel Oxide/ Nickel oxide/ Aluminium absence of oxygen
Aluminium Oxide Pressure: Pressure: and air to prevent
Oxide 1 atm 1 ~ 25 bar coke formation
Air is supplied into the Catalyst:
Feed Ratio: 2.5 system as oxygen source Temperature: Nickel-based
to 5.0 1, 500 ~ 1, 600 °C.
(Steam to
methane)

49
N2 Air Pure Nitrogen, obtained through the ASU using Air as Feedstock
Feedstock

Operating - Pressure Swing Adsoription Technology


Parameters Air inlet Pressure: 4 – 13 bar
Air inlet Temperature: 10- 25 °C
Carbon Molecular Sieve
Yield/ 96.05 % 70 ~ 75 % 50 ~ 80 % ~ 53 % 100 %
Selectivity
Gross 𝑈𝑆𝐷 𝑈𝑆𝐷 𝑈𝑆𝐷 𝑈𝑆𝐷 𝑈𝑆𝐷
+13.54 +28.55 +6.963 +11.323 +6.485
Profit 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3 𝑘𝑔 𝑁𝐻3
Remarks Most Commonly in used Highest CO2 Emission Highest Electrical Sustainable Waste -
Consumption as Feedstock
Banned by several - Less Profitablity Less
countries Profitablity

50
Table 1.17: Ultimate Scoresheet of All Reaction Pathway.
Reaction Pathway I II III IV V
Method Steam Reforming Coal Gasification Alkaline Biomass Pyrolysis Outsourcing
Electrolysers Hydrogen
Ammonia Synthesis Process 5
(15% of the total score) (Same Ammonia synthesis process)
N2 and H2 Feedstock 5 4 2 1 3
(H2: High Availability, with (H2: High Availability, with (H2: High Availability, with (H2: Seasonal Availability, with (H2: High Availability, with
Availability and Process comparatively low cost; comparatively low cost; High operating cost; comparatively High cost; comparatively Medium cost;
Operating Parameter N2: Freely accessible with air) N2: Requires Separation N2: Requires Separation N2: Requires Separation
Technology)
N2: Requires Separation
Technology)
(15% of the total score) Technology) Technology)

Overall Yield/ Selectivity 4 3 2 1 5


(15% of the total score) (Highest Overall Yield)

Gross Profit (Profitability) 4 5 2 3 1


(25% of the total score) (Highest Gross Profit) (Lowest Gross Profit)
Profitability Scores 3.1 3.05 1.85 1.80 2.20
= 𝟎. 𝟏𝟓 × 𝐀𝐦𝐦𝐨𝐧𝐢𝐚 + 𝟎. 𝟏𝟓 × 𝐅𝐞𝐞𝐝𝐬𝐭𝐨𝐜𝐤 + (Most Profitable)
𝟎. 𝟏𝟓 × 𝐒𝐞𝐥𝐞𝐜𝐭𝐢𝐯𝐢𝐭𝐲 + 𝟎. 𝟏𝟓 × 𝐆𝐫𝐨𝐬𝐬𝐏𝐫𝐨𝐟𝐢𝐭
Environmental Impact 3 1 5 4 3
(30% of the total score) (HIgh GHG emission, uses of (Highest GHG emission, uses (Neglegible GHG emission, (Low GHG emission, (Same with SMR because
MDEA for CO separation) of MDEA for CO separation) sustainable feedstock) sustainable feedstock) current industry uses SMR)

Environmental Impact Scores 0.9 0.3 1.5 1.2 0.9


= 𝟎. 𝟑 × 𝐄𝐧𝐯𝐢𝐫𝐨𝐧𝐦𝐞𝐧𝐭𝐚𝐥 𝐈𝐦𝐩𝐚𝐜𝐭 (Not environmental Friendly) (Green Process)
Feasibility 4.00 3.35 3.35 3.00 3.10
= 𝐏𝐫𝐨𝐟𝐢𝐭𝐚𝐛𝐢𝐥𝐢𝐭𝐲 𝐬𝐜𝐨𝐫𝐞 (Highest, best reaction) (Least Feasibility)
+ 𝐄𝐧𝐯𝐢𝐫𝐨𝐧𝐦𝐞𝐧𝐭𝐚𝐥 𝐈𝐦𝐩𝐚𝐜𝐭 𝐒𝐜𝐨𝐫𝐞

51
1.5 Plant and Process Safety Consideration
1.5.1 Chemical and Physical Properties of the Identified Chemicals
Safety Data Sheet (SDS) lists the chemical and physical properties of a substance that may be
required to determine the potential hazards of the substance. It is available from the chemical
manufacturer or a private library developed by the chemical plant. (Crowl and Louvar, 2011) The
chemical properties of the identified chemicals and catalysts are summarised in Table 1.18 and
Table 1.19 respectively. The physical properties of the identified chemicals and catalysts are
summarised in Table 1.20 and Table 1.21 respectively. For catalysts, the supports are not taken
into consideration because of the lack of information and it is easier to analyse the catalyst’s
properties based on its main composition. Besides, the SDS of Low Temperature Shift catalyst,
which is made up of copper oxide, zinc oxide and alumina, is not available.

1.5.2 Flammability and Toxicity Properties of the Identified Chemicals


According to Crowl and Louvar (2011), chemicals present a substantial hazard in the form of fires
and explosions. The essential elements for combustion are fuel, an oxidizer, and an ignition source.
There are a few terms used to measure the flammability of chemicals, which are, auto-ignition
temperature and flammability limits. Auto-ignition temperature is a fixed temperature above which
adequate energy is available in the environment to provide an ignition source. On the other hand,
the mixture of vapour and air will not burn when the composition is lower than the lower
flammability (LFL) as it is too lean for combustion. The mixture is also not combustible when the
composition is too rich, that is, when it is above the upper flammable limit (LFL). Thus, the
mixture is flammable only when the composition is between the LFL and the UFL. The LFL and
UFL of the identified chemicals are obtained from Mannan (2005).

The toxicity of a chemical is a property describing its effect on biological organisms. Toxic
hazard is the likelihood of damage to biological organisms based on exposure resulting from
transport and other physical methods of usage. The main routes for toxicants to enter biological
organisms are ingestion, inhalation, injection and dermal absorption. Threshold limit value (TLV)
refers to airborne concentrations that correspond to conditions under which no adverse effects are
expected during a worker’s lifetime. TLV-time weighted average (TWA) is measured based a
conventional 8-hour workday and a 40-hour workweek, to which nearly all workers may be
repeatedly exposed. (Crowl and Louvar, 2011)

National Fire Protection Association (NFPA) Diamond provides a quick means for
emergency response personnel to recognize the chemical hazards that may face during a fire or

52
other emergency. It consists of four separate areas shown in Figure 1.19. The respective areas
correspond to health, fire, stability and special hazards. The respective hazards are indicated by a
number, with the number 0 representing minimal hazard and the number 4 representing the greatest
hazard. (Crowl and Louvar, 2011)

Figure 1.19: NFPA Rating Label. (SafetySign.com, 2020)


The NFPA rating, LEL and UEL, TLV-TWA as well as toxicology of the identified
chemicals are listed in Table 1.22. The same properties for the identified catalysts are listed in
Table 1.23.

1.5.3 Possible Consequences and Safety Measures of the Identified Hazards


Ammonia, carbon monoxide, hydrogen, hydrogen sulphide and methane are the five main
chemicals that are highly rated in NFPA, means that they are associated with health and fire
hazards that require special attention. The occurrence of leakage of these chemicals, fire accidents
or explosions can lead to the destruction of the plant and property, as well as injuries or even deaths.
Thus, the possible consequences of the accidents caused by the identified hazards must be
determined. Besides, appropriate safety measures must be implemented in order to minimize the
occurrence of the accidents and harmful effects brought by those hazards, as well as the downtime
of the unit operations.

Hydrogen sulphide are rated at 4 in NFPA health hazards. It has extremely low TLV-TWA
value with only 1 ppm. It could be fatal if inhaled. Ammonia and carbon monoxide are both rated
at 3 in NFPA health hazards, and they have the same TLV-TWA values of 25 ppm. Thus, the

53
personnel within the plant area must wear appropriate personal protective equipment in order to
avoid any contact with the chemical. Besides, a gas leakage detector must be installed for the
equipment containing this chemical and give alarm even though there is only a minor leakage so
that the personnel can take immediate action to correct the operation. Plus, it is advisable that the
processing units of this chemical must be located at somewhere well-ventilated.

In terms of fire hazards, carbon monoxide, hydrogen, hydrogen sulphide and methane are
all rated at 4 in NFPA. Carbon monoxide and hydrogen have the widest range between LFL and
UFL, while hydrogen, hydrogen sulphide and methane have the lowest value of LFL. According
to Crowl and Louvar (2011), there are several design considerations that should be taken into the
account for those unit operations that process high flammability chemicals in order to minimize
the possibilities of fires and explosions. For instance, corrosion-resistant equipment and explosion-
proof local exhaust system must be used.

In addition, an inert gas can be added to a combustible mixture to reduce the concentration
of oxygen. The inert gas is usually nitrogen or carbon dioxide. The system consists of a regulator
designed to maintain a fixed positive inert pressure to save inert gas usage and improve safety.
(Crowl and Louvar, 2011)

Besides, when pumping fluids into a vessel through a pipe on top of the vessel, the
electrostatic hazard can be reduced by adding an enlarged section of pipe just before entering the
vessel. This hold provides time for charge reduction by relaxation. All associated piped and
equipment systems must also be grounded to avoid sparks (Crowl and Louvar, 2011)

Furthermore, ventilation should be applied to dilute the explosive vapours with air to
prevent explosion and to confine the hazardous flammable mixtures. For ventilation within storage
area, there should be a system interlocked to sound an alarm when ventilation fails. Inlet and
exhausts should also be located to provide air movement across the entire area. Recirculation
should be permitted but stopped when air concentrations exceed 25% of LFL. Whereas for
ventilation within the process area, the concentrations should be kept at a 5-ft radius from all
resources to below 25% of LFL. (Crowl and Louvar, 2011)

Moreover, vessels that operate under severe condition require water protection to keep the
vessel walls cool during fires. High surface temperatures can cause metal failure at pressures far
below the vessel’s maximum allowable working pressure with potentially disastrous consequences.
Unprotected vessels with no insulation or water spray can fail within minutes if there is
hydrocarbon spill. Thus, deluge system is designed to keep the vessel cool, flush away potentially

54
hazardous spills, and assist to knock down gas clouds. It also provides enough time to transfer
material out of a storage tank into another safer area. It is usually opened when the flammable gas
concentration is approximately 25% of the LFL or when a fire is detected through heat. (Crowl
and Louvar, 2011)

According to Ojha and Dhiman (2010), ammonia gas can be safely vented to atmosphere
during emergency situations and plant upsets, provided that the discharge point is sufficiently high
to prevent the downwind plume hitting the ground before the ammonia concentration has diluted
to insignificant levels. Adequately sized liquid knock-out pots are required to prevent liquid
droplets being discharged to atmosphere because the plume is then no longer buoyant, and the
ammonia plume will hit the ground much earlier with a much higher concentration.

A summary of the possible consequences and safety measures of the identified hazards is
listed in Table 1.24.

1.5.4 List of SDS Sources


Sources and links for all the identified chemicals and catalysts are listed in Table 1.25.

55
Table 1.18: Chemical Properties of the Identified Chemicals.
Chemical Name CAS No Chemical Formula Molecular Density Reactivity
Weight (g/mol) (kg/m3)
Ammonia 7664-41-7 NH3 17.03 0.7704 • Reacts with halogens and oxidants
• Attacks metals and their alloys
• Dissolves in water and evolves heat
Carbon Dioxide 124-38-9 CO2 44.01 1.826 • Unreactive
• Given off during fermentation
Carbon Monoxide 630-08-0 CO 28.01 1.153 • Stable and unreactive
• Combustible when in contact with
oxidizers
Compressed Air 132259-10-0 - 28.975 1.2 -
Hydrogen 1333-74-0 H2 2.02 1.3295 • Highly reactive with oxidizers
Hydrogen Sulphide 7783-06-4 H2S 34 1.36 • Non-reactive even under fire exposure
condition
Methane 74-82-8 CH4 16.05 0.06776 • Stable and unreactive
• Highly reactive with strong oxidizers
Nitrogen 7727-37-9 N2 28.0 1.165 • Inert
Oxygen 7782-44-7 O2 32.0 1.33 • Stable under normal conditions
• Reactive with combustible substances
Water 7732-18-5 H2O 18.0 998.23 • Universal solvent
Zinc Oxide 1314-13-2 ZnO 81.38 5610 • Stable and non-reactive
Zinc Sulphide 1314-98-3 ZnS 97.474 4100 • Stable and non-reactive

56
Table 1.19: Chemical Properties of the Identified Catalysts.
Chemical Name CAS No Chemical Formula Molecular Weight (g/mol) Density (kg/m3) Reactivity
Cobalt Molybdenum 922735-42-0 CoMo4 442.773 - Non-reactive
Iron (III) Oxide 1309-37-1 Fe2O3 159.6922 5240 Non-reactive
Iron (IV) Oxide 1317-61-9 Fe3O4 231.5386 5180 Non-reactive
N-Methyldiethanolamine 105-59-9 C5H13NO2 119.16 1038 Non-reactive
Nickel 7440-02-0 Ni 58.70 8908 Non-reactive
Nickel (II) Oxide 1313-99-1 NiO 74.7 6670 Non-reactive

Table 1.20: Physical Properties of the Identified Chemicals.


Chemical Name Melting Point Boiling Point Auto-ignition Odour Colour Physical State
(℃) (℃) Temperature
(℃)
Ammonia –77.7 –33 651 Pungent Colourless Gas
Carbon Dioxide - - - Odourless Colourless Gas
Carbon Monoxide –211.6 –191.52 607 Odourless Colourless Gas
Compressed Air - –194.3 - Odourless Colourless Gas
Hydrogen –259.15 –253 500-571 Odourless Colourless Gas
Hydrogen Sulphide –86 –60.3 260 Rotten eggs Colourless Gas
Methane –187.6 –161.48 537 Odourless Colourless Gas
Nitrogen –210 –196 - Odourless Colourless Gas
Oxygen –219 –183 - Odourless Colourless Gas
Water 0 100 - Odourless Colourless Liquid
Zinc Oxide 1975 - - Odourless Off-white Solid
Zinc Sulphide 1700 - - - Off-white Solid

57
Table 1.21: Physical Properties of the Identified Catalysts.
Chemical Name Melting Point Boiling Point Auto-ignition Odour Colour Physical State
(℃) (℃) Temperature
(℃)
Cobalt Molybdenum - - - - - Solid
Iron (III) Oxide 1565 - - - Red brown to black Solid
Iron (IV) Oxide 1588.9 - - Odourless Black Solid
N-Methyldiethanolamine –21 243 265 Amine-like Light yellow Liquid
Nickel 1455 2730 400 Odourless Brown Solid
Nickel (II) Oxide 1960 - - Odourless Black Solid

Table 1.22: Hazardous Properties of the Identified Chemicals.


Chemical Name NFPA Rating (Health/ Fire/ Reactivity) LFL and UFL TLV-TWA (ppm) Toxicology
Ammonia 3/1/0 LFL: 15 % 25 • Serious eye damage
UFL: 28 % • Severe skin burns

Carbon Dioxide 2/0/0 - 5000 • Asphyxiation


Carbon Monoxide 2/4/0 LFL: 12.5 % 25 • Suppress the oxygen uptake by
UFL: 74 % haemoglobin
• Damage to organs
• Asphyxiating
• Damage the unborn child
Compressed Air 0/0/0/ - - -
Hydrogen 1/4/0 LFL: 4 % - -
UFL: 75 %
Hydrogen 4/4/0 LFL: 4 % 1 • Respiratory irritation
Sulphide UFL: 44 %
Methane 1/4/0 LFL: 5 % - -

58
UFL: 17 %
Nitrogen 0/0/0/ - - -
Oxygen 0/0/0/ - - -
Water 0/0/0/ - - -
Zinc Oxide 1/0/0 - 2 mg/m3 -
Zinc Sulphide 0/0/0/ - - -

Table 1.23: Hazardous Properties of the Identified Catalysts.


Chemical Name NFPA Rating (Health/ Fire/ Reactivity) LFL and UFL TLV-TWA (mg/m3) Toxicology
Cobalt Molybdenum 0/0/0/ - - • Irritation
Iron (III) Oxide 1/0/0 - 5 -
Iron (IV) Oxide 1/0/0 - - -
N-Methyldiethanolamine 1/1/0/ LFL: 0.9 % - • Irritation
UFL: 8.4 %
Nickel 2/3/0 - 1.5 • Irritation
• Drowsiness and dizziness
Nickel (II) Oxide 2/0/0 - 0.2 • Irritation

Table 1.24: Potential Consequences and Safety Measures of the Identified Hazards.
Chemical Name Associated Hazards Potential Consequences Safety Measures
Ammonia • Flammable gas • Injuries to plant personnel • Use only with adequate ventilation
• Forms explosive mixtures with air • Fatal accident • Use process enclosures to keep worker
• Contains gas under pressure; may exposure to airborne contaminants below
explode if heated any recommended or statutory limits
• May displace oxygen and cause • Use explosion-proof ventilation
rapid suffocation equipment
• Harmful if inhaled

59
• Causes severe skin burns and eye
damage
• Very toxic to aquatic life
Carbon • Extremely flammable gas • Leaking of gas fire • Product to be handled in a closed system
Monoxide • Contains gas under pressure; may • Leaked flammable vapours may and under strictly controlled conditions
explode if heated create an explosive re-ignition • Provide adequate general and local
hazard exhaust ventilation
• Injuries to plant personnel • Preferably use permanent leak-tight
installations
• Gas detectors should be used when toxic
gases may be released
• Consider the use of a work permit
system e.g. for maintenance activities
Hydrogen • Extremely flammable gas • Leaking of gas fire • Use only with adequate ventilation
• May form explosive mixtures with • Leaked flammable vapours may • Use process enclosures to keep worker
air create an explosive re-ignition exposure to airborne contaminants below
• Contains gas under pressure; may hazard any recommended or statutory limits
explode if heated • Injuries to plant personnel • Use explosion-proof ventilation
• May displace oxygen and cause • System shutdown equipment
rapid suffocation. • Fatal accident
• Burns with invisible flame
Hydrogen • Extremely flammable gas • Leaking of gas fire • Use corrosion-resistant equipment
Sulphide • Contains gas under pressure; may • Leaked flammable vapours may • Use an explosion-proof local exhaust
explode if heated create an explosive re-ignition system
• Very toxic to aquatic life hazard • General ventilation must be adequate to
• May form explosive mixtures with • Injuries to plant personnel meet exposure standards
air • Use explosion proof equipment and
lighting
Methane • Extremely flammable gas • Leaking of gas fire • Use only with adequate ventilation
• May form explosive mixtures with • Leaked flammable vapours may • Use process enclosures to keep worker
air create an explosive re-ignition exposure to airborne contaminants below
hazard any recommended or statutory limits
60
• Contains gas under pressure; may • Injuries to plant personnel • Use explosion-proof ventilation
explode if heated • System shutdown equipment
• May displace oxygen and cause • Fatal accident
rapid suffocation

61
Table 1.25: List of Sources and Links for All Identified Chemicals.
Chemical Name Source and Year Link
Ammonia (Airgas, 2019) https://www.airgas.com/msds/001003.pdf
Carbon Dioxide (Airgas, 2020) https://www.airgas.com/msds/001013.pdf
Carbon (Airgas, 2017) https://www.airgas.com/msds/001014.pdf
Monoxide
Compressed (Praxair, 2019) https://www.praxair.com/-
Air /media/corporate/praxairus/documents/sds/air-
medipure-plasma-n2o2-safety-data-sheet-sds-
p4560.pdf?la=en&rev=dabc69aed1fb4d3194b715
1e7b93fda1
Hydrogen (Airgas, 2018) https://www.airgas.com/msds/001026.pdf
Hydrogen (Praxair, 2016) http://www.praxair.ca/-/media/corporate/praxair-
Sulphide canada/documents-en/safety-data-sheets-
en/hydrogen-sulfide-sds-e-4611.pdf
Methane (Airgas, 2019) https://www.airgas.com/msds/001033.pdf
Nitrogen (Air Liquide, 2018) http://alsafetydatasheets.com/download/dk/Nitrog
en_NOAL_0089A_DK_EN.pdf
Oxygen (Universal Industrial http://www.uigi.com/SDS_gaseous_O2.pdf
Gases, 2018)
Water (LabChem, 2018) http://www.labchem.com/tools/msds/msds/LC267
50.pdf
Zinc Oxide (Global Safety https://beta-
Management, 2015) static.fishersci.com/content/dam/fishersci/en_US/
documents/programs/education/regulatory-
documents/sds/chemicals/chemicals-z/S25641.pdf
Zinc Sulphide (Global Safety https://beta-
Management, 2015) static.fishersci.com/content/dam/fishersci/en_US/
documents/programs/education/regulatory-
documents/sds/chemicals/chemicals-z/S25643.pdf
Cobalt (Molbase, 2020) http://www.molbase.com/moldata/2480446.html
Molybdenum
Iron (III) Oxide (Fischer Scientific, http://dept.harpercollege.edu/chemistry/msds/Iron
2009) %20(III)%20Oxide%20Anhydrous%20Fisher.pdf
Iron (IV) Oxide (Thermo Fisher https://www.fishersci.com/store/msds?partNumbe
Scientific, 2018) r=I119500&productDescription=FERRIC+OUS+
OXIDE+BLK+PUR+500G&vendorId=VN00033
897&countryCode=US&language=en
N- (Groupe Veritas, http://www.hmlindia.com/MSDS/Methyldiethanol
Methyldiethan- 2015); (CAMEO amine.pdf
olamine Chemicals, n.d.) https://cameochemicals.noaa.gov/chemical/7103
Nickel (Thermo Fisher https://www.fishersci.com/shop/msdsproxy?produ
Scientific, 2018) ctName=AC193610250&productDescription=NI
CKEL
Nickel (II) (Thermo Fisher https://www.fishersci.com/shop/msdsproxy?produ
Oxide Scientific, 2018) ctName=AC223120025&productDescription=NI
CKEL

62
1.6 Plant Location
The selection of plant location is regarded as one of the most crucial aspects in a project planning
since it plays a significant role on the profitability of the project as well the opportunities for plant
expansion. Moreover, the selected location must be able to manufacture and deliver the product to
customers at minimum cost. Therefore, many criteria such as geographic location, proximity to
markets, accessibility, raw materials availability, economical and societal impact and many more
are carefully analysed to select the most beneficial location. Three locations such as Russia,
Australia and China are analysed and compared to yield the most suitable plant location.

1.6.1 Oryol Industrial Park, Oryol Region, Russia


Economic Aspect

Chemical and petrochemical sector still stands as a bright spot in today’s Russia chemical industry.
The chemicals manufactured in Russia are strongly dependant on the country’s abundance natural
resources and raw feedstock. (Dyakonov, Ziyatdinov and Lyzhina, 2014) Russia has the eighth
largest oil reserves, second largest coal reserves and the largest natural gas reserves in the world.
(Gas Exporting Countries Forum (GECF), 2016) The manufacture of ammonia in Russia remains
in an advantageous stage because the natural gas can be obtained easily. Hence, the cost of
importing the raw materials can be reduced.

These natural resources bring a lot of benefits for Russian manufacturers. For example, a
lot of foreign investors brought their project into Russia for the sake of the utilization of those
natural resources as the raw materials. Russia is the second largest ammonia exporter in the world.
In 2017, Russia exported ammonia that worth $789M to several countries such as Ukraine,
Belgium, Finland and Turkey. (Simoes, 2017) Besides, ammonia produced in Russia is used in the
production process of urea. The 3 new urea plants in Russia will need about 1.1 million tonnes of
ammonia per year in order for the plant to run in full capacity. (Mitchell and Wallace,2018)

Geography, Accessibility and Transportation

Oryol Industrial Park is located near to the Razdolnaya Street in Oryol region. This industrial park
is officially launched in 2006 and currently still in operating. The entire industrial park is managed
by Managing Company Osnova, one of the private facility management companies in Russia. The
overview of the location can be viewed in Figure 1.20.

63
Figure 1.20: The Location of Oryol Region. (Zhuravskiy and Pazdnikov, 2013)

Oryol Industrial Park,


Russia

Figure 2.21: The Location of Oryol Industrial Park. (Google Maps, 2020)
64
Figure 3.22: The Surroundings of Oryol Industrial Park. (Google Maps, 2020)

Oryol Industrial Park is located in a place that contains low-density of residents. As shown
in Figure 1.22, east and south area of the industrial park are undeveloped area which are mostly
forest, while the north side has a moderate-density residential area that is separated by a railway.
There are some automobile repair factories present at the west side of the industrial park. In the
city of Oryol, there are two major railway lines which are Moscow-Kharkov line and Bryansk-
Yelets line. Hence, the industrial park can be reached easily via train, and the distribution or
transportation of products will be at ease. (Global Investment Center, 2015)

Besides, the industrial park has some built-in railway lines so that people can travel from
one place to another easily and the relocation of chemical substances will be more convenient. The
distance between the industrial park and the nearest federal highway is just within 2 km. The
presence of this highway can help to avoid the traffic congestion problem in the city and shorten
the travelling time. Apart from that, Yuzhny Airport is located 6 km southwest of Oryol, and it is
the nearest airport that can be accessed from the industrial park. Thus, it can help to improve the
efficiency of importing some materials and exporting small quantity of ammonia.

Utilities, Services & Facilities

The facility management company of Oryol Industrial Park has provided various types of facilities
and services for all the tenants. For instance, the park offers logistics services, security services,
legal services, site cleaning and waste removal and transportation of the tenants’ personnel and
provision of individual transport. Furthermore, there is an individual cargo offloading facility
within the production premises. This can help to reduce manpower needed to deliver the chemicals
or other materials and also save the operational cost of the plant. The other facilities provided are,
railway lines within the park, own boiler facility to provide heating energy, electrical energy
65
available, continuous supply of gas, own water-intake structure to supply water, wastewater and
sewage treatment facilities, parking lots and warehouses.

Socio-Economic Impacts

With the presence of ammonia plant at Oryol Industrial Park, there are some significant impacts
on the society and economic of that area. For example, creation of job opportunities for local
residents. The ammonia plant will create more than 500 permanent jobs for the residents around
Oryol Industrial Park. Some temporary jobs are provided during the peak of construction. The
local people are employed to build the plant’s facility. Besides, local spending will be increased
and enhances the local economy, as when the local residents have job, their spending budget will
increase and the capability to purchase will become higher. Moreover, the population in the city
will be increased as well. Due to more job opportunities, some people will move to the city of
Oryol. This will increase the population in this region.

Government Incentives & Programs

Russian government has provided some incentives for those who are interested to invest or start-
up a new business in Russia. Table 1.26 below shows the types of incentives given to the investor.

Table 1.26: Incentives Provided by Russian Government. (KPMG, 2018)


Incentive Benefits for investors
Special Investment • Reduction in profit tax and property tax
Contracts (SPIC) • Investors’ tax burden will not increase
• For projects that invested more than 3 million roubles,
“Single Supplier” status is given
• Shorter procedures to get the “Russian Manufacturer” status
• Subsidies from government
Regional Investment • 0% profit tax rate on profit tax due to Federal budget
Projects (RIP) • Profit tax can be reduced or exempted due to Regional
budget
• Property tax on fixed assets used in the project can be
exempted or reduced

Potential Suppliers and Partnerships (Customers)

Russia has a lot of companies that have experienced in constructing and designing an ammonia
plant. Hence, with the help from the companies listed in Table 1.27, the ammonia plant can be run
at full capacity and higher efficiency.

66
Table 1.27: Potential Partners or Suppliers.
Company Description
KBR, Inc. Implement their licensed PURIFIER process in the
ammonia plant in order to remove inert from the raw
natural gas
Spectransgarant Provide chemical bulk transportation service to deliver
(Rail Garant transportation the ammonia
group)
Gazprom Provide the main raw materials which is natural gas
directly to the plant
SGS Russia Provide inspection, verification, quality control and
certification services.

The major competitors in Russia are EuroChem and URALCHEM as shown in Table 1.28.
These two companies are the largest and second largest ammonia producer in Russia in the year
of 2018 respectively. Therefore, the plant location chosen should be further away from these two
competitors in order to reduce the chance of direct competition.

Table 1.28: Competitors of Ammonia Production in the Same Vicinity.


Company Plant Location Plant Capacity (mtpa)
EuroChem Kingisepp, Russia 1.00
URALCHEM Perm, Russia 1.25

67
1.6.2 Kwinana Industrial Park, Perth, Western Australia, Australia
According to the U.S Energy Information Administration (2019), Australia is forecasted to be the
world’s largest natural gas exporter, since it has already outperformed Qatar’s export capacity of
liquefied natural gas (LNG). Moreover, in the span of 9 years, Australia’s production capacity of
LNG increased by 8.8 billion cubic feet per day. Figure 1.23 clearly illustrates the production
export capacity of various Australian companies throughout the years. Likewise, due to the
exuberant amount of natural gas, the augmentation of large-scale industries that consumes natural
gas has been vigorously encouraged by the Western Australian state government. Therefore, it is
very convenient to develop an ammonia manufacturing plant in Western Australia via the steam
reforming of methane pathway due to the copious availability of the required raw material.

Figure 1.23: LNG Export Capacity of Australia from 2005 – 2019. Source: (Zaretskaya, 2019)
In addition, few of the major key players in the Western Australian (WA) economy are the
agricultural, industrial chemicals and mining sectors. The prosperous agricultural industry uses
ammonia as the starting material to synthesis the fertilizers. The demand on fertilizers spiked
greatly due to the huge demand of food in Australia thence the need to fertilize vast areas of lands.
For instance, a market analysis conducted by Coherent Market Insights (2020), reported that more
than 19 million hectares of land of WA was fertilized. On the other hand, the mining industry
requires explosives such as trinitrotoluene (TNT), and nitro-glycerine to service their daily
operations, in like manner that uses ammonia as the starting material to manufacture these
explosives.

Furthermore, the growth market of ammonia is predicted to thrust further due the rising
standards of living and disposable income of the people. It is induced by the soaring appeal towards
the usage of ammonia based household cleaning products. Presently, considerable amount of the
starting material required to produce these compounds in the agriculture and mining industries are
imported. Hence, the establishment of a local ammonia manufacturing plant would present a more

68
economically-friendly alternative to the importation of ammonia. Along with, the ammonia plant
would have an eloquent beneficence towards the WA state’s economy by securing a supply of raw
material from a local establishment as well as revenues generated from the export of ammonia.
(Coherent Market Insights, 2020)

Geography, Accessibility and Transportation

The desired plant is to be situated at the Kwinana Strategic Industrial Area (SIA) at the southern
suburbs of Perth, Western Australia at the geological coordinates of (-32.223044, 115.774417).
The Kwinana Industrial Park (KIP) is located 60 km south of Perth’s metropolitan and 15 km south
of Fremantle. This region is designated as the premier heavy industrial zone known as the Western
Trade Coast. Since, it is a heavy industrial zone, the KIP is equipped with various services and
required infrastructures such as natural gas pipeline, freight railway and jetty.

According to the regulations by the Town of Kwinana Town Planning Scheme No.1 and
the Metropolitan Regional Scheme (MRS), the planned site for the ammonia plant is zoned as
“Industrial” of which expands to north, south and east with Cockburn Sound to the west. Withal,
there’s a recreational reserve and park further to the south east that portrays as a buffer between
the KIP and urban zone at Medina. The proposed ammonia site is located on the Mason Road and
to a certain extent nearby to the Kwinana Beach Road as observed in Figure 1.24. The site is
located to the east of Kleenheat Production Facility and to the west of IPM Operation &
Maintenance Kwinana Pty Ltd. The landscape of the site is generally a flat landform with minimal
vegetation.

Proposed
Location of
Ammonia
Plant

69
Figure 1.24: Terrain View of the Proposed Ammonia Plant. (Google Maps, 2020)

Proposed Location
of Ammonia Plant

Figure 1.25: Map of Kwinana Strategic Industrial Area. (Industrial Lands Authority, 2020)

The Kwinana Industrial Park (KIP) is strategically located to enhance the accessibility to
the industrial area. The ammonia plant at this location can be easily accessed by various mode of
transport be it land, air or sea. Firstly, the KIP is equipped with deep-water port with bulk handling
capacity such as the Kwinana Bulk Terminal currently known as the Fremantle Ports. It can be
observed from Figure 1.26, the port is located within a seven minutes-drive from the site of the
ammonia plant. This is advantageous as the ammonia can be easily exported to the global market
to these ports with minimal time and logistics costs via a mobile loading arm that loads the
ammonia onto ships. The local transport of ammonia will make use of the readily available
distribution network to directly supply to customers in KIP and other regions of WA.

70
Proposed
Location
of
Ammonia
Plant

Figure 1.26: Distance between Plant and Kwinana Bulk Jetty. (Google Maps, 2020)

Next, the Perth International Airport is less than a 40 minutes-drive from the plant. Perth Airport
is considered at the fourth busiest airport in Australia with over 40 airlines flying in and out of the
airport daily. There are also various air freighters such as Qantas Freight and Toll Priority that are
involved in the cargo transportations to over 500 different destinations globally. In addition, due
to the vastness of WA, the KIP is equipped with an integrated freight railway network that connects
the remote, regional and metropolitan WA. The freight railway network is able to deliver the
products to the market at minimal cost, and increases the efficiency of the operations of logistics
and transport of goods. The freight railway network in the metropolitan area is depicted in Figure
1.28, connects the KIP to the Fremantle Harbour. Besides, the suggested ammonia plant is easily
accessed by train since the nearest railway station, the Kwinana Train Station is located within an
8 minutes-drive. Hence, it would ease the commute of the workers to the plant.

71
Proposed
Location
of
Ammonia
Plant

Figure 1.27: Distance to the Nearest Airport. (Google Maps, 2020)

Fremantle Harbour

Kwinana
Industrial Park

Figure 1.28: Freight Railway Network of Kwinana. (Industrial Lands Authority, 2020)

72
Proposed
Location
of
Ammonia
Plant

Figure 1.29: Distance to Kwinana Train Station. (Google Maps, 2020)

Utilities, Services & Facilities

The Kwinana Industrial Park is equipped with various facilities and services. Firstly, the KIP is
equipped with natural gas supply line which is detrimental to the manufacturing of ammonia in
our plant, thence the installation costs of gas pipeline can be reduced. In terms of utilities, the KIP
is well supplied with electricity and raw water since it is located nearby a power generation facility
as well as a desalination plant that is able to provide the ammonia plant with clean water for daily
operations usage. Numerous services are provided by the KIP such as logistics, security solutions,
in-house wastewater treatment, telecom network, fire prevention services as well as emergency
response team. (Industrial Lands Authority, 2020) Furthermore, the user facilities provided are
such as wide roads to reduce traffic congestion, workers’ accommodation, infrastructure corridor
and parking lots.

Socio-Economic Impacts

The establishment of the ammonia plant in KIP has several key impacts towards the society of
WA. Firstly, the nearest residential area is located 3 kilometres east of the KIP are Medina and
Calista. Therefore, throughout the life cycle of this project, an estimated more than 400 people
would be employed during the construction phase and more would be recruited for the sales,
production, maintenance and distribution of ammonia. Hence, the locals would relish these
benefits and the economy of the state of WA would increase significantly. (Industrial Lands
Authority, 2020)

73
Government Incentives & Programs

The Australian Government has developed various tax incentives and support programs to promote
the growth of manufacturers, production and export of Australian goods to the global market.
(Australian Trade and Investment Commission, 2020) The various programs are listed in Table
1.29.

Table 1.29: Programs Developed by the Australian Government.


Incentive Information
The Major Project • To promote investment of private sector in production
Facilitation (MPF) enterprises.
Program • Receive assistance in government approvals for major projects.
• Tailored facilitation services.
• Identification of potential and competitive Australian suppliers.
Austrade Investment • Provides free consultation services regarding the exportation
Assistance Program of goods from Australia.
• Provides investors with the necessary information in regards to
business establishment in Australia.
Capital investment • Offshore banking transactions with minimal tax rate of 10%.
incentives
Australian Innovation • Reduced tax rate of up to 10% compared to 21% corporate tax
and rate.
Manufacturing (AIM) • To increase the commercial viability of taking R&D-based
Incentive technology to Australian and global market.
• 12.5% refundable R&D tax credit.
Foreign income tax • Australian companies are entitled to claim foreign income tax
offsets (FITO) paid that is an assessable income to void double taxation.
• Tax claim is only limited to amount more than AUD 1000.

Potential Suppliers and Partnerships (Customers)

The Kwinana Industrial Park is strategically located to encourage co-operations with various other
key manufacturing industries players. Moreover, the ammonia plant at KIP allows various
symbiotic relationship with numerous other companies as well as potential customers to consume
the ammonia produced by this plant. Ammonia and carbon dioxide is used as a starting material
to manufacture urea-based fertilizers, hence both the desired product, ammonia and carbon dioxide
by-product can be monetized by selling it off to fertilizer manufactures. The potential partnerships
with such companies has been tabulated in Table 1.30.

74
Table 1.30: Potential Partners or Suppliers That Can Be Approached.
Relationship Company Description
Supplier Kleenheat • Natural gas supplier that supplies detrimental
Production Facility raw material required for production of
ammonia.
Service Doina Engineering • Fabrication and construction of the plant during
Provider and Construction the commission.
Pty Ltd • Provides repair and maintenance services to the
throughout the life cycle of the plant.
Supplier Synergy Cockburn • Second largest power station in WA.
Site • Provides the required amount of electrical
power supply to the plant.
Service Kwinana Water • Waste water treatment plant
Provider Recycling Plant • Able to treat effluent discharge from the plant
before being discharged into Cockburn Sound.
• Ensures sustainable usage of water resources.
Service Boom Logistics • Provides logistics solutions for heavy
Provider machineries
Customers Nutrian Liquid • Potential customers to consume ammonia and
Fertilisers, Summit carbon dioxide for the production of urea based
Fertilisers, Bailey’s fertilizers.
Fertilizers

Competitors

Due to the abundant availability of natural gas, there are several manufacturers that has been
established in Australia that manufacturers ammonia. The largest ammonia manufacturer in
Australia is located in Western Australia, CBSP. Apart from producing ammonia, CBSP also
produces ammonium nitrate as well as manufactures fertilizers for Wesfarmers Ltd. Yara
International, one of the leading manufacturers of ammonia has a plant located in Pilbara, WA
with their world-scale largest ammonia production facility. Thirdly, Orica’s ammonia plant at
Kooragang Island is a potential competitor too. The production capacity of each companies and
location are tabulated below.

Table 1.31: Competitors of Ammonia Production in the Same Vicinity.


Company Plant Location Plant Capacity (mtpa)
CBSP Kwinana, WA, Australia 0.2550
Yara International Pilbara, WA, Australia 0.8000
Orica Ltd Kooragang Island, NSW, Australia 0.3600

75
1.6.3 PT. Indonesia Morowali Industrial Park (IMIP), Sulawesi Tengah Region,
Indonesia
Economic Aspect

Indonesia chemical industry has demonstrated a stable production and growth throughout the past.
The increase in the demand of the fertiliser in large scale and lower cost, simulating the growth of
the ammonia plant in ammonia. For example, the recent project of KBR in 2016 of a 2, 200 MTPD
natural gas- fed ammonia plant in Palembang, Indonesia.

Furthermore, based on the high natural gas production in Indonesia, it shows potential to
be able to obtain the natural gas locally to reduce the import duty tax, and the transportation cost
(the construction of piping to channel from the natural gas production plant to the ammonia plant).
From year 2013-2018, Indonesia had consistently produced 74.5 ±0.5 Gm^3 of natural gas
throughout the years (Yearbook.enerdata.net, 2020), with consistent domestic consumption of 42
±1 Gm^3 of natural gas within the same time frame (Yearbook.enerdata.net, 2020). The balance
32 Gm3 of natural is then exported for the generation of profits for the production plant. From this,
in is safe to deduce that in Indonesia, natural gas can be obtained from the local markets with lower
cost, hence generating higher profit for the ammonia plant.

In this proposed location, Indonesia Morowali industrial park (IMIP) is analysed and
considered, to determine the potential and profitability of the new ammonia plant to be constructed.

Geography, Accessibility and Transportation

Indonesia Morowali Industrial Park (IMIP) is an industrial park that is located at the city of
Bahodopi, Morowali regency, Central Sulawesi Province, in the Indonesia (as shown in Figure
1.30). This industrial park is officially launched at 2013 and currently still in operating. The entire
industrial park is managed by two companies from China (Shanghai Decent Investment (Group)
Co., Ltd.) and Indonesia (Indonesia PT Bintangdelapan Group), that cooperates in a joint
investment. IMIP is the industrial park located at city Bahodopi with abundant of nickel and iron
resources. Hence, it shows high potential to become the industrial park of nickel-based industry,
such as Natural Gas- Fed Ammonia synthesis, which requires nickel-based catalyst for the steam
reforming process (Imip.co.id, 2020).

76
Figure 1.30: The Location Of Morowali Region. (Zhuravskiy and Pazdnikov, 2013)

Indonesia Morowali Industrial Park (IMIP) is located a place that contains low-density of
residents. As shown in Figure 1.31, IMIP is surrounded by undeveloped area in almost all
directions, which are mostly forests and ocean, while the north side has a moderate-density
residential area that near the port/ jetty. As mentioned in the previous part, IMIP is an industrial
park based on the mining activities in that area. In IMIP, minerals like Nickel and Iron are mined
in the mining area on the east side of the industrial area.

In the city of Bahodopi, the jetty and airports are available and easily accessible, as the
distance between the terminals and the industrial park is within 20 minutes driving distance (2.4
km northeast of IMIP, or 12 minutes’ drive for BDM port Jetty from IMIP, and 7.4 km Northeast,
or 20 minutes’ drive for IMIP Airport from IMIP respectively). With the presence of these facilities,
the plants can be easily accessed by suppliers (raw materials, catalysts, reagents, and etc),
marketers (customers and investors), and workers (local and foreign workers). Thus, it can help to
improve the efficiency of import some materials and export small quantity of ammonia.

77
Figure 1.31: The location and surrounding of Indonesia Morowali Industrial Park, Indonesia
(Google Maps, 2020).
Utilities, Services & Facilities
The facility management company of IMIP has provided various type of facilities and services for
all the tenants in the industrial park. For instance, the park offers logistics services, security
services (PT. Morowali Sekuriti Servis), parking lots (Pakiran Utama PT IMP), site cleaning and
waste removal and transportation of the tenants’ personnel and provision of individual transport.
Furthermore, there is an individual cargo offloading facility within the production premises,
smooth logistic and customs services. This can help to reduce manpower, time, and cost required
to export the products and also save the operational cost of the plant. The other facilities provided
in IMIP are listed below (Indonesia Morowali Industrial Park (IMIP), 2020):

i. Two Coal-Fired Plants (PLTU) with the capacity of 65 × 2 𝑀𝑊 and 2 × 150 𝑀𝑊for the
electrical supply for the plant, multiple unit ensure stable output of electrical generation.
ii. Seaport and Airport for the ease of transportation of products.
iii. Clean Water Treatment, clean utilities which does not require more cost in installing water
treatment system.

78
iv. A polytechnic and Stage I Innovation Centre, that is supported by government, which also
ensure the local labour force is sufficient for the plant.
v. Two towers of Vertical Housing (Rusunawa) for workers, also build and supported by
government as an initiative for supporting the local industrial park activities
vi. Electrical energy available in the industrial park (466, 000 KW of electricity generating
capacity)
vii. Wastewater and sewage treatment facilities

Socio-Economic Impacts
With the presence of ammonia plant at Indonesia Morowali Industrial Park (IMIP), there are some
significant impacts on the society and economic of that area. For example, creation of job
opportunities for local residents. Similar to the Oryols industrial park, the ammonia plant will
create more than 500 permanent jobs for the residents around IMIP, in sectors like transportation,
warehouse, managers, engineers, marketers, and etc. Not only permanent job, some temporary
jobs are provided during the peak of construction. The local people are employed to build the
plant’s facility.

Besides, increase the population in the city of Bahodopi, and show improvement in local
facilities. Due to more job opportunities, more people will move into the city of Bahodopi, as
labours, professionals, and such, hence resulting in the increase the population in this region. The
public transportation sector will show the need to improve, in order to accommodate with the
increase of the new residents in the city, to allow them travel from industrial area to residential
area.

In terms of labour cost, one of the most attractive part for the construction of ammonia
plant in Indonesia is the relatively low labour cost as compare to the other countries. As in Table
1.32, the labour rate per month were considered as low with USD 255/ month, with 196.5 % lower
as compared to the rate in Australia, or 486.7% lower as compared to the rate in Germany.

Table 1.32 Labour Cost Comparison of Indonesia and Other Countries.


Location Rate (USD/ month) Source
Malaysia* 231 (ILOSTAT, 2020)
Indonesia** 255 (Kendalindustrialpark.co.id, 2020)
Australia* 756 (ILOSTAT, 2020)
Germany* 1496 (ILOSTAT, 2020)
*Calculated with assumption that 9 hours per day, 50 weeks per months.
**Calculated using the average of the monthly paid for different place in Indonesia.

79
Government Incentives & Programs
Indonesia government has provided some incentives for those who are interested to invest or start-
up a new business in Indonesia. Table 1.33 below shows the types of incentives given to the
investor. In short, the investors show potentials to enjoy tax reduction for the investment with
large-capacity ammonia plant (with more than 200 workers), employment of interns, and initiating
Research and Development (R&D) programmes.

Table 1.33: Incentives Provided by Indonesian Government.


Incentive Benefits for investors
• Net Income Reduction in 60 % of the total investment in
GR 45/2019 the form of tangible fixed assets
(Tax exemption for labour o For industries that employs at least 200 workers,
intensive industries) with labour cost not exceeding 15 % of
production costs
(ASEAN Briefing, 2019) • Gross Income reduction (< 200% total cost) for
companies that initiates apprenticeship programs or
training activities (e.g. Industrial Training Programs)
• Gross income reduction (<300 %) of total costs incurred
in building the R&D facilities.

• Two towers of Vertical Housing (Rusunawa) for


Local Ministry subsidies for workers - by the Ministry of Public Works and Housing
IMIP • Trained more than 300 human resources for local
industries - by Ministry of Industry
(Indonesia Morowali Industrial • A Polytechnic and Stage I Innovation Centre - by
Park (IMIP), 2020) Ministry of Industry
• Detailed Spatial Planning (RDTR) in the vicinity of the
industrial zone - by Ministry of Industry.

Potential Suppliers and Partnerships (Customers)


Indonesia Morowali Industrial Park shows high potential for the new ammonia plant location, due
to its high accessibility and potential collaborations with the local industry within the park. Hence,
with the help from the companies listed in Table 1.35, the ammonia plant can be run at full capacity
and higher efficiency. Besides, the raw materials (natural gas) can also easily obtained from the
natural gas production plant in Indonesia as shown in Table 1.34 below.

Table 1.34: Potential Local Natural Gas Suppliers That Can Be Approached.
Company Description
HUSKY- CNOOC Madura Local Supplier of Natural Gas, allow the potential for lower
Limited cost for raw material.
Pertamina Hulu Mahakam Local Supplier of Natural Gas, allow the potential for lower
cost for raw material.
80
PT. BP Petrochemicals Local Supplier of Natural Gas, allow the potential for lower
Indonesia cost for raw material.

Table 1.35: Potential Local Partners or Suppliers That Can Be Approached.


Company Description
Tim Kendaraan Potential suppliers and customers for the ammonia plant. The factory
Ferronickel SMI fabricates steel, which utilises ammonia as the nitrogen donor for the steel.
& PT. GCNS It also produces nickels which may be the supplier for the nickel catalyst in
the reformer.
Oxygen Plant Able to provide nitrogen gas and oxygen in case equipment malfunction for
Fatufia, the air supply of ammonia plant. Also act as potential supplier for second-
Bahodopi handed equipment in-case of emergency.
Workshop Potential supplier for the mechanical equipment for the plant.
Mekanik ITSS
Baging Plant Potential contractor to build the ammonia synthesis plant.

Competitors

The major competitors in Indonesia are PT Panca Amara Utama and PT Pupuk Sriwidjaja
Palembang. These two companies are the top ammonia producer in Indonesia in the year of 2018.
Therefore, the plant location chosen should be further away from these two competitors in order
to reduce the chance of direct competition. As in Figure 1.32, most of the large competitors are
located on the west side of Indonesia. IMIP which located at the east of Indonesia is suitable for
the location of the ammonia plant, to reduce the impact of competition in the local market.

Figure 1.32: The Location of Ammonia Synthesis Plant Competitors in Indonesia.

Table 1.36: The Plant Location for Competitor Company and Their Plant Capacity.
Company Plant Location Plant Capacity (mtpa)
PT Panca Amara Utama Jakarta Selatan 0.70
(Toyo Engineering Corperation,
2013)
81
PT Pupuk Sriwidjaja Palembang Palembang, 0.73
(Kbr.com, 2020) Indonesia

1.6.4 Selection of the Most Optimal Plant Location


Based on Table 1.37, various aspects of plant location have been analysed and compared to. Firstly,
the economic feasibility is high in both Australia (KIP) and Russia (Oryol) due to huge availability
of natural gas as well as the high demand for ammonia, while Indonesia (IMIP) displays moderate
demand for ammonia. On the other hand, both Australia and Indonesia are strategically located
nearby the jetty so that the produced goods can easily be exported to the global market.

In addition, all three plant locations are able to develop the local economy of the country
as well as reduce unemployment rate in that area. However, the labour cost of Indonesia seems to
be the most remunerative. Indubitably, the government incentives provided by the Australian and
Indonesian governments are quite advantageous compared to the Russian authorities. Besides, the
number of competitors is the lowest among the three in Indonesia.

Despite that, the strategic location of Australia allows numerous partnerships among the
proponents of the Kwinana Industrial Park to form an integrated network of self-sustaining
industries. Moreover, the facilities provided by the KIP are very lucrative, since it is well-equipped
with state-of-the-art logistic facility (Local and International) and natural-gas-line.

Hence, in the view of all aspects, it can be concluded that the ammonia plant in Australia
is deemed to be the most strategic location as well as cost effective due to the various incentives
provided by the Australian authority as well as the possible collaborations with other proponents
of KIP.

82
Table 1.37: Benchmarking the Various Aspects of All Plant Locations.
Country Russia Australia Indonesia
Location Oryol Industrial Park, Kwinana Industrial Park, PT. Indonesia
Oryol Region, Russia Perth, Western Australia, Morowali Industrial
Australia Park (IMIP), Sulawesi
Tengah Region,
Indonesia.
Economic High due to abundant High due to abundant Moderate
Feasibility natural resources natural resources
Geography Located away from Located close to Remote location and
and residential area and residential area, however very high accessibility
Accessibility moderate accessibility very high accessibility via land, air and
since only via land. via land, air and water. water.
Facilities Moderate High High
Socio- High since can improve High since can improve High and cheapest
Economic the local economy and the local economy and labour cost.
Impact reduce unemployment reduce unemployment
rate. rate.
Government Low High Moderate
Incentives
Customers Moderate Numerous Moderate
and
Partnerships
Competitors High Moderate Low

83
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APPENDICES

APPENDIX A
1. Calculation of the Price of Natural Gas

Figure A-1: Lower Heating Value Of Methane Obtained From Aspen HYSYS.
𝐿𝑜𝑤𝑒𝑟 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝐶𝐻4 (𝐿𝐻𝑉) = 8.027 × 105 . 𝑘𝐽/𝑘𝑚𝑜𝑙

According to the US Energy Information Administration, the price of natural gas as of 24th
January 2020 was at 1.98 USD/ MMBtu.

𝑈𝑆𝐷
𝑀𝑎𝑟𝑘𝑒𝑡 𝑝𝑟𝑖𝑐𝑒 𝑜𝑓 𝑁𝑎𝑡𝑢𝑟𝑎𝑙 𝐺𝑎𝑠 ( )
𝑘𝑔
1.98 𝑈𝑆𝐷 1 𝑘𝑚𝑜𝑙 8.027 × 105 𝑘𝐽 9.478 × 10−7 𝑀𝑀𝐵𝑡𝑢
= × × ×
1 𝑀𝑀𝐵𝑡𝑢 16.05 𝑘𝑔 1 𝑘𝑚𝑜𝑙 𝑘𝐽
𝑀𝒂𝒓𝒌𝒆𝒕 𝒑𝒓𝒊𝒄𝒆 𝒐𝒇 𝑵𝒂𝒕𝒖𝒓𝒂𝒍 𝑮𝒂𝒔 = 𝟎. 𝟎𝟗𝟑𝟖𝟔 𝑼𝑺𝑫/𝒌𝒈

2. Calculation of the Price of Hydrogen Gas


Price from online source = 200 𝑈𝑆𝐷 𝑝𝑒𝑟 6𝑚3 𝑜𝑓 𝑝𝑢𝑟𝑒 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 150 𝑏𝑎𝑟
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 25°𝐶
According to Aspen HYSYS,

89
Figure A-2: Density of hydrogen gas at 150 bar from Aspen HYSYS
Density at 150 bar at room temperature, 𝜌 = 11.50 𝑘𝑔/𝑚3

𝑈𝑆𝐷 200 𝑈𝑆𝐷 1𝑚3


𝑃𝑟𝑖𝑐𝑒 𝑜𝑓 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 ( )= ×
𝑘𝑔 6𝑚3 11.50 𝑘𝑔

𝑈𝑆𝐷 𝑈𝑆𝐷
𝑃𝑟𝑖𝑐𝑒 𝑜𝑓 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 ( ) = 2.899
𝑘𝑔 𝑘𝑔

90
3. Price and Suppliers of Chemicals
Table A-1: Comprehensive List of Chemicals Sources.

Chemical Industry Supplier Price/unit Reference Website


Involved
Chengdu Taiyu https://www.alibaba.com/product-detail/Factory-price-of-
Industrial Gases Co., ammonia-gas-
Ammonia Refrigerant 7.00 USD/kg
Ltd. pure_62461128733.html?spm=a2700.galleryofferlist.0.0.
de341cbeluEqeo
Chongqing Chizhan https://www.alibaba.com/product-detail/99-9-99-999-
Carbon Industry and Trade Carbon-
Manufacturing 2.50 USD/kg
Dioxide Development Co., Dioxide_62413697138.html?spm=a2700.7724857.normal
Ltd. List.137.7bcc1102ytr6TM
Chengdu Taiyu https://www.alibaba.com/product-detail/99-95-99-99-
Carbon Organic Industrial Gases Co., industrial-
8.00 USD/kg
Monoxide Chemical Ltd. co_62164329854.html?spm=a2700.7724857.normalList.2
2.310f1d4ewrKbmu&s=p
Thang Long Capital https://www.alibaba.com/product-detail/Wholesale-
Charcoal Joint Stock cheap-price-INDUSTRIAL-
Fuel 0.40 USD/kg
(Carbon) Company CHARCOAL_50038822874.html?spm=a2700.7724857.n
ormalList.37.7a4a5cb34ahjgf
Shanghai Eternal https://www.alibaba.com/product-detail/99-999-
Faith Industry Co., Industrial-high-purity-
Hydrogen Manufacturing 200 USD/unit
Ltd. hydrogen_1889966278.html?spm=a2700.galleryofferlist.
0.0.e9ba7ce2uXm3KD
Natural Subjected to local https://www.eia.gov/dnav/ng/ng_pri_sum_dcu_nus_m.ht
Manufacturing 1.98 USD/mmBtu
Gas supplier m
Industrial Subjected to local https://www.cityofbryan.net/commercialindustrial-
Water Grade Water in supplier 0.0023 USD/ kg metering-rates/
US

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